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WO2019189327A1 - Photosensitive resin composition, cured film, laminate, and application of these - Google Patents

Photosensitive resin composition, cured film, laminate, and application of these Download PDF

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Publication number
WO2019189327A1
WO2019189327A1 PCT/JP2019/013121 JP2019013121W WO2019189327A1 WO 2019189327 A1 WO2019189327 A1 WO 2019189327A1 JP 2019013121 W JP2019013121 W JP 2019013121W WO 2019189327 A1 WO2019189327 A1 WO 2019189327A1
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WO
WIPO (PCT)
Prior art keywords
group
resin composition
photosensitive resin
acid
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/013121
Other languages
French (fr)
Japanese (ja)
Inventor
慶 福原
悠 岩井
健志 川端
青島　俊栄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to JP2020509175A priority Critical patent/JP7068441B2/en
Publication of WO2019189327A1 publication Critical patent/WO2019189327A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photosensitive resin composition, a method for producing a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, a semiconductor device, and a storage stabilizer.
  • Polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation, and thus are applied to various uses (for example, see Non-Patent Documents 1 and 2).
  • the use is not particularly limited, when a semiconductor device for mounting is taken as an example, it can be used as a material for an insulating film or a sealing material, or as a protective film thereof. It is also used as a base film and coverlay for flexible substrates.
  • the above polyimide resins and the like generally have low solubility in solvents. Therefore, a method of dissolving in a solvent in a state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor is often used.
  • Patent Document 1 a negative photosensitive resin composition containing a polyimide precursor having a (meth) acryloyloxy group and a photopolymerization initiator in a predetermined amount is employed.
  • a cured product having high transparency as a resin composition and having a high Young's modulus can be obtained after thermosetting.
  • a cured product having a high Young's modulus can be obtained by curing with the above technique so as to be suitable for an interlayer insulating film or the like.
  • the polymer precursor can be cured by heating, but due to its properties, curing during storage tends to proceed and the stability of the resin may be lacking. On the other hand, if a formulation that suppresses the cyclization of the precursor to prevent curing is taken, the curability is inferior and the required characteristics during film formation may not be satisfied.
  • the present invention provides a photosensitive resin composition that has good adhesion to the metal material layer and can achieve excellent storage stability while maintaining sufficient curability, a method for producing the photosensitive resin composition, It aims at providing the manufacturing method of a cured film, a laminated body, a cured film, the manufacturing method of a laminated body, a semiconductor device, and a storage stabilizer.
  • the present inventor has repeatedly studied and experimented on the composition containing the polymer precursor from various viewpoints regarding its components, addition amount, preparation conditions, and the like.
  • the inventors have found that the above-mentioned problems can be solved by using a specific acid having a single bond of sulfur and nitrogen for the polymer precursor, and have completed the present invention.
  • the above problems have been solved by the following means ⁇ 1> and ⁇ 2> to ⁇ 26>.
  • a photosensitive resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and an acid having a single bond of nitrogen and sulfur.
  • ClogP which is a logarithm of the water / octanol distribution coefficient of the acid, is ⁇ 2.1 or more and 1.2 or less.
  • ⁇ 4> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the acid has a molecular weight of 300 or less.
  • ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the acid has a cyclic structure.
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the acid has a sultam structure.
  • ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the acid is represented by the following formula (S1-1); In formula (S1-1), R 12 is a hydrogen atom or a substituent, and R 13 and R 14 are each independently a hydrogen atom or a substituent.
  • S1-1 The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising at least one of a photopolymerization initiator, a radical polymerizable compound, and a solvent.
  • ⁇ 10> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 9>, which is used for forming an interlayer insulating film for a rewiring layer.
  • a method for producing a photosensitive resin composition comprising adding an acid having a single bond of nitrogen and sulfur to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. .
  • ⁇ 15> The method for producing a photosensitive resin composition according to any one of ⁇ 11> to ⁇ 14>, wherein the acid has a molecular weight of 300 or less.
  • ⁇ 16> The method for producing a photosensitive resin composition according to any one of ⁇ 11> to ⁇ 15>, wherein the acid is represented by any of the following formulas (S1) to (S4);
  • L 11 represents a single bond or a linking group
  • L 12 represents a linking group
  • R 11 represents a hydrogen atom or a substituent
  • R 21 represents a substituent
  • R 31 Represents a substituent
  • R 41 represents a hydrogen atom or a substituent
  • R 42 represents a substituent
  • R 43 represents OH, NH 2 or N 3 .
  • ⁇ 17> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 18> The cured film according to ⁇ 17>, wherein the film thickness is 1 to 30 ⁇ m.
  • ⁇ 19> A laminate having two or more cured films according to ⁇ 17> or ⁇ 18>.
  • ⁇ 20> The laminate according to ⁇ 19>, having a metal layer between the cured films.
  • ⁇ 21> A method for producing a cured film, comprising a film forming step of forming a film by applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10> to a substrate.
  • ⁇ 22> The method for producing a cured film according to ⁇ 21>, including an exposure step of exposing the film and a development step of developing the film.
  • ⁇ 23> The method for producing a cured film according to ⁇ 22>, wherein the developer used for the development contains 90% by mass or more of an organic solvent.
  • ⁇ 24> The method for producing a cured film according to ⁇ 22> or ⁇ 23>, including a step of heating the film after the development step.
  • ⁇ 25> A method for producing a laminate, wherein the method for producing a cured film according to any one of ⁇ 21> to ⁇ 24> is performed a plurality of times.
  • ⁇ 26> A semiconductor device having the cured film according to ⁇ 17> or ⁇ 18> or the laminate according to ⁇ 19> or ⁇ 20>.
  • the cured film has good adhesion to the metal material layer, and excellent storage stability can be realized while maintaining sufficient curability.
  • the manufacturing method of the photosensitive resin composition which has the effect, a cured film, a laminated body, the manufacturing method of a cured film, the manufacturing method of a laminated body, a semiconductor device, and a storage stabilizer can be provided.
  • ⁇ is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • EUV light extreme ultraviolet rays
  • X-rays or electron beams electron beams.
  • solid content is the mass percentage of the other component except a solvent with respect to the gross mass of a composition.
  • the temperature is 23 ° C. unless otherwise specified.
  • a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel.
  • the photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention” or “the resin composition of the present invention”) is selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. And an acid having a single bond of nitrogen and sulfur (hereinafter sometimes referred to as “specific acid”). Thereby, favorable storage stability and adhesiveness can be realized.
  • a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is stored for a long period of time, a ring closure reaction is likely to occur. On the other hand, at the time of curing, it is necessary to appropriately advance cyclization.
  • the storage stability of the photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is an important issue.
  • the cured film obtained by curing the photosensitive resin composition is hygroscopic. Therefore, the adsorbed moisture may reduce the adhesion between the substrate and the cured film. Such a decrease in adhesion becomes a problem when, for example, a rewiring layer is formed in a semiconductor device.
  • the present invention by adding a specific acid to the photosensitive resin composition, the ring-closing reaction of the polymer precursor over time can be suppressed without excessively inhibiting the curing reaction due to cyclization. And stability during storage can be improved. Furthermore, moisture absorption of the photosensitive resin composition can be prevented by the action of the specific acid, and adhesion to the substrate when cured can be improved.
  • the photosensitive resin composition of this invention contains the acid (specific acid) which has a single bond of nitrogen and sulfur. Certain acids contain a single bond of nitrogen and sulfur (NS), but such a bond increases the acidity of the hydrogen atom substituting for the nitrogen atom, so that the acidity is moderate. Furthermore, in the present invention, it preferably has a —NS ( ⁇ O) 2 — structure. By setting it as such a structure, since the acidity of the hydrogen atom which the nitrogen atom substituted is raised more, the effect of this invention is exhibited more effectively.
  • the specific acid preferably has a pka of 0 or more and 4.0 or less.
  • the lower limit is preferably ⁇ 10 or more, more preferably ⁇ 5 or more, and even more preferably 1 or more.
  • As an upper limit it is preferable that it is 3.8 or less, and it is more preferable that it is 3.7 or less.
  • By setting the pKa to 1 or more the effect of improving the stability of film properties is more effectively exhibited.
  • By setting the pKa to 4.0 or less storage stability at room temperature is prevented by inhibiting hydrolysis in the resist solution. The effect of improving the performance is more effectively exhibited.
  • pKa represents pKa in an aqueous solution, and examples thereof include those described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). A lower value indicates a higher acid strength.
  • pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Further, by using the following software package 1, a value based on a Hammett's substituent constant and a database of known literature values can be obtained by calculation. The value of pKa in this specification indicates a value obtained by calculation using this software package.
  • Software Package 1 Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)
  • the specific acid preferably has a ClogP of ⁇ 2.1 or more and 1.2 or less.
  • the lower limit is preferably ⁇ 2.1 or more, more preferably ⁇ 1.75 or more, and further preferably ⁇ 1.50 or more.
  • As an upper limit it is preferable that it is 1.2 or less, It is more preferable that it is 1.18 or less, It is further more preferable that it is 1.16 or less.
  • ClogP means logP (log [water / octanol partition coefficient]) predicted by calculation from the chemical structure. In this specification, ClogP uses a value calculated by Chem Draw Pro 12.0.
  • the specific acid preferably has a molecular weight of 300 or less.
  • the specific acid is preferably stable to light having a wavelength of 365 nm.
  • the specific acid preferably has a cyclic structure.
  • the specific acid preferably has a sultam structure.
  • the specific acid is preferably represented by any of the following formulas (S1) to (S4).
  • L 11 represents a single bond or a linking group
  • L 12 represents a linking group
  • R 11 represents a hydrogen atom or a substituent
  • R 21 represents a substituent
  • R 31 Represents a substituent
  • R 41 represents a hydrogen atom or a substituent
  • R 42 represents a substituent
  • R 43 represents OH, NH 2 or N 3 .
  • the linking group of L 11 is preferably an aromatic linking group (aromatic hydrocarbon linking group, heteroaromatic linking group) or an alkylene group.
  • the aromatic linking group may have a substituent T described later, preferably has 1 to 22 carbon atoms, more preferably has 1 to 18 carbon atoms, and still more preferably has 1 to 10 carbon atoms.
  • Specific examples of the aromatic linking group include a linking group having a ring Aro or a ring Arh described in the polymer precursor described later, and more specifically, AR-1 to AR-1 described in the polymer precursor described later.
  • AR-10 linking group may be mentioned.
  • a phenylene group which may have a substituent T is preferable.
  • the alkylene group may have a substituent T, preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 3 carbon atoms, and particularly ethylene that may have a substituent T Is preferred.
  • the linking group of L 12 is preferably a linking group L described later, preferably an alkylene group or a carbonyl group, and more preferably a carbonyl group.
  • the alkylene group may have a substituent T described later, preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 3 carbon atoms, and may particularly have a substituent T.
  • a methylene group is preferred.
  • L 11 and L 12 may be bonded to each other to form a ring.
  • the ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
  • the substituent of R 11 is an aromatic group (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and specific examples thereof include a group having ring Aro or ring Arh described later)
  • an alkyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples include Alk described later
  • R 11 is preferably a hydrogen atom.
  • the substituent of R 21 is an aromatic group (preferably having a carbon number of 1 to 22, preferably 1 to 18, more preferably 1 to 10. Specific examples include groups having a ring Aro or a ring Arh described later). Or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples thereof include an alkyl group Alk described later).
  • a preferable aromatic group is more preferable, and a phenyl group which may have a substituent T is more preferable.
  • the optional substituent T here is preferably a carboxyl group or a nitro group.
  • —SO 2 NH 2 in formula (S3) may be —SO 2 NHR 22 or —SO 2 NR 22 R 23 .
  • R 22 and R 23 are each independently a substituent T, and are aromatic groups (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms; A group having Aro or ring Arh) or an alkyl group which may be linear or cyclic, and may be linear or branched (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms) Is preferred.
  • R 22 and R 23 may be bonded to each other to form a ring.
  • the ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
  • the substituent of R 31 is an aromatic group (preferably having a carbon number of 1 to 22, preferably 1 to 18, more preferably 1 to 10, and specific examples include a group having a ring Aro or a ring Arh described later). Or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples thereof include an alkyl group Alk described later).
  • a preferable aromatic group is more preferable, and a phenyl group which may have a substituent T is more preferable.
  • the arbitrary substituent T here is preferably a carboxyl group.
  • R 41 is preferably a hydrogen atom.
  • R 42 is preferably a substituent T, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and specific examples thereof include an alkyl group Alk described below) or
  • An aromatic group preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and specific examples include a group having a ring Aro or a ring Arh described later
  • a cycloalkyl group The number of carbon atoms is preferably 3 to 24, more preferably 3 to 12, still more preferably 3 to 6, and even more preferably a cyclohexyl group.
  • R 41 and R 42 may be bonded to each other to form a ring.
  • the ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
  • the substituent T may be substituted on each group via the following linking group L. The same applies to the following formulas (S1-1), (S1-2), and (S4) to (S6).
  • R 43 represents OH, NH 2 or N 3 , among which OH is preferable.
  • the formula (S1) is preferably the formula (S1-1).
  • R 12 is a hydrogen atom or a substituent
  • R 13 and R 14 are each independently a hydrogen atom or a substituent.
  • R 13 and R 14 may be bonded to each other or condensed to form a ring.
  • R 12 is the same as R 11 .
  • R 13 and R 14 are substituents, they are aromatic groups (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and further preferably 1 to 10 carbon atoms; specific examples thereof include a group having ring Aro or ring Arh described later. Or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples include Alk described later).
  • the ring formed by combining or condensing R 13 and R 14 is an aromatic hydrocarbon ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms).
  • Ring Aro is mentioned below, and a benzene ring is more preferred, or an aromatic heterocycle (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 and more preferably 3 to 6). Ring).
  • the formula (S1-1) is more preferably the following formula (S1-2).
  • R 12 has the same meaning as R 12 in formula (S1-1).
  • R 15 to R 18 are each independently a hydrogen atom or a substituent (for example, substituent T). When R 15 and R 16 are substituents, R 15 and R 16 may be bonded to each other or condensed to form a ring. When R 16 and R 17 are substituents, R 16 and R 17 may be bonded to each other or condensed to form a ring. When R 17 and R 18 are substituents, R 17 and R 18 may be bonded to each other or condensed to form a ring.
  • the preferred ring formed by R 15 and R 16 , R 16 and R 17 , R 17 and R 18 is the same as the ring formed by R 13 and R 14 .
  • the specific acid is preferably a compound having a ring structure.
  • the ring structure is an aromatic hydrocarbon ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms, and specific examples thereof include ring Aro, and a benzene ring is more preferable), aromatic Group heterocycle (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms, and specific examples include ring Arh) or alicyclic ring (for example, preferably having 3 to 24 carbon atoms) 3 to 12 is more preferable, and 3 to 6 is more preferable, and a specific example is a cyclohexane ring (the alicyclic ring exemplified here is referred to as Acy).
  • Ring Aro, sensation Arh, and ring Acy may have a substituent T as long as the effects of the present invention are exhibited.
  • the ring structures exemplified here may be collectively referred to as tCy.
  • the reason why the effects of the present invention can be obtained by using an acid having a ring structure in this way is an improvement in stacking properties with a polymer.
  • the acid having a ring structure is preferably represented by any of the following formulas (S5) to (S8).
  • Cy represents a ring structure group, and is preferably the ring tCy described above. Ring Cy may have a substituent T as long as the effects of the present invention are exhibited.
  • L 12 , R 41 and R 43 have the same definitions as those defined in formulas (S1) and (S4), respectively, and preferred ranges are also the same.
  • —SO 2 NH 2 in formula (S6) may be —SO 2 NHR 22 or —SO 2 NR 22 R 23 .
  • R 22 and R 23 are each independently a substituent T, and are aromatic groups (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms; A group having Aro or ring Arh) or an alkyl group which may be linear or cyclic, and may be linear or branched (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms) Is preferred.
  • R 22 and R 23 may be bonded to each other to form a ring.
  • the ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
  • an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms
  • an alkenyl group preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms
  • an alkoxyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms
  • an aryl group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms.
  • a heteroaryl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 4; examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom
  • An arylalkyl group preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 11 carbon atoms
  • a hydroxyl group an amino group (0 to 2 carbon atoms).
  • acyl group Preferably 0-12, more preferably 0-6, thiol group, carboxyl group, nitro group, acyl group (2-12 carbon atoms are preferred, 2-6 are more preferred, and 2-3 are especially preferred)
  • an acyloxy group preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms
  • an aryloyl group preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and 7 to 11 carbon atoms.
  • a hetero atom may be present in the alkylene chain of the substituent T.
  • the alkyl group, alkenyl group, aryl group, and arylalkyl group of the substituent T may be further substituted with other substituents.
  • RN is a hydrogen atom or an organic group.
  • the organic group include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, To 10 are more preferable), or an arylalkyl group (preferably having a carbon number of 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11).
  • the linking group L is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), An arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), and heteroarylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms).
  • the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom), an oxygen atom, a sulfur atom, a carbonyl group, —NR N —, or a combination thereof.
  • the number of atoms constituting the linking group L is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6, excluding hydrogen atoms.
  • the number of atoms connected to the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more.
  • the content of the specific acid in the solid content is preferably 0.10% by mass or more, more preferably 0.15% by mass or more, and 0.20% by mass or more. More preferably. As an upper limit, it is preferable that it is 2.0 mass% or less, It is more preferable that it is 1.8 mass% or less, It is further more preferable that it is 1.6 mass% or less.
  • the content of the specific acid with respect to 100 parts by mass of the polymer precursor is preferably 0.15 parts by mass or more, more preferably 0.18 parts by mass or more, and 0.20 parts by mass or more. More preferably.
  • the action of a specific acid can be sufficiently exerted, and it is preferable for storage stability.
  • the specific acid may be used alone or in combination. When using a plurality of items, the total amount is within the above range. Moreover, you may use a specific acid in combination with another acid. For example, it does not prevent use in combination with acetic acid or the like.
  • the specific acid preferably occupies the main component of an acid other than the polymer precursor, more preferably 80% by mass or more, and 90% by mass or more. More preferably, it is more preferably 95% by mass or more, and even more preferably 99% by mass or more.
  • the specific acid may be added to the photosensitive resin composition at any timing. For example, it may be added during or after the synthesis of the polymer precursor described later, or when the composition is prepared. Especially, adding during the synthesis
  • “synthesizing” refers to, for example, the time when the polymer precursor has undergone a process including a synthesis process and a purification process. During the synthesis, a polymer precursor drying step may be further performed. Thus, by mix
  • the photosensitive resin composition of the present invention includes at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor.
  • a polyimide precursor is more preferable, and a polyimide precursor including a structural unit represented by the following formula (1) is more preferable.
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently Represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 are each independently an oxygen atom or NH, preferably an oxygen atom.
  • R 111 represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group composed of an aromatic group, an aromatic heterocyclic group, or a combination thereof, and has 2 to 20 carbon atoms.
  • an aromatic group having 6 to 20 carbon atoms is more preferable.
  • R 111 is preferably derived from a diamine.
  • Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine.
  • One type of diamine may be used, or two or more types may be used.
  • the diamine is a straight chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof.
  • a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.
  • A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—, —S ( ⁇ O) 2 —, —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O— , —C ( ⁇ O) —, —S— and —SO 2 — are more preferable, and —CH 2 —, —O—, —S—, —SO 2 —, —C ( More preferably, it is a divalent group selected from the group consisting of CF 3 ) 2 — and —C (CH 3 ) 2 —.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether
  • diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also a preferred example.
  • Preferred is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine containing no aromatic ring.
  • Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark).
  • EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2 -Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. Not.
  • x, y, and z are average values.
  • R 111 is preferably represented by -Ar 0 -L 0 -Ar 0- from the viewpoint of the flexibility of the resulting cured film.
  • Ar 0 is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and particularly preferably 6 to 10), and is preferably a phenylene group.
  • L 0 represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—, —S ( ⁇ O). 2 represents a group selected from —NHCO— and combinations thereof.
  • a preferred range is synonymous with A described above.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance.
  • the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
  • R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or A trifluoromethyl group.
  • Examples of the monovalent organic group represented by R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
  • R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
  • Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.
  • R 115 in formula (1) represents a tetravalent organic group.
  • the tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
  • R 112 has the same meaning as A, and the preferred range is also the same.
  • tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
  • R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (1).
  • tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
  • R 113 and R 114 in Formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group.
  • the radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.
  • R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom)
  • To 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
  • R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH 2 CH (OH) CH 2 —, and ethylene group, propylene group, trimethylene group, and —CH 2 CH (OH) CH 2 — are more preferable. Particularly preferably, R 200 is a methyl group and R 201 is an ethylene group.
  • An alkyl group etc. are mentioned. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
  • the acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group.
  • R113 or R114 As the monovalent organic group represented by R113 or R114, a substituent that improves the solubility of the developer is preferably used.
  • R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 113 or R 114 is preferably a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
  • the alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group).
  • the alkyl group may be linear, branched or cyclic.
  • linear or branched alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable.
  • alkyl group exemplified here is called Alk
  • aromatic group examples include an aromatic hydrocarbon group and an aromatic heterocyclic group.
  • Specific examples of the aromatic hydrocarbon group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring.
  • Aromatic heterocyclic groups include substituted or unsubstituted pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, India Lysine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring,
  • the polyimide precursor preferably has a fluorine atom in the structural unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.
  • an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1).
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A).
  • a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. is there.
  • R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
  • the structural unit represented by the formula (1) may be one type, but may be two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included.
  • the polyimide precursor may also contain other types of structural units in addition to the structural unit of the above formula (1).
  • a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the structural units is the structural unit represented by the formula (1).
  • 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the structural units is the structural unit represented by the formula (1).
  • 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
  • the molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
  • an organic solvent is preferably used for the reaction.
  • One or more organic solvents may be used.
  • the organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • solid precipitation can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble.
  • the polybenzoxazole precursor preferably includes a structural unit represented by the following formula (2).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.
  • R 121 represents a divalent organic group.
  • the divalent organic group include aliphatic groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and aromatic groups (preferably having 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable.
  • the aromatic group constituting R 121 include R 111 in the above formula (1).
  • R 121 is preferably derived from 4,4′-oxydibenzoyl chloride.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the formula (1), and preferred ranges are also the same.
  • R 122 is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
  • R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferred range is also the same.
  • the polybenzoxazole precursor may contain other types of structural units in addition to the structural unit of the above formula (2). It is preferable that a precursor contains the diamine residue represented by a following formula (SL) as another kind of structural unit at the point which can suppress generation
  • SL diamine residue represented by a following formula (SL) as another kind of structural unit at the point which can suppress generation
  • Z has an a structure and a b structure
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)
  • R 2s Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)
  • at least one of R 3s , R 4s , R 5s and R 6s is aromatic.
  • a group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), the rest being a hydrogen atom or 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more Preferably, it is an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, which may be the same or different.
  • the polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.
  • preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000.
  • the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight within the above range, it is possible to reduce both the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor and to suppress the warp and to improve the solubility.
  • the acid dianhydride group is further removed from the tetracarboxylic dianhydride in terms of improving alkali solubility. It is preferable that a tetracarboxylic acid residue remaining later is included as a structural unit. Examples of such tetracarboxylic acid residue, and examples of R 115 in formula (1).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
  • the molecular weight dispersity (number average molecular weight / weight average molecular weight) of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the content of the polymer precursor is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass with respect to the total solid content of the composition. More preferably, it is more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the composition. Preferably, it is 98 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 95 mass% or less.
  • the photosensitive resin composition of this invention may contain only 1 type of polymer precursors, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention preferably contains a solvent.
  • a known solvent can be arbitrarily used as the solvent.
  • the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone , ⁇ -valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
  • alkyl oxyacetates for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl al
  • 3-alkyloxypropionic acid alkyl esters for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
  • 2-alkyloxypropionic acid alkyl esters for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
  • Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
  • the sulfoxides for example, dimethyl sulfoxide is preferable.
  • Preferred examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
  • a form in which two or more kinds of solvents are mixed is also preferable from the viewpoint of improving the coated surface properties.
  • the mixed solvent is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably an amount such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass from the viewpoint of applicability, and is an amount such that 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, still more preferably 40 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness and coating method.
  • the solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators.
  • a radical photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm).
  • the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • the photosensitive resin composition contains a photo radical polymerization initiator
  • the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light.
  • a substrate such as a semiconductor wafer
  • the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the electrode pattern. is there.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
  • ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kaya Cure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • hydroxyacetophenone compounds As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
  • the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • IRGACURE-819 and IRGACURE-TPO which are commercially available products can be used.
  • the metallocene compound include IRGACURE-784 (manufactured by BASF).
  • an oxime compound is more preferable.
  • the exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photobase generator.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
  • Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • an oxime compound (an oxime photopolymerization initiator) as a radical photopolymerization initiator.
  • the oxime-based photopolymerization initiator has a linking group of> C ⁇ N—O—C ( ⁇ O) — in the molecule.
  • Commercially available products include IRGACURE OXE 01, IRGACURE OXE02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF Corp.), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, JP 2012-014052)
  • a polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA Corporation
  • DFI-091 manufactured by Daitokemix Co., Ltd.
  • oxime compounds include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471.
  • oxime compounds having a specific substituent as disclosed in JP-A-2007-267979 there are oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
  • Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.
  • More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is even more preferable.
  • photo radical polymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc.
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyldimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R I00 represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, An alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,
  • R I01 is a group represented by formula (II), the same as R I00 R I02 to R I04 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms
  • radical photopolymerization initiator compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can be used.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.5 to 15% by mass, and more preferably 1.0 to 10% by mass.
  • the photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.
  • the photosensitive resin composition of the present invention preferably contains a radical polymerizable compound.
  • a radical polymerizable compound a compound having a radical polymerizable group can be used.
  • the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl group, vinyl group, (meth) acryloyl group, and allyl group.
  • the radical polymerizable group is preferably a (meth) acryloyl group.
  • the number of radical polymerizable groups contained in the radical polymerizable compound may be one or two or more.
  • the radical polymerizable compound preferably has two or more radical polymerizable groups, and preferably has three or more radical polymerizable groups. More preferred.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.
  • the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more polymerizable groups, and preferably contains a trifunctional or higher functional radical polymerizable compound. More preferably, at least one kind is included. Further, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher functional radically polymerizable compound.
  • the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.
  • radical polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • the radical polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure.
  • examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having a carbonic acid or a cardo resin. Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-1-040337, JP-B-1-040336, and JP-A-02-025493. And vinyl phosphonic acid compounds. Further, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
  • radical polymerizable compound examples include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku ( A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl group via an ethylene glycol residue or a propylene glycol residue A
  • radical polymerizable compounds examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60 which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- manufactured by Nippon Kayaku Co., Ltd.
  • radical polymerizable compound examples include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, and the like. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Further, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as radically polymerizable compounds. It can also be used.
  • the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphate group.
  • the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
  • a radically polymerizable compound having a group is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentayl.
  • a compound that is erythritol examples include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • a preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film.
  • Monofunctional radically polymerizable compounds include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • Acrylic acid derivatives N-vinyl pyrrolidone, N-vinyl compounds such as N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc.
  • Le compounds are preferably used.
  • As the monofunctional radically polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the photosensitive resin composition of this invention can further contain polymeric compounds other than the radically polymerizable compound mentioned above.
  • polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
  • Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.
  • R 104 represents a t-valent organic group having 1 to 200 carbon atoms
  • R 105 represents a group represented by —OR 106 or —OCO—R 107
  • R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 107 represents an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by —OR 406 or —OCO—R 407
  • R 406 represents a hydrogen atom or a carbon atom.
  • R 407 represents an organic group having 1 to 10 carbon atoms.
  • R 504 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 505 represents a group represented by —OR 506 or —OCO—R 507.
  • R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • NIKACALAC examples include MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diacetylmethyl-p-cresol, and the like. It is done.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • Epoxy compound compound having an epoxy group
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.
  • the epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed.
  • the polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.
  • epoxy compound examples include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane.
  • Epicron (registered trademark) 850-S Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade names, and the
  • an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance.
  • Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
  • oxetane compound compound having oxetanyl group
  • examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
  • Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.
  • a benzoxazine compound (compound having benzoxazolyl group))
  • a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.
  • benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo An oxazine compound is mentioned. These may be used alone or in combination of two or more.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • the polymerizable compound one kind may be used alone, or two or more kinds may be mixed and used. When using 2 or more types together, it is preferable that the total amount becomes said range.
  • the photosensitive resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
  • the migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Sal
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A.
  • the compounds described in paragraph 0052 and the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition. More preferably, the content is 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass. Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.
  • the photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4 ′.
  • -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-tert
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of WO2015 / 125469 can also be used.
  • the following compound can be used (Me is a methyl group).
  • the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferably 0.02 to 3% by mass, more preferably 0.05 to 2.5% by mass. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion with a metal material used for electrodes and wirings.
  • metal adhesion improvers include silane coupling agents.
  • silane coupling agent examples include compounds described in paragraphs 0062 to 0073 of JP-A No. 2014-191002, compounds described in paragraphs 0063 to 0071 of WO 2011/080992, and JP-A No. 2014-191252.
  • Et represents an ethyl group.
  • the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0 to 100 parts by mass of the polymer precursor.
  • the range is from 5 to 5 parts by mass.
  • Adhesion between the cured film and the metal layer after the curing step is improved by setting it to the above lower limit or more, and heat resistance and mechanical properties of the cured film after the curing step are improved by setting the upper limit or less. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
  • the photosensitive resin composition of the present invention may contain a thermal base generator.
  • the thermophotobase generator is preferably one that generates a base by heat.
  • the thermal base generator is preferably a salt of a quaternary ammonium cation and a carboxylic acid anion.
  • the quaternary ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-4).
  • R Y1 is n Y-valent (n Y is an integer of 1 to 12) represents an organic group is preferably a n Y-valent hydrocarbon group.
  • the hydrocarbon group include an n Y valent group containing an alkane (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3), and an n Y valent group containing an alkene (2 carbon atoms).
  • n Y valent group containing an aromatic hydrocarbon preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 carbon atoms.
  • R Y1 is preferably an aromatic hydrocarbon group.
  • R Y1 may have the above-described substituent T as long as the effects of the present invention are not impaired.
  • R Y2 to R Y5 each independently represents a hydrogen atom or a hydrocarbon group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), and an alkyl group (having a carbon number of 1 to 36).
  • 36 is preferred, 1 to 24 is more preferred, 1 to 23 is more preferred, an alkenyl group (preferably having 2 to 36 carbon atoms, more preferred is 2 to 24, still more preferred being 2 to 23), and an alkynyl group (having carbon numbers).
  • 1 to 36 are preferred, 1 to 24 are more preferred, 1 to 23 are more preferred, and an aryl group (preferably having 6 to 22 carbon atoms, more preferred is 6 to 18 and even more preferred is 6 to 10).
  • the alkyl group, alkenyl group and alkynyl group may be cyclic or chain-like, and in the case of a chain, may be linear or branched and may have a substituent T.
  • R Y6 represents an alkyl group (preferably having a carbon number of 1 to 36, preferably 2 to 24, more preferably 4 to 18), or an alkenyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, and 4 to 18).
  • an alkynyl group preferably having 2 to 36 carbon atoms, more preferably 2 to 24, more preferably 4 to 18
  • an aryl group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms.
  • the alkyl group, alkenyl group and alkynyl group may be cyclic or chain-like, and in the case of a chain, it may be linear or branched.
  • a linking group containing a hetero atom for example, one having a hetero atom in the linking group L
  • a linking group containing a hetero atom for example, one having a hetero atom in the linking group L
  • an oligoalkylene group (the number of carbon atoms in the structural unit is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3, the number of repetitions is preferably 2 to 100, more preferably 2 to 60, and more preferably 2 to 30 is more preferable).
  • n Y represents an integer of 1 to 12, more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 3.
  • n X represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
  • Two or more of R Y2 to R Y6 may be bonded to each other to form a ring.
  • R Y7 to R Y16 have the same meaning as R N (R N may have a substituent T). However, R Y7 to R Y9 are not all hydrogen atoms.
  • R Y7 and R Y8 are carboxyalkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms; preferably 1 to 12 carboxyl groups). 1 to 6 are more preferable, and 1 to 3 are more preferable.
  • R Y9 is preferably an aromatic group, and is preferably an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10).
  • an alkoxycarbonyl group substituted with an aromatic group is preferred (the alkoxyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and the aromatic group preferably has 6 to 22 carbon atoms). 6 to 18 are more preferable, and 6 to 14 are more preferable.
  • R Y11 and R Y13 are preferably hydrogen atoms.
  • R Y13 is preferably a hydrogen atom
  • R Y10 , R Y11 , R Y12 and R Y16 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). ⁇ 3 are more preferred).
  • R Y11 and R Y16 , R Y10 and R Y12 are preferably bonded to form a ring to form a bicyclo compound. Specific examples include diazabicyclononene and diazabicycloundecene.
  • the carboxylate anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is represented by the following formula (X1). It is preferable.
  • EWG represents an electron withdrawing group.
  • the electron-withdrawing group means a group in which Hammett's substituent constant ⁇ m exhibits a positive value.
  • ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642.
  • the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group (hereinafter the same).
  • EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3). More preferably), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 6 carbon atoms). 10 is more preferable), and represents a hydroxyl group or a carboxyl group.
  • Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms).
  • R x1 to R x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed, and when the ring is formed, the linking group L may be interposed in the middle.
  • These alkyl group, alkenyl group, aryl group, and Ar may have a substituent T as long as the effects of the present invention are not impaired.
  • Ar preferably has a carboxyl group (preferably 1 to 3). * Represents a bonding position.
  • Np represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.
  • the molecular weight of the thermal base generator in the present invention is preferably 100 or more and less than 2000, and more preferably 200 to 1000.
  • Specific examples of the thermal base generator in the present invention include, in addition to the compounds used in the examples described later, an acidic compound that generates a base when heated to 40 ° C. or higher described in International Publication No. 2015/199219 and pKa1 of 0 to Illustrative are ammonium salts having four anions and an ammonium cation, the contents of which are incorporated herein.
  • the content of the thermal base generator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.
  • the upper limit is more preferably 10% by mass or less, and further preferably 5% by mass or less.
  • 1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the composition of this invention can also be set as the structure which does not contain a thermal base generator substantially. “Substantially free” means less than 0.01% by mass, more preferably less than 0.005% by mass, based on the total solid content of the composition.
  • the photosensitive resin composition of the present invention has various additives, for example, a thermal radical polymerization initiator, a thermal acid generator, a sensitizing dye, and a chain transfer agent, as necessary, as long as the effects of the present invention are not impaired.
  • a thermal radical polymerization initiator for example, a thermal radical polymerization initiator, a thermal acid generator, a sensitizing dye, and a chain transfer agent, as necessary, as long as the effects of the present invention are not impaired.
  • Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, and the like can be added.
  • the total addition amount is preferably 3% by mass or less based on the solid content of the composition.
  • the composition of the present invention may contain a photoacid generator.
  • a photoacid generator By containing the photoacid generator, an acid is generated in the exposed area, and the solubility of the exposed area in the alkaline aqueous solution is increased. Therefore, it can be used as a positive photosensitive resin composition.
  • the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts.
  • a quinonediazide compound is preferably used because it exhibits an excellent dissolution inhibiting effect and a positive composition with high sensitivity and low film thickness can be obtained.
  • the content of the photoacid generator is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the polymer precursor. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed. Only one type of photoacid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the photosensitive resin composition used in the present invention may contain a photobase generator.
  • the photocuring accelerator in the present invention is preferably one that generates a base upon exposure (photobase generator), and does not exhibit activity under normal conditions of room temperature and normal pressure. Particularly preferably, those which generate a base (basic substance) when carried out. Since the base generated by exposure works as a catalyst for curing the polymer precursor by heating, it can be suitably used.
  • known photocuring accelerators can be used.
  • the base component was neutralized by forming a salt, such as a transition metal compound complex, a compound having an ammonium salt structure, or an amidine moiety made latent by forming a salt with a carboxylic acid. Examples include ionic compounds, and nonionic compounds in which a base component is made latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.
  • Examples of the photocuring accelerator according to the present invention include a photocuring accelerator having a cinnamic acid amide structure as disclosed in JP2009-080452A and WO2009 / 123122, and JP2006-188951A.
  • Examples of the photocuring accelerator having an oxime structure include, but are not limited to, and other known photocuring accelerator structures can be used.
  • photocuring accelerator examples include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205A, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.
  • photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.
  • the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • 1 type (s) or 2 or more types can be used for a photocuring accelerator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator without departing from the gist of the present invention.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be promoted together with the cyclization of the polymer precursor, so that higher heat resistance can be achieved.
  • Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. %, And more preferably 5 to 15% by mass.
  • the thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.
  • the photosensitive resin composition of the present invention may contain a thermal acid generator.
  • the thermal acid generator generates an acid by heating, promotes cyclization of the polymer precursor, and further improves the mechanical properties of the cured film.
  • Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
  • 0.01 mass part or more is preferable with respect to 100 mass parts of polymer precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable.
  • the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.
  • the thermal acid generator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the photosensitive resin composition of the present invention may contain a sensitizing dye.
  • a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a photo radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a thermal base generator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
  • the content of the sensitizing dye is 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention.
  • the content is 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the photosensitive resin composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
  • As the chain transfer agent for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc. can be preferably used.
  • the content of the chain transfer agent is 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Preferably, it is 1 to 10% by mass, more preferably 1 to 5% by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
  • surfactant various types may be added to the photosensitive resin composition of the present invention.
  • various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the following surfactants are also preferable.
  • the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferable that the content is 0.005 to 1.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.
  • the photosensitive resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the surface of the composition is dried during the coating process. May be unevenly distributed.
  • the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferred. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
  • the water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of the coated surface properties.
  • the metal content of the photosensitive resin composition of the present invention is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and even more preferably less than 0.5 ppm by weight from the viewpoint of insulation.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention.
  • Examples include a method in which the raw material constituting the photosensitive resin composition of the invention is subjected to filter filtration, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation is performed under the conditions in which contamination is suppressed as much as possible. be able to.
  • the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, from the viewpoint of wiring corrosion. More preferably less than ppm. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.
  • a conventionally known storage container can be used as the storage container for the photosensitive resin composition of the present invention.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and the 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the photosensitive resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and can be performed by a conventionally known method.
  • the present invention also includes adding an acid to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, wherein the acid has a single bond of nitrogen and sulfur.
  • a method for producing a photosensitive resin composition, which is stable with respect to light having a wavelength of 365 nm, is provided.
  • the acid is preferably added during the synthesis of the polymer precursor.
  • the filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and further preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore sizes or materials may be used in combination.
  • Various materials may be filtered a plurality of times.
  • circulation filtration may be used. Moreover, you may pressurize and filter.
  • the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the cured film of the present invention is formed by curing the photosensitive resin composition of the present invention.
  • the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.
  • the laminate of the cured film of the present invention may be formed by laminating two or more layers, further 3 to 7 layers.
  • the laminate having two or more cured films of the present invention preferably has a metal layer between the cured films.
  • Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
  • the fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like.
  • patterning may be performed by etching a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above. Regarding these uses, for example, Science & Technology Co., Ltd.
  • the cured film in the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching of molded parts, and the production of protective lacquers and dielectric layers in electronics, in particular, microelectronics.
  • the method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention.
  • the photosensitive resin composition of the present invention is applied to a substrate to form a film (layer forming step), and the layered photosensitive resin composition is heated at 80 to 450 ° C. A heating step of heating.
  • the film forming step (layer forming step) is followed by an exposure step of exposing the film, and the exposed photosensitive resin composition layer (film, ie, resin layer).
  • the manufacturing method which has the image development process which develops is mentioned.
  • the exposed resin layer can be further cured by including a heating step of heating (preferably heating at 80 to 450 ° C.).
  • the composition is cured in advance by exposure, and then subjected to desired processing (for example, the following lamination) if necessary, and further cured by heating. be able to.
  • the manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention.
  • a film forming step layer forming step
  • a heating step of a photosensitive resin composition or
  • a laminated body can be obtained by laminating a cured film.
  • the manufacturing method which concerns on preferable embodiment of this invention includes the film
  • the type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited.
  • a semiconductor manufacturing substrate is particularly preferable, and a silicon substrate is more preferable.
  • a resin layer or a metal layer becomes a board
  • coating is preferable. Specifically, as a means to apply, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And an inkjet method.
  • a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable.
  • a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
  • the coating method can be appropriately selected depending on the shape of the substrate, and a spin coat method, a spray coat method, an ink jet method or the like is preferable for a circular substrate such as a wafer, and a slit coat method, a spray coat method, an ink jet method or the like for a rectangular substrate.
  • the method is preferred.
  • the spin coating method for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
  • the manufacturing method of this invention may include the process of drying in order to remove a solvent after forming a photosensitive resin composition layer and after a film
  • a preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C.
  • Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the manufacturing method of this invention may also include the exposure process which exposes the said photosensitive resin composition layer.
  • the amount of exposure is not particularly defined as long as the photosensitive resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and to irradiate 200 to 8000 mJ / cm 2 . It is more preferable.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and is preferably 240 to 550 nm.
  • the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h. Line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and the like.
  • the exposure by a high pressure mercury lamp is especially preferable, and the exposure by i line
  • the production method of the present invention may include a development processing step of performing development processing on the exposed photosensitive resin composition layer.
  • the development method is not particularly limited as long as a desired pattern can be formed.
  • development methods such as paddle, spray, immersion, and ultrasonic wave can be employed.
  • Development is performed using a developer.
  • the developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed.
  • the developer preferably contains an organic solvent, and more preferably the developer contains 90% by mass or more of the organic solvent.
  • the developer preferably contains an organic solvent having a ClogP value of ⁇ 1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3.
  • organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkyl oxyacetate alkyl eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • a preferred example of the sulfoxide is dimethyl sulfoxide.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • 50% by mass or more of all components is preferably an organic solvent, more preferably 70% by mass or more is an organic solvent, and further preferably 90% by mass or more is an organic solvent. Further, 100% by mass of the developer may be an organic solvent.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly defined, but it can be usually 20 to 40 ° C.
  • rinsing may be further performed.
  • the rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition.
  • the rinse time is preferably 5 seconds to 1 minute.
  • the production method of the present invention preferably includes a heating step after the film forming step (layer forming step), the drying step, or the developing step.
  • a heating step it is preferable to include a step of heating the film after the development step.
  • the cyclization reaction of the polymer precursor proceeds.
  • the composition of this invention may contain radically polymerizable compounds other than a polymer precursor, hardening of radically polymerizable compounds other than an unreacted polymer precursor can also be advanced at this process.
  • the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 to 500 ° C., more preferably 80 to 450 ° C., further preferably 140 to 350 ° C., still more preferably 160 to 250 ° C., and 170 to 220 ° C. Is most preferred. Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C.
  • the temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature.
  • the temperature of the dried film (layer) is, for example, 30% higher than the boiling point of the solvent contained in the photosensitive resin composition.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film.
  • the reason is not certain, it is considered that the ethynyl groups of the polymer precursors between layers proceed with a crosslinking reaction at this temperature.
  • Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. You may perform the pre-processing process of these.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film.
  • the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C. Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polymer precursor.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.
  • a metal layer forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.
  • existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • the production method of the present invention preferably further includes a lamination step.
  • the lamination step refers to the film formation step (layer formation step) and the heating step again on the surface of the cured film (resin layer) or metal layer, or the film formation step (layer formation step), the exposure step, and It is a series of steps including performing the development processing steps in the order described above. It goes without saying that the laminating step may further include the drying step and the heating step.
  • a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process.
  • An example of the surface activation treatment is plasma treatment.
  • the lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
  • the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers. That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition film formation step (layer formation step) and the heating step, or the film formation step ( It is preferable to perform the layer forming step), the exposure step, and the development processing step (further, if necessary) in the order described above. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.
  • the present invention also discloses a semiconductor device having the cured film or laminate of the present invention.
  • a semiconductor device using the photosensitive resin composition of the present invention for the formation of the interlayer insulating film for the rewiring layer refer to the description in paragraphs 0213 to 0218 and the description in FIG. The contents of which are incorporated herein.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes.
  • a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • saccharin (B-1) 20 mL ethyl alcohol and 200 mL ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 25600 and a number average molecular weight of 8600.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • N-cyclohexylsulfamic acid (B-2), 20 mL of ethyl alcohol and 200 mL of ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
  • 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 23600 and a number average molecular weight of 8200.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution of 76.0 g of diamine (a) dissolved in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C., and the mixture was stirred for 1 hour, and then 20 mL of Ethyl alcohol and 200 mL of ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 22500 and a number average molecular weight of 8200.
  • reaction mixture was then cooled to ⁇ 10 ° C., and a solution of 34.35 g diisopropylcarbodiimide in 80 mL ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • reaction mixture was then cooled to ⁇ 10 ° C., and a solution of 34.35 g diisopropylcarbodiimide in 80 mL ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • reaction mixture was then cooled to ⁇ 10 ° C., and a solution of 34.35 g diisopropylcarbodiimide in 80 mL ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution obtained by dissolving 25.1 g of 4,4′-diaminodiphenyl ether in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C., and the mixture was stirred for 1 hour. 20 mL of ethyl alcohol and 200 mL of ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8500.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes.
  • a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • saccharin (B-1) 20 mL ethyl alcohol and 200 mL ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 24,600 and a number average molecular weight of 8,300.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution obtained by dissolving 25.1 g of 4,4′-diaminodiphenyl ether in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C., and the mixture was stirred for 1 hour. 20 mL of ethyl alcohol and 200 mL of ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8500.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • reaction mixture was cooled to ⁇ 10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture over 60 minutes at ⁇ 10 ⁇ 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of ⁇ -butyrolactone was added dropwise to the reaction mixture at ⁇ 10 ⁇ 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour.
  • N-cyclohexylsulfamic acid (B-2), 20 mL of ethyl alcohol and 200 mL of ⁇ -butyrolactone were added.
  • the precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
  • 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8400.
  • the obtained powdery polyimide precursor had a weight average molecular weight of 23800 and a number average molecular weight of 8800.
  • the obtained powdery polybenzoxazole precursor had a weight average molecular weight of 25000 and a number average molecular weight of 8500.
  • ⁇ Preparation of photosensitive resin composition The resin was mixed with the components described in Tables 1 and 2 below to prepare a coating solution for the photosensitive resin composition as a uniform solution. Each photosensitive resin composition was pressure filtered through an ADVANTEC filter having a pore width of 0.8 ⁇ m.
  • the photosensitive resin composition layer on the Cu wafer was subjected to a binary photomask (square pattern hole pattern, 200 ⁇ m pitch, mask) at an exposure wavelength of 365 nm (i-line) using a stepper (Nikon NSR 2005 i9C). And an exposure energy of 400 mJ / cm 2 .
  • a binary photomask square pattern hole pattern, 200 ⁇ m pitch, mask
  • an exposure energy 400 mJ / cm 2 .
  • ⁇ Development process> The exposed photosensitive resin composition layer was immersed in cyclopentanone for 60 seconds and developed. ⁇ Curing process> Next, the photosensitive resin composition layer after the development treatment was heated at a temperature rising rate of 5 ° C./min, and after reaching 230 ° C., the temperature was maintained for 3 hours.
  • ⁇ Adhesion evaluation> The cured film was allowed to stand for 1000 hours under conditions of 121 ° C. and 100% RH using a high accelerated life test apparatus (PC-422R8D, Hirayama Seisakusho).
  • the peel strength between the substrate and the cured film was measured using a bond tester (Condor Sigma, XYZTEC) on a cured film having a pattern angle of 100 ⁇ m on copper (Cu) wafers before and after the test.
  • a 200 ⁇ m needle was used at room temperature and the peeling rate was 10 ⁇ m / s, and the distance between the substrate and the needle was 2 ⁇ m.
  • the adhesion before the test was 50 gf (1N is 102.0 gf), and the rate of decrease in adhesion before and after ((peeling force after test ⁇ peeling force before test) / peeling force before test) was calculated. .
  • solvent DMSO Dimethyl sulfoxide It means that N-methylpyrrolidone / ethyl lactate was blended at 128.80 / 32.20, and ⁇ -butyrolactone / DMSO (dimethyl sulfoxide) was blended at 128.80 / 32.20.
  • the photosensitive resin composition used in the present invention in combination with the polymer precursor and the specific acid showed sufficient adhesion and realized high storage stability.
  • Comparative Examples 2 and 3 in which the acid itself was not used, the storage stability was inferior (D) and the adhesion was insufficient (D).
  • Comparative Example 1 when the acid was used but did not satisfy the specific requirements (Comparative Example 1), the storage stability was low (C), and the adhesion was insufficient (D). From these results, it was found that the photosensitive resin composition of the present invention can exhibit excellent performance in the production of semiconductor devices and their products.
  • the photosensitive resin composition A-1 was pressure filtered through an ADVANTEC filter having a pore width of 1.0 ⁇ m, and then spun onto the surface of the resin substrate on which the copper thin layer was formed (3500 rpm, 30 seconds). Applied.
  • the photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (Nikon NSR1505i6). The exposure was performed through a mask at an exposure amount of 200 mJ / cm 2 at a wavelength of 365 nm. After exposure, it was baked, developed with cyclopentanone for 30 seconds, and rinsed with PGMEA for 20 seconds to obtain a pattern. Subsequently, it heated at 230 degreeC for 3 hours, and formed the interlayer insulation film for rewiring layers. This interlayer insulation film for rewiring layers was excellent in insulation.

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Abstract

Provided are: a photosensitive resin composition including at least one polymer precursor selected from the group consisting of polyimide precursors and polybenzoxazole precursors, and an acid having a single bond of nitrogen and sulfur; a method for manufacturing the photosensitive resin composition; a cured film; a laminate; a method for manufacturing the cured film; a method for manufacturing the laminate; a semiconductor device; and a preservation stabilizer.

Description

感光性樹脂組成物、硬化膜、積層体およびこれらの応用Photosensitive resin composition, cured film, laminate and applications thereof

　本発明は、感光性樹脂組成物、感光性樹脂組成物の製造方法、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法、半導体デバイスおよび保存安定剤に関する。 The present invention relates to a photosensitive resin composition, a method for producing a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, a semiconductor device, and a storage stabilizer.

　ポリイミド樹脂、ポリベンゾオキサゾール樹脂は、耐熱性および絶縁性に優れるため、様々な用途に適用されている（例えば、非特許文献１、２参照）。その用途は特に限定されないが、実装用の半導体デバイスを例に挙げると、絶縁膜や封止材の材料、あるいはその保護膜としての利用が挙げられる。また、フレキシブル基板のベースフィルムやカバーレイなどとしても用いられている。
　上記のポリイミド樹脂等は、一般に、溶剤への溶解性が低い。そのため、環化反応前のポリマー前駆体、具体的には、ポリイミド前駆体やポリベンゾオキサゾール前駆体の状態で溶剤に溶解する方法がよく用いられる。これにより、優れた取り扱い性を実現することができ、上述のような各製品を製造する際に基板などに多様な形態で塗布して加工することができる。その後、加熱してポリマー前駆体を環化して硬化した製品を形成することができる。ポリイミド樹脂等がもつ高い性能に加え、このような製造上の適応性に優れる観点から、その産業上の応用展開がますます期待されている。 Polyimide resins and polybenzoxazole resins are excellent in heat resistance and insulation, and thus are applied to various uses (for example, see Non-Patent Documents 1 and 2). Although the use is not particularly limited, when a semiconductor device for mounting is taken as an example, it can be used as a material for an insulating film or a sealing material, or as a protective film thereof. It is also used as a base film and coverlay for flexible substrates.
The above polyimide resins and the like generally have low solubility in solvents. Therefore, a method of dissolving in a solvent in a state of a polymer precursor before the cyclization reaction, specifically, a polyimide precursor or a polybenzoxazole precursor is often used. Thereby, the excellent handleability can be realized, and when manufacturing each product as described above, it can be applied and processed in various forms on a substrate or the like. Thereafter, it can be heated to cyclize the polymer precursor to form a cured product. In addition to the high performance possessed by polyimide resins, etc., from the viewpoint of excellent adaptability in production, industrial application development is expected more and more.

　上記の特性を利用して、ポリイミド樹脂等を層間絶縁膜の保護膜として適用することが試みられている。例えば、特許文献１の技術では、（メタ）アクリロイルオキシ基を有するポリイミド前駆体と光重合開始剤とを所定量で含むネガ型感光性樹脂組成物を採用している。これにより、樹脂組成物として透明性が高く、かつ熱硬化後にはヤング率の高い硬化体を得ることができることが記載されている。 It has been attempted to apply a polyimide resin or the like as a protective film for an interlayer insulating film using the above characteristics. For example, in the technique of Patent Document 1, a negative photosensitive resin composition containing a polyimide precursor having a (meth) acryloyloxy group and a photopolymerization initiator in a predetermined amount is employed. Thus, it is described that a cured product having high transparency as a resin composition and having a high Young's modulus can be obtained after thermosetting.

国際公開第２０１３／１６８６７５号International Publication No. 2013/168675

サイエンス＆テクノロジー株式会社「ポリイミドの高機能化と応用技術」２００８年４月Science & Technology Co., Ltd. “High-performance polyimide and applied technology” April 2008 柿本雅明／監修、ＣＭＣテクニカルライブラリー「ポリイミド材料の基礎と開発」２０１１年１１月発行Masaaki Enomoto / Supervision, CMC Technical Library “Basics and Development of Polyimide Materials” November 2011

　上記の技術により、層間絶縁膜等に適するように硬化させることによって、ヤング率の高い硬化体を得ることができる。しかし、この種の絶縁膜等として利用するに当たり、さらに検討すべき特性項目は様々に残されている。例えば、樹脂と金属や金属酸化物等で構成された金属材料の層との密着性については、さらなる検討が求められる。また、上述のようにポリマー前駆体は加熱により硬化させることができるが、その特性がゆえに、保存時の硬化が進みやすく樹脂の安定性を欠くことがある。他方、硬化を防ぐために前駆体の環化を抑制する処方をとると、逆に硬化性が劣ることとなり製膜時の要求特性を満たせないことがある。
　そこで本発明は、金属材料の層との良好な密着性を有し、十分な硬化性を維持しつつ優れた保存安定性を実現できる感光性樹脂組成物、感光性樹脂組成物の製造方法、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法、半導体デバイスおよび保存安定剤の提供を目的とする。 A cured product having a high Young's modulus can be obtained by curing with the above technique so as to be suitable for an interlayer insulating film or the like. However, there are various remaining characteristic items that should be further examined when used as this type of insulating film. For example, further study is required for the adhesion between the resin and the metal material layer made of metal, metal oxide, or the like. Further, as described above, the polymer precursor can be cured by heating, but due to its properties, curing during storage tends to proceed and the stability of the resin may be lacking. On the other hand, if a formulation that suppresses the cyclization of the precursor to prevent curing is taken, the curability is inferior and the required characteristics during film formation may not be satisfied.
Accordingly, the present invention provides a photosensitive resin composition that has good adhesion to the metal material layer and can achieve excellent storage stability while maintaining sufficient curability, a method for producing the photosensitive resin composition, It aims at providing the manufacturing method of a cured film, a laminated body, a cured film, the manufacturing method of a laminated body, a semiconductor device, and a storage stabilizer.

　上記課題のもと、本発明者はポリマー前駆体を含む組成物について、その成分や添加量、調製条件等について様々な観点から検討と実験を繰り返した。その結果、ポリマー前駆体に対し、硫黄と窒素の単結合を有する特定の酸を組み合わせて用いることで、上記の課題を解決しうることを見出し、本発明を完成するに至った。具体的には、下記手段＜１＞および＜２＞～＜２６＞により、上記課題は解決された。 Based on the above problems, the present inventor has repeatedly studied and experimented on the composition containing the polymer precursor from various viewpoints regarding its components, addition amount, preparation conditions, and the like. As a result, the inventors have found that the above-mentioned problems can be solved by using a specific acid having a single bond of sulfur and nitrogen for the polymer precursor, and have completed the present invention. Specifically, the above problems have been solved by the following means <1> and <2> to <26>.

＜１＞ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体と、窒素と硫黄の単結合を有する酸とを含む、感光性樹脂組成物。
＜２＞上記酸のｐｋａが０以上４．０以下である、＜１＞に記載の感光性樹脂組成物。
＜３＞上記酸の水／オクタノール分配係数の対数である、ＣｌｏｇＰが－２．１以上１．２以下である、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞上記酸の分子量が３００以下である、＜１＞～＜３＞のいずれか１つに記載の感光性樹脂組成物。
＜５＞上記酸が環状構造を有する、＜１＞～＜４＞のいずれか１つに記載の感光性樹脂組成物。
＜６＞上記酸がスルタム構造を有する、＜１＞～＜４＞のいずれか１つに記載の感光性樹脂組成物。
＜７＞上記酸が下記式（Ｓ１）～（Ｓ４）のいずれかで表される、＜１＞～＜４＞のいずれか１つに記載の感光性樹脂組成物；

Figure JPOXMLDOC01-appb-C000004
　式（Ｓ１）～（Ｓ４）中、Ｌ１１は単結合または連結基を表し、Ｌ１２は連結基を表し、Ｒ１１は水素原子または置換基を表し、Ｒ２１は置換基を表し、Ｒ３１は置換基を表し、Ｒ４１は水素原子または置換基を表し、Ｒ４２は置換基を表し、Ｒ４３はＯＨ、ＮＨ２またはＮ３を表す。
＜８＞上記酸が下記式（Ｓ１－１）で表される、＜１＞～＜４＞のいずれか１つに記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000005
 　式（Ｓ１－１）中、Ｒ１２は水素原子または置換基であり、Ｒ１３およびＲ１４はそれぞれ独立に水素原子または置換基である。
＜９＞さらに、光重合開始剤、ラジカル重合性化合物および溶剤の少なくとも１種を含む、＜１＞～＜８＞のいずれか１つに記載の感光性樹脂組成物。
＜１０＞再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜９＞のいずれか１つに記載の感光性樹脂組成物。
＜１１＞ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体に、窒素と硫黄の単結合を有する酸を添加することを含む、感光性樹脂組成物の製造方法。
＜１２＞上記酸を、上記ポリマー前駆体の合成中に添加する、＜１１＞に記載の感光性樹脂組成物の製造方法。
＜１３＞上記酸のｐｋａが０以上４．０以下である、＜１１＞または＜１２＞に記載の感光性樹脂組成物の製造方法。
＜１４＞上記酸のＣｌｏｇＰが－２．１以上１．２以下である、＜１１＞～＜１３＞のいずれか１つに記載の感光性樹脂組成物の製造方法。
＜１５＞上記酸の分子量が３００以下である、＜１１＞～＜１４＞のいずれか１つに記載の感光性樹脂組成物の製造方法。
＜１６＞上記酸が下記式（Ｓ１）～（Ｓ４）のいずれかで表される、＜１１＞～＜１５＞のいずれか１つに記載の感光性樹脂組成物の製造方法；
Figure JPOXMLDOC01-appb-C000006
 　式（Ｓ１）～（Ｓ４）中、Ｌ１１は単結合または連結基を表し、Ｌ１２は連結基を表し、Ｒ１１は水素原子または置換基を表し、Ｒ２１は置換基を表し、Ｒ３１は置換基を表し、Ｒ４１は水素原子または置換基を表し、Ｒ４２は置換基を表し、Ｒ４３はＯＨ、ＮＨ２またはＮ３を表す。
＜１７＞＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物を硬化してなる硬化膜。
＜１８＞膜厚が１～３０μｍである、＜１７＞に記載の硬化膜。
＜１９＞＜１７＞または＜１８＞に記載の硬化膜を２層以上有する、積層体。
＜２０＞上記硬化膜の間に金属層を有する、＜１９＞に記載の積層体。
＜２１＞＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
＜２２＞上記膜を露光する露光工程および上記膜を現像する現像工程を有する、＜２１＞に記載の硬化膜の製造方法。
＜２３＞上記現像に用いられる現像液が有機溶剤を９０質量％以上含む、＜２２＞に記載の硬化膜の製造方法。
＜２４＞上記現像工程後に膜を加熱する工程を含む、＜２２＞または＜２３＞に記載の硬化膜の製造方法。
＜２５＞＜２１＞～＜２４＞のいずれか１つに記載の硬化膜の製造方法を複数回行なう、積層体の製造方法。
＜２６＞＜１７＞もしくは＜１８＞に記載の硬化膜または＜１９＞もしくは＜２０＞に記載の積層体を有する、半導体デバイス。 <1> A photosensitive resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and an acid having a single bond of nitrogen and sulfur.
<2> The photosensitive resin composition according to <1>, wherein the acid has a pka of 0 or more and 4.0 or less.
<3> The photosensitive resin composition according to <1> or <2>, wherein ClogP, which is a logarithm of the water / octanol distribution coefficient of the acid, is −2.1 or more and 1.2 or less.
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the acid has a molecular weight of 300 or less.
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid has a cyclic structure.
<6> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid has a sultam structure.
<7> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid is represented by any of the following formulas (S1) to (S4);
Figure JPOXMLDOC01-appb-C000004
 In the formulas (S1) to (S4), L 11 represents a single bond or a linking group, L 12 represents a linking group, R 11 represents a hydrogen atom or a substituent, R 21 represents a substituent, and R 31 Represents a substituent, R 41 represents a hydrogen atom or a substituent, R 42 represents a substituent, and R 43 represents OH, NH 2 or N 3 .
<8> The photosensitive resin composition according to any one of <1> to <4>, wherein the acid is represented by the following formula (S1-1);
Figure JPOXMLDOC01-appb-C000005
 In formula (S1-1), R 12 is a hydrogen atom or a substituent, and R 13 and R 14 are each independently a hydrogen atom or a substituent.
<9> The photosensitive resin composition according to any one of <1> to <8>, further comprising at least one of a photopolymerization initiator, a radical polymerizable compound, and a solvent.
<10> The photosensitive resin composition according to any one of <1> to <9>, which is used for forming an interlayer insulating film for a rewiring layer.
<11> A method for producing a photosensitive resin composition, comprising adding an acid having a single bond of nitrogen and sulfur to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. .
<12> The method for producing a photosensitive resin composition according to <11>, wherein the acid is added during the synthesis of the polymer precursor.
<13> The method for producing a photosensitive resin composition according to <11> or <12>, wherein the acid has a pka of 0 or more and 4.0 or less.
<14> The method for producing a photosensitive resin composition according to any one of <11> to <13>, wherein ClogP of the acid is from -2.1 to 1.2.
<15> The method for producing a photosensitive resin composition according to any one of <11> to <14>, wherein the acid has a molecular weight of 300 or less.
<16> The method for producing a photosensitive resin composition according to any one of <11> to <15>, wherein the acid is represented by any of the following formulas (S1) to (S4);
Figure JPOXMLDOC01-appb-C000006
 In the formulas (S1) to (S4), L 11 represents a single bond or a linking group, L 12 represents a linking group, R 11 represents a hydrogen atom or a substituent, R 21 represents a substituent, and R 31 Represents a substituent, R 41 represents a hydrogen atom or a substituent, R 42 represents a substituent, and R 43 represents OH, NH 2 or N 3 .
<17> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <10>.
<18> The cured film according to <17>, wherein the film thickness is 1 to 30 μm.
<19> A laminate having two or more cured films according to <17> or <18>.
<20> The laminate according to <19>, having a metal layer between the cured films.
<21> A method for producing a cured film, comprising a film forming step of forming a film by applying the photosensitive resin composition according to any one of <1> to <10> to a substrate.
<22> The method for producing a cured film according to <21>, including an exposure step of exposing the film and a development step of developing the film.
<23> The method for producing a cured film according to <22>, wherein the developer used for the development contains 90% by mass or more of an organic solvent.
<24> The method for producing a cured film according to <22> or <23>, including a step of heating the film after the development step.
<25> A method for producing a laminate, wherein the method for producing a cured film according to any one of <21> to <24> is performed a plurality of times.
<26> A semiconductor device having the cured film according to <17> or <18> or the laminate according to <19> or <20>.

　本発明の感光性樹脂組成物によれば、その硬化膜が金属材料の層との良好な密着性を有し、十分な硬化性を維持しつつ優れた保存安定性を実現することができる。また、その効果を有する感光性樹脂組成物の製造方法、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法、半導体デバイスおよび保存安定剤を提供することができる。 According to the photosensitive resin composition of the present invention, the cured film has good adhesion to the metal material layer, and excellent storage stability can be realized while maintaining sufficient curability. Moreover, the manufacturing method of the photosensitive resin composition which has the effect, a cured film, a laminated body, the manufacturing method of a cured film, the manufacturing method of a laminated body, a semiconductor device, and a storage stabilizer can be provided.

　以下において、本発明の内容について詳細に説明する。なお、本明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。 Hereinafter, the contents of the present invention will be described in detail. In the present specification, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

　以下に記載する本発明における構成要素の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
　本明細書における基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「（メタ）アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において、固形分とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、温度は、特に述べない限り２３℃を指すものとする。
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィ（ＧＰＣ測定）に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００およびＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用いることによって求めることができる。溶離液は特に述べない限り、ＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。また、検出は特に述べない限り、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。 The description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) acryl” represents both “acryl” and “methacryl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, solid content is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. The temperature is 23 ° C. unless otherwise specified.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.

　本発明の感光性樹脂組成物（以下、単に、「本発明の組成物」または「本発明の樹脂組成物」ということがある）は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体と、窒素と硫黄の単結合を有する酸（以下、これを「特定の酸」ということがある）とを含むことを特徴とする。これにより、良好な保存安定性および密着性を実現することができる。
　ポリイミド前駆体やポリベンゾオキサゾール前駆体を含む感光性樹脂組成物を長期間保存すると、閉環反応が生じやすくなる。一方で、硬化時には、適切に環化を進行させる必要がある。そのため、ポリイミド前駆体やポリベンゾオキサゾール前駆体を含む感光性樹脂組成物の保存安定性は、重要な課題となっている。
　一方、感光性樹脂組成物を硬化した硬化膜には吸湿性がある。そのため、吸収した水分により基板と硬化膜の密着力を低下させることがある。このような密着性の低下は、例えば半導体デバイスにおいて再配線層を形成する場合に問題となる。
　これに対し、本発明においては、感光性樹脂組成物に特定の酸を添加することによって、環化による硬化反応を過度に阻害することなく、ポリマー前駆体の経時での閉環反応を抑止することができ、保存時の安定性を向上することができる。さらには、上記の特定の酸の作用により感光性樹脂組成物の吸湿を防ぐことができ、硬化させたときの基板との密着性を良化することができる。 The photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention” or “the resin composition of the present invention”) is selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. And an acid having a single bond of nitrogen and sulfur (hereinafter sometimes referred to as “specific acid”). Thereby, favorable storage stability and adhesiveness can be realized.
When a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is stored for a long period of time, a ring closure reaction is likely to occur. On the other hand, at the time of curing, it is necessary to appropriately advance cyclization. Therefore, the storage stability of the photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is an important issue.
On the other hand, the cured film obtained by curing the photosensitive resin composition is hygroscopic. Therefore, the adsorbed moisture may reduce the adhesion between the substrate and the cured film. Such a decrease in adhesion becomes a problem when, for example, a rewiring layer is formed in a semiconductor device.
In contrast, in the present invention, by adding a specific acid to the photosensitive resin composition, the ring-closing reaction of the polymer precursor over time can be suppressed without excessively inhibiting the curing reaction due to cyclization. And stability during storage can be improved. Furthermore, moisture absorption of the photosensitive resin composition can be prevented by the action of the specific acid, and adhesion to the substrate when cured can be improved.

＜特定の酸＞
　本発明の感光性樹脂組成物は、窒素と硫黄の単結合を有する酸（特定の酸）を含む。特定の酸は窒素と硫黄の単結合（Ｎ－Ｓ）を含むが、このような結合が、窒素原子の置換している水素原子の酸性度を高めるため、適度な酸性度となる。さらに、本発明では、－Ｎ－Ｓ（＝Ｏ）２－構造を有することが好ましい。このような構成とすることにより、窒素原子の置換している水素原子の酸性度をより高めることから、本発明の効果がより効果的に発揮される。
　特定の酸は、ｐｋａが０以上４．０以下であることが好ましい。下限値としては、－１０以上であることが好ましく、－５以上であることがより好ましく、１以上であることがさらに好ましい。上限としては、３．８以下であることが好ましく、３．７以下であることがより好ましい。ｐＫａを１以上とすることにより、膜物性の安定性向上という効果がより効果的に発揮され、４．０以下とすることにより、レジスト液中の加水分解を阻害することで室温での保存安定性向上という効果がより効果的に発揮される。特に、ｐＫａを１．０～２．０の範囲とすることにより、銅に対する腐食をより効果的に抑制でき好ましい。
　ここでｐＫａとは、水溶液中でのｐＫａのことを表し、例えば、化学便覧（ＩＩ）（改訂４版、１９９３年、日本化学会編、丸善株式会社）に記載のものが挙げられる。この値が低いほど酸強度が大きいことを示している。水溶液中でのｐＫａは、具体的には、無限希釈水溶液を用い、２５℃での酸解離定数を測定することにより実測することができる。また、下記ソフトウェアパッケージ１を用いて、ハメットの置換基定数および公知文献値のデータベースに基づいた値を、計算により求めることもできる。本明細書におけるｐＫａの値は、このソフトウェアパッケージを用いて計算により求めた値を示している。
ソフトウェアパッケージ１：　Ａｄｖａｎｃｅｄ　Ｃｈｅｍｉｓｔｒｙ　Ｄｅｖｅｌｏｐｍｅｎｔ　（ＡＣＤ／Ｌａｂｓ）　Ｓｏｆｔｗａｒｅ　Ｖ８．１４　ｆｏｒ　Ｓｏｌａｒｉｓ　（１９９４－２００７　ＡＣＤ／Ｌａｂｓ） <Specific acid>
The photosensitive resin composition of this invention contains the acid (specific acid) which has a single bond of nitrogen and sulfur. Certain acids contain a single bond of nitrogen and sulfur (NS), but such a bond increases the acidity of the hydrogen atom substituting for the nitrogen atom, so that the acidity is moderate. Furthermore, in the present invention, it preferably has a —NS (═O) 2 — structure. By setting it as such a structure, since the acidity of the hydrogen atom which the nitrogen atom substituted is raised more, the effect of this invention is exhibited more effectively.
The specific acid preferably has a pka of 0 or more and 4.0 or less. The lower limit is preferably −10 or more, more preferably −5 or more, and even more preferably 1 or more. As an upper limit, it is preferable that it is 3.8 or less, and it is more preferable that it is 3.7 or less. By setting the pKa to 1 or more, the effect of improving the stability of film properties is more effectively exhibited. By setting the pKa to 4.0 or less, storage stability at room temperature is prevented by inhibiting hydrolysis in the resist solution. The effect of improving the performance is more effectively exhibited. In particular, it is preferable to set the pKa in the range of 1.0 to 2.0 because corrosion against copper can be more effectively suppressed.
Here, pKa represents pKa in an aqueous solution, and examples thereof include those described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). A lower value indicates a higher acid strength. Specifically, pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Further, by using the following software package 1, a value based on a Hammett's substituent constant and a database of known literature values can be obtained by calculation. The value of pKa in this specification indicates a value obtained by calculation using this software package.
Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

　特定の酸は、そのＣｌｏｇＰが－２．１以上１．２以下であることが好ましい。下限値としては、－２．１以上であることが好ましく、－１．７５以上であることがより好ましく、－１．５０以上であることがさらに好ましい。上限としては、１．２以下であることが好ましく、１．１８以下であることがより好ましく、１．１６以下であることがさらに好ましい。ＣｌｏｇＰが上記範囲内であることで塗布時の面内均一性および密着力向上の効果がある。
　本明細書で「ＣｌｏｇＰ」とは、化学構造から計算により予測されたｌｏｇＰ（ｌｏｇ［水／オクタノール分配係数］）を意味する。本明細書におけるＣｌｏｇＰはＣｈｅｍ　Ｄｒａｗ　Ｐｒｏ　１２．０で計算された値を用いている。 The specific acid preferably has a ClogP of −2.1 or more and 1.2 or less. The lower limit is preferably −2.1 or more, more preferably −1.75 or more, and further preferably −1.50 or more. As an upper limit, it is preferable that it is 1.2 or less, It is more preferable that it is 1.18 or less, It is further more preferable that it is 1.16 or less. When ClogP is within the above range, there is an effect of improving in-plane uniformity and adhesion at the time of coating.
As used herein, “ClogP” means logP (log [water / octanol partition coefficient]) predicted by calculation from the chemical structure. In this specification, ClogP uses a value calculated by Chem Draw Pro 12.0.

　特定の酸は、その分子量が３００以下であることが好ましい。
　また、特定の酸は波長３６５ｎｍの光に対して安定であることが好ましい。 The specific acid preferably has a molecular weight of 300 or less.
The specific acid is preferably stable to light having a wavelength of 365 nm.

　特定の酸は、環状構造を有することが好ましい。環状構造を有することにより、溶剤への溶解性が向上し、かつ、ポリマーとのスタッキング性がより向上する傾向にある。
　特定の酸はスルタム構造を有することが好ましい。 The specific acid preferably has a cyclic structure. By having a cyclic structure, the solubility in a solvent is improved, and the stacking property with a polymer tends to be further improved.
The specific acid preferably has a sultam structure.

　また、特定の酸は、下記式（Ｓ１）～（Ｓ４）のいずれかで表されることが好ましい。

Figure JPOXMLDOC01-appb-C000007
The specific acid is preferably represented by any of the following formulas (S1) to (S4).
Figure JPOXMLDOC01-appb-C000007

　式（Ｓ１）～（Ｓ４）中、Ｌ１１は単結合または連結基を表し、Ｌ１２は連結基を表し、Ｒ１１は水素原子または置換基を表し、Ｒ２１は置換基を表し、Ｒ３１は置換基を表し、Ｒ４１は水素原子または置換基を表し、Ｒ４２は置換基を表し、Ｒ４３はＯＨ、ＮＨ２またはＮ３を表す。 In the formulas (S1) to (S4), L 11 represents a single bond or a linking group, L 12 represents a linking group, R 11 represents a hydrogen atom or a substituent, R 21 represents a substituent, and R 31 Represents a substituent, R 41 represents a hydrogen atom or a substituent, R 42 represents a substituent, and R 43 represents OH, NH 2 or N 3 .

　Ｌ１１の連結基は芳香族連結基（芳香族炭化水素連結基、複素芳香族連結基）またはアルキレン基が好ましい。芳香族連結基は、後述する置換基Ｔを有していてもよく、炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい。芳香族連結基の具体例としては、後述のポリマー前駆体の所で述べる環Ａｒｏまたは環Ａｒｈを有する連結基が挙げられ、より具体的には後述のポリマー前駆体の所で述べるＡＲ－１～ＡＲ－１０の連結基が挙げられる。なかでも特に置換基Ｔを有していてもよいフェニレン基（特に下記ＡＲ－３の連結構造）が好ましい。アルキレン基としては、置換基Ｔを有していてもよく、炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましく、特に置換基Ｔを有していてもよいエチレンが好ましい。
　Ｌ１２の連結基は後述する連結基Ｌが好ましく、アルキレン基またはカルボニル基が好ましく、カルボニル基がより好ましい。アルキレン基は、後述する置換基Ｔを有していてもよく、炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましく、特に置換基Ｔを有していてもよいメチレン基が好ましい。
　Ｌ１１とＬ１２とは互いに結合して環を形成していてもよい。ここで形成される環としては、炭素数１～６の環であることが好ましく、３～７員の含窒素複素環であることが好ましい。
　Ｒ１１の置換基は、芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい、具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）またはアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい。具体例としては後記Ａｌｋが挙げられる）が好ましい。ただしＲ１１は水素原子が好ましい。
　Ｒ２１の置換基は、芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい。具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）またはアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい、具体例としては後記アルキル基Ａｌｋが挙げられる）が好ましく、置換基Ｔを有していてもよい芳香族基がより好ましく、置換基Ｔを有していてもよいフェニル基がさらに好ましい。ここでの任意の置換基Ｔはカルボキシル基またはニトロ基が好ましい。
　式（Ｓ３）の－ＳＯ２ＮＨ２は、－ＳＯ２ＮＨＲ２２または－ＳＯ２ＮＲ２２Ｒ２３になってもよい。ここでＲ２２およびＲ２３はそれぞれ独立して置換基Ｔであり、芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい、具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）または鎖状でも環状でもよく、直鎖でも分岐でもよいアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい）が好ましい。Ｒ２２とＲ２３とは互いに結合して環を形成していてもよい。ここで形成される環としては、炭素数１～６の環であることが好ましく、３～７員の含窒素複素環であることが好ましい。
　Ｒ３１の置換基は、芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい、具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）またはアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい、具体例としては後記アルキル基Ａｌｋが挙げられる）が好ましく、置換基Ｔを有していてもよい芳香族基がより好ましく、置換基Ｔを有していてもよいフェニル基がさらに好ましい。ここでの任意の置換基Ｔはカルボキシル基が好ましい。
　Ｒ４１は水素原子が好ましい。Ｒ４１の置換基としてはＲ４２の例が挙げられる。
　Ｒ４２は置換基Ｔであることが好ましく、アルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい、具体例としては後記アルキル基Ａｌｋが挙げられる）または芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい、具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）が好ましく、シクロアルキル基（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましい、シクロヘキシル基が一層好ましい）がより好ましい。
　Ｒ４１とＲ４２は互いに結合して環を形成していてもよい。ここで形成される環としては、炭素数１～６の環であることが好ましく、３～７員の含窒素複素環であることが好ましい。
　なお、置換基Ｔは下記連結基Ｌを介して各基に置換していてもよい。これは、下記式（Ｓ１－１）、（Ｓ１－２）、（Ｓ４）～（Ｓ６）についても同様である。
　Ｒ４３はＯＨ、ＮＨ２またはＮ３を表すが、なかでもＯＨが好ましい。 The linking group of L 11 is preferably an aromatic linking group (aromatic hydrocarbon linking group, heteroaromatic linking group) or an alkylene group. The aromatic linking group may have a substituent T described later, preferably has 1 to 22 carbon atoms, more preferably has 1 to 18 carbon atoms, and still more preferably has 1 to 10 carbon atoms. Specific examples of the aromatic linking group include a linking group having a ring Aro or a ring Arh described in the polymer precursor described later, and more specifically, AR-1 to AR-1 described in the polymer precursor described later. AR-10 linking group may be mentioned. Of these, a phenylene group which may have a substituent T (particularly, a connection structure of AR-3 below) is preferable. The alkylene group may have a substituent T, preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 3 carbon atoms, and particularly ethylene that may have a substituent T Is preferred.
The linking group of L 12 is preferably a linking group L described later, preferably an alkylene group or a carbonyl group, and more preferably a carbonyl group. The alkylene group may have a substituent T described later, preferably has 1 to 12 carbon atoms, more preferably has 1 to 6 carbon atoms, still more preferably has 1 to 3 carbon atoms, and may particularly have a substituent T. A methylene group is preferred.
L 11 and L 12 may be bonded to each other to form a ring. The ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
The substituent of R 11 is an aromatic group (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and specific examples thereof include a group having ring Aro or ring Arh described later) Alternatively, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples include Alk described later) is preferable. However, R 11 is preferably a hydrogen atom.
The substituent of R 21 is an aromatic group (preferably having a carbon number of 1 to 22, preferably 1 to 18, more preferably 1 to 10. Specific examples include groups having a ring Aro or a ring Arh described later). Or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples thereof include an alkyl group Alk described later). A preferable aromatic group is more preferable, and a phenyl group which may have a substituent T is more preferable. The optional substituent T here is preferably a carboxyl group or a nitro group.
—SO 2 NH 2 in formula (S3) may be —SO 2 NHR 22 or —SO 2 NR 22 R 23 . Here, R 22 and R 23 are each independently a substituent T, and are aromatic groups (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms; A group having Aro or ring Arh) or an alkyl group which may be linear or cyclic, and may be linear or branched (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms) Is preferred. R 22 and R 23 may be bonded to each other to form a ring. The ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
The substituent of R 31 is an aromatic group (preferably having a carbon number of 1 to 22, preferably 1 to 18, more preferably 1 to 10, and specific examples include a group having a ring Aro or a ring Arh described later). Or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples thereof include an alkyl group Alk described later). A preferable aromatic group is more preferable, and a phenyl group which may have a substituent T is more preferable. The arbitrary substituent T here is preferably a carboxyl group.
R 41 is preferably a hydrogen atom. Examples of the substituent for R 41 include R 42 .
R 42 is preferably a substituent T, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms, and specific examples thereof include an alkyl group Alk described below) or An aromatic group (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms, and specific examples include a group having a ring Aro or a ring Arh described later) is preferable, and a cycloalkyl group ( The number of carbon atoms is preferably 3 to 24, more preferably 3 to 12, still more preferably 3 to 6, and even more preferably a cyclohexyl group.
R 41 and R 42 may be bonded to each other to form a ring. The ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.
The substituent T may be substituted on each group via the following linking group L. The same applies to the following formulas (S1-1), (S1-2), and (S4) to (S6).
R 43 represents OH, NH 2 or N 3 , among which OH is preferable.

　式（Ｓ１）は式（Ｓ１－１）であることが好ましい。

Figure JPOXMLDOC01-appb-C000008
The formula (S1) is preferably the formula (S1-1).
Figure JPOXMLDOC01-appb-C000008

　式（Ｓ１－１）中、Ｒ１２は水素原子または置換基であり、Ｒ１３およびＲ１４はそれぞれ独立に水素原子または置換基である。Ｒ１３とＲ１４が置換基であるときＲ１３とＲ１４は互いに結合または縮合して環を形成していてもよい。 In formula (S1-1), R 12 is a hydrogen atom or a substituent, and R 13 and R 14 are each independently a hydrogen atom or a substituent. When R 13 and R 14 are substituents, R 13 and R 14 may be bonded to each other or condensed to form a ring.

　Ｒ１２の好ましい範囲はＲ１１と同じである。
　Ｒ１３およびＲ１４は置換基であるとき芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい、具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）またはアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい、具体例としては後記Ａｌｋが挙げられる）が好ましい。Ｒ１３とＲ１４が結合または縮合して形成される環としては、芳香族炭化水素環（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましく、具体例としては後記環Ａｒｏが挙げられ、ベンゼン環が一層好ましい）または芳香族複素環（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましく、具体例としては後記環Ａｒｈを構成する環が挙げられる）が挙げられる。 The preferred range of R 12 is the same as R 11 .
When R 13 and R 14 are substituents, they are aromatic groups (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and further preferably 1 to 10 carbon atoms; specific examples thereof include a group having ring Aro or ring Arh described later. Or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and specific examples include Alk described later). The ring formed by combining or condensing R 13 and R 14 is an aromatic hydrocarbon ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms). Ring Aro is mentioned below, and a benzene ring is more preferred, or an aromatic heterocycle (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 and more preferably 3 to 6). Ring).

　式（Ｓ１－１）はさらに下記式（Ｓ１－２）であることが好ましい。

Figure JPOXMLDOC01-appb-C000009
The formula (S1-1) is more preferably the following formula (S1-2).
Figure JPOXMLDOC01-appb-C000009

　式（Ｓ１－２）中、Ｒ１２は式（Ｓ１－１）におけるＲ１２と同義である。
　Ｒ１５～Ｒ１８はそれぞれ独立に水素原子または置換基（例えば置換基Ｔ）である。Ｒ１５とＲ１６が置換基であるときＲ１５とＲ１６は互いに結合または縮合して環を形成していてもよい。Ｒ１６とＲ１７が置換基であるときＲ１６とＲ１７は互いに結合または縮合して環を形成していてもよい。Ｒ１７とＲ１８が置換基であるときＲ１７とＲ１８は互いに結合または縮合して環を形成していてもよい。Ｒ１５とＲ１６、Ｒ１６とＲ１７、Ｒ１７とＲ１８が形成する環の好ましいものは、Ｒ１３とＲ１４が形成する環と同じである。 Wherein (S1-2), R 12 has the same meaning as R 12 in formula (S1-1).
R 15 to R 18 are each independently a hydrogen atom or a substituent (for example, substituent T). When R 15 and R 16 are substituents, R 15 and R 16 may be bonded to each other or condensed to form a ring. When R 16 and R 17 are substituents, R 16 and R 17 may be bonded to each other or condensed to form a ring. When R 17 and R 18 are substituents, R 17 and R 18 may be bonded to each other or condensed to form a ring. The preferred ring formed by R 15 and R 16 , R 16 and R 17 , R 17 and R 18 is the same as the ring formed by R 13 and R 14 .

　本発明の別の好ましい実施形態として、特定の酸は、環構造を有する化合物であることが好ましい。環構造としては芳香族炭化水素環（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましく、具体例としては環Ａｒｏが挙げられ、ベンゼン環が一層好ましい）、芳香族複素環（炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましく、具体例としては環Ａｒｈが挙げられる）、または脂環（例えば、炭素数３～２４が好ましく、３～１２がより好ましく、３～６がさらに好ましい。具体例としては、シクロヘキサン環が好ましい。ここで例示した脂環をＡｃｙと称する）が挙げられる。環Ａｒｏ、感Ａｒｈ、環Ａｃｙは、本発明の効果を奏する範囲で置換基Ｔを有していてもよい。ここで例示した環構造を総称してｔＣｙと呼ぶことがある。このように環構造を有する酸を用いることにより本発明の効果を奏する理由としては、ポリマーとのスタッキング性向上が挙げられる。 As another preferred embodiment of the present invention, the specific acid is preferably a compound having a ring structure. The ring structure is an aromatic hydrocarbon ring (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms, and specific examples thereof include ring Aro, and a benzene ring is more preferable), aromatic Group heterocycle (preferably having 3 to 24 carbon atoms, more preferably 3 to 12 carbon atoms, still more preferably 3 to 6 carbon atoms, and specific examples include ring Arh) or alicyclic ring (for example, preferably having 3 to 24 carbon atoms) 3 to 12 is more preferable, and 3 to 6 is more preferable, and a specific example is a cyclohexane ring (the alicyclic ring exemplified here is referred to as Acy). Ring Aro, sensation Arh, and ring Acy may have a substituent T as long as the effects of the present invention are exhibited. The ring structures exemplified here may be collectively referred to as tCy. The reason why the effects of the present invention can be obtained by using an acid having a ring structure in this way is an improvement in stacking properties with a polymer.

　環構造を有する酸は、下記式（Ｓ５）～（Ｓ８）のいずれかで表されることが好ましい。

Figure JPOXMLDOC01-appb-C000010
The acid having a ring structure is preferably represented by any of the following formulas (S5) to (S8).
Figure JPOXMLDOC01-appb-C000010

　式（Ｓ５）～（Ｓ８）において、Ｃｙは環構造の基を表し、上記の環ｔＣｙであることが好ましい。環Ｃｙは本発明の効果を奏する範囲で置換基Ｔを有していてもよい。
　式（Ｓ５）および（Ｓ８）中、Ｌ１２、Ｒ４１およびＲ４３はそれぞれ式（Ｓ１）および（Ｓ４）で定義されるものと同義であり、好ましい範囲も同じである。
　式（Ｓ６）の－ＳＯ２ＮＨ２は、－ＳＯ２ＮＨＲ２２または－ＳＯ２ＮＲ２２Ｒ２３になってもよい。ここでＲ２２およびＲ２３はそれぞれ独立して置換基Ｔであり、芳香族基（炭素数１～２２が好ましく、１～１８がより好ましく、１～１０がさらに好ましい、具体例としては後記環Ａｒｏまたは環Ａｒｈを有する基が挙げられる）または鎖状でも環状でもよく、直鎖でも分岐でもよいアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６がさらに好ましい）が好ましい。Ｒ２２とＲ２３とは互いに結合して環を形成していてもよい。ここで形成される環としては、炭素数１～６の環であることが好ましく、３～７員の含窒素複素環であることが好ましい。 In the formulas (S5) to (S8), Cy represents a ring structure group, and is preferably the ring tCy described above. Ring Cy may have a substituent T as long as the effects of the present invention are exhibited.
In formulas (S5) and (S8), L 12 , R 41 and R 43 have the same definitions as those defined in formulas (S1) and (S4), respectively, and preferred ranges are also the same.
—SO 2 NH 2 in formula (S6) may be —SO 2 NHR 22 or —SO 2 NR 22 R 23 . Here, R 22 and R 23 are each independently a substituent T, and are aromatic groups (preferably having 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 10 carbon atoms; A group having Aro or ring Arh) or an alkyl group which may be linear or cyclic, and may be linear or branched (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6 carbon atoms) Is preferred. R 22 and R 23 may be bonded to each other to form a ring. The ring formed here is preferably a ring having 1 to 6 carbon atoms, and preferably a 3- to 7-membered nitrogen-containing heterocycle.

　置換基Ｔとしては、アルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）、アルケニル基（炭素数２～２４が好ましく、２～１２がより好ましく、２～６が特に好ましい）、アルコキシル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、ヘテロアリール基（炭素数１～１２が好ましく、１～６がより好ましく、１～４がさらに好ましい；ヘテロ原子としては例えば窒素原子、酸素原子、硫黄原子が挙げられる）、アリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）、ヒドロキシル基、アミノ基（炭素数０～２４が好ましく、０～１２がより好ましく、０～６が特に好ましい）、チオール基、カルボキシル基、ニトロ基、アシル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、アシルオキシ基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、アリーロイル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が特に好ましい）、アリーロイルオキシ基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が特に好ましい）、(メタ)アクリロイル基、(メタ)アクリロイルオキシ基、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子）、オキソ基（＝Ｏ）、イミノ基（＝ＮＲＮ）、アルキリデン基（＝Ｃ（ＲＮ）２）などが挙げられる。置換基Ｔのアルキレン鎖にはヘテロ原子が介在していてもよい。置換基Ｔが有するアルキル基、アルケニル基、アリール基、アリールアルキル基には、さらにその他の置換基が置換していてもよい。
　ＲＮは水素原子または有機基である。有機基としては、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、またはアリールアルキル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１がさらに好ましい）が好ましい。 As the substituent T, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) or an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms) 2 to 6 are particularly preferred), an alkoxyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). Preferably 6 to 10), a heteroaryl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and even more preferably 1 to 4; examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom) An arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, more preferably 7 to 11 carbon atoms), a hydroxyl group, an amino group (0 to 2 carbon atoms). Preferably 0-12, more preferably 0-6, thiol group, carboxyl group, nitro group, acyl group (2-12 carbon atoms are preferred, 2-6 are more preferred, and 2-3 are especially preferred) Preferably), an acyloxy group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), an aryloyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and 7 to 11 carbon atoms). Is particularly preferred), an aryloyloxy group (preferably having a carbon number of 7 to 23, more preferably 7 to 19, and particularly preferably 7 to 11), a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (for example, , fluorine atom, chlorine atom, bromine atom, iodine atom), oxo (= O), imino (= NR N), an alkylidene group (= C (R N) 2 ) are like . A hetero atom may be present in the alkylene chain of the substituent T. The alkyl group, alkenyl group, aryl group, and arylalkyl group of the substituent T may be further substituted with other substituents.
RN is a hydrogen atom or an organic group. Examples of the organic group include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, To 10 are more preferable), or an arylalkyl group (preferably having a carbon number of 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11).

　連結基Ｌは、アルキレン基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニレン基（炭素数２～１２が好ましく、２～６がより好ましい）、アリーレン基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、ヘテロアリーレン基（炭素数１～１２が好ましく、１～６がより好ましく、１～４がさらに好ましい；ヘテロ原子としては例えば窒素原子、酸素原子、硫黄原子が挙げられる）、酸素原子、硫黄原子、カルボニル基、－ＮＲＮ－、またはその組合せにかかる基である。連結基Ｌを構成する原子の数は水素原子を除いて、１～２４であることが好ましく、１～１２がより好ましく、１～６が特に好ましい。連結基の連結する原子数は１０以下であることが好ましく、８以下であることがより好ましい。下限としては、１以上である。 The linking group L is an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms), An arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), and heteroarylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 4 carbon atoms). Preferred examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom), an oxygen atom, a sulfur atom, a carbonyl group, —NR N —, or a combination thereof. The number of atoms constituting the linking group L is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6, excluding hydrogen atoms. The number of atoms connected to the linking group is preferably 10 or less, and more preferably 8 or less. The lower limit is 1 or more.

　特定の酸の具体例としては下記の化合物が例示されるが、本発明がこれにより限定して解釈されるものではない。
 

Figure JPOXMLDOC01-appb-C000011




Specific examples of the specific acid include the following compounds, but the present invention is not construed as being limited thereto.

Figure JPOXMLDOC01-appb-C000011



Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012

Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013

Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014

Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015

Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016

Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017

Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018

　感光性樹脂組成物において、特定の酸の含有量は、固形分中、０．１０質量％以上であることが好ましく、０．１５質量％以上であることがより好ましく、０．２０質量％以上であることがさらに好ましい。上限としては、２．０質量％以下であることが好ましく、１．８質量％以下であることがより好ましく、１．６質量％以下であることがさらに好ましい。
　ポリマー前駆体１００質量部に対しては、特定の酸の含有量は、０．１５質量部以上であることが好ましく、０．１８質量部以上であることがより好ましく、０．２０質量部以上であることがさらに好ましい。上限としては、２．５質量部以下であることが好ましく、２．２５質量部以下であることがより好ましく、２．０質量部以下であることがさらに好ましい。
　この量を上記の範囲とすることで、特定の酸の作用を十分に発揮させることができ、また、保存安定性のため好ましい。
　特定の酸は、１種を用いても複数のものを用いてもよい。複数のものを用いる場合はその合計量が上記の範囲となる。また、特定の酸は他の酸と組み合わせて用いてもよい。例えば、酢酸などと組み合わせて用いることを妨げるものではない。
　ただし、本発明の組成物に含まれる酸のなかでは、上記特定の酸がポリマー前駆体以外の酸の主成分を占めることが好ましく、８０質量％以上であることがより好ましく、９０質量％以上であることがさらに好ましく、９５質量％以上であることが一層好ましく、９９質量％以上であることがより一層好ましい。 In the photosensitive resin composition, the content of the specific acid in the solid content is preferably 0.10% by mass or more, more preferably 0.15% by mass or more, and 0.20% by mass or more. More preferably. As an upper limit, it is preferable that it is 2.0 mass% or less, It is more preferable that it is 1.8 mass% or less, It is further more preferable that it is 1.6 mass% or less.
The content of the specific acid with respect to 100 parts by mass of the polymer precursor is preferably 0.15 parts by mass or more, more preferably 0.18 parts by mass or more, and 0.20 parts by mass or more. More preferably. As an upper limit, it is preferable that it is 2.5 mass parts or less, It is more preferable that it is 2.25 mass parts or less, It is further more preferable that it is 2.0 mass parts or less.
By making this quantity into the above-mentioned range, the action of a specific acid can be sufficiently exerted, and it is preferable for storage stability.
The specific acid may be used alone or in combination. When using a plurality of items, the total amount is within the above range. Moreover, you may use a specific acid in combination with another acid. For example, it does not prevent use in combination with acetic acid or the like.
However, among the acids contained in the composition of the present invention, the specific acid preferably occupies the main component of an acid other than the polymer precursor, more preferably 80% by mass or more, and 90% by mass or more. More preferably, it is more preferably 95% by mass or more, and even more preferably 99% by mass or more.

　特定の酸はどのタイミングで感光性樹脂組成物に添加してもよいが、例えば、後述するポリマー前駆体の合成中または合成後、あるいは組成物を調製する際に添加してもよい。なかでも、ポリマー前駆体の合成中に添加することが好ましい。ここで、合成中とは、例えば、ポリマー前駆体が合成工程および精製工程を含む工程を経ている時点を指す。合成中には更にポリマー前駆体の乾燥工程が行なわれてもよい。このように合成中に配合することにより、ポリマー前駆体中に特定の酸がより均一に分散し、本発明の効果がより効果的に発揮される。 The specific acid may be added to the photosensitive resin composition at any timing. For example, it may be added during or after the synthesis of the polymer precursor described later, or when the composition is prepared. Especially, adding during the synthesis | combination of a polymer precursor is preferable. Here, “synthesizing” refers to, for example, the time when the polymer precursor has undergone a process including a synthesis process and a purification process. During the synthesis, a polymer precursor drying step may be further performed. Thus, by mix | blending during a synthesis | combination, a specific acid disperse | distributes more uniformly in a polymer precursor, and the effect of this invention is exhibited more effectively.

＜ポリマー前駆体＞
　本発明の感光性樹脂組成物は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体を含む。ポリマー前駆体としては、ポリイミド前駆体がより好ましく、下記式（１）で表される構成単位を含むポリイミド前駆体であることがさらに好ましい。 <Polymer precursor>
The photosensitive resin composition of the present invention includes at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. As the polymer precursor, a polyimide precursor is more preferable, and a polyimide precursor including a structural unit represented by the following formula (1) is more preferable.

＜＜ポリイミド前駆体＞＞
　ポリイミド前駆体としては下記式（１）で表される構成単位を含むことが好ましい。このような構成とすることにより、より膜強度に優れた組成物が得られる。

Figure JPOXMLDOC01-appb-C000019
　Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す。 << Polyimide precursor >>
As a polyimide precursor, it is preferable that the structural unit represented by following formula (1) is included. By setting it as such a structure, the composition excellent in film | membrane intensity | strength is obtained.
Figure JPOXMLDOC01-appb-C000019
 A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113 and R 114 each independently Represents a hydrogen atom or a monovalent organic group.

　Ａ１およびＡ２は、それぞれ独立に、酸素原子またはＮＨであり、酸素原子が好ましい。 A 1 and A 2 are each independently an oxygen atom or NH, preferably an oxygen atom.

　Ｒ１１１は、２価の有機基を表す。２価の有機基としては、直鎖または分岐の脂肪族基、環状の脂肪族基、および芳香族基、芳香族複素環基、またはこれらの組み合わせからなる基が例示され、炭素数２～２０の直鎖の脂肪族基、炭素数３～２０の分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数６～２０の芳香族基、または、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族基がより好ましい。
　Ｒ１１１は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖または分岐の脂肪族、環状の脂肪族または芳香族ジアミンなどが挙げられる。ジアミンは、１種のみ用いてもよいし、２種以上用いてもよい。
　具体的には、ジアミンは、炭素数２～２０の直鎖脂肪族基、炭素数３～２０の分岐または環状の脂肪族基、炭素数６～２０の芳香族基、または、これらの組み合わせからなる基を含むものであることが好ましく、炭素数６～２０の芳香族基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。 R 111 represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group composed of an aromatic group, an aromatic heterocyclic group, or a combination thereof, and has 2 to 20 carbon atoms. A straight chain aliphatic group, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And an aromatic group having 6 to 20 carbon atoms is more preferable.
R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. One type of diamine may be used, or two or more types may be used.
Specifically, the diamine is a straight chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable. The following are mentioned as an example of an aromatic group.

Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020

　式中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－および－ＳＯ２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、および、－Ｃ（ＣＨ３）２－からなる群から選択される２価の基であることがさらに好ましい。 In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (═O) 2 —, —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O— , —C (═O) —, —S— and —SO 2 — are more preferable, and —CH 2 —, —O—, —S—, —SO 2 —, —C ( More preferably, it is a divalent group selected from the group consisting of CF 3 ) 2 — and —C (CH 3 ) 2 —.

　ジアミンとしては、具体的には、１，２－ジアミノエタン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，４－ジアミノブタンおよび１，６－ジアミノヘキサン；１，２－または１，３－ジアミノシクロペンタン、１，２－、１，３－または１，４－ジアミノシクロヘキサン、１，２－、１，３－または１，４－ビス（アミノメチル）シクロヘキサン、ビス－（４－アミノシクロヘキシル）メタン、ビス－（３－アミノシクロヘキシル）メタン、４，４’－ジアミノ－３，３’－ジメチルシクロヘキシルメタンおよびイソホロンジアミン；メタおよびパラフェニレンジアミン、ジアミノトルエン、４，４’－および３，３’－ジアミノビフェニル、４，４’－ジアミノジフェニルエーテル、３，３－ジアミノジフェニルエーテル、４，４’－および３，３’－ジアミノジフェニルメタン、４，４’－および３，３’－ジアミノジフェニルスルホン、４，４’－および３，３’－ジアミノジフェニルスルフィド、４，４’－および３，３’－ジアミノベンゾフェノン、３，３’－ジメチル－４，４’－ジアミノビフェニル、２，２’－ジメチル－４，４’－ジアミノビフェニル（４，４’-ジアミノ-２，２’-ジメチルビフェニル）、３，３’－ジメトキシ－４，４’－ジアミノビフェニル、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）プロパン、２，２－ビス（３－ヒドロキシ－４－アミノフェニル）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、４，４’－ジアミノパラテルフェニル、４，４’－ビス（４－アミノフェノキシ）ビフェニル、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、ビス［４－（２－アミノフェノキシ）フェニル］スルホン、１，４－ビス（４－アミノフェノキシ）ベンゼン、９，１０－ビス（４－アミノフェニル）アントラセン、３，３’－ジメチル－４，４’－ジアミノジフェニルスルホン、１，３－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（３－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェニル）ベンゼン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、３，３’－ジメチル－４，４’－ジアミノジフェニルメタン、４，４’－ジアミノオクタフルオロビフェニル、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、９，９－ビス（４－アミノフェニル）－１０－ヒドロアントラセン、３，３’，４，４’－テトラアミノビフェニル、３，３’，４，４’－テトラアミノジフェニルエーテル、１，４－ジアミノアントラキノン、１，５－ジアミノアントラキノン、３，３－ジヒドロキシ－４，４’－ジアミノビフェニル、９，９’－ビス（４－アミノフェニル）フルオレン、４，４’－ジメチル－３，３’－ジアミノジフェニルスルホン、３，３’，５，５’－テトラメチル－４，４’－ジアミノジフェニルメタン、２－（３’，５’－ジアミノベンゾイルオキシ）エチルメタクリレート、２，４－および２，５－ジアミノクメン、２，５－ジメチル－パラフェニレンジアミン、アセトグアナミン、２，３，５，６－テトラメチル－パラフェニレンジアミン、２，４，６－トリメチル－メタフェニレンジアミン、ビス（３－アミノプロピル）テトラメチルジシロキサン、２，７－ジアミノフルオレン、２，５－ジアミノピリジン、１，２－ビス（４－アミノフェニル）エタン、ジアミノベンズアニリド、ジアミノ安息香酸のエステル、１，５－ジアミノナフタレン、ジアミノベンゾトリフルオライド、１，３－ビス（４－アミノフェニル）ヘキサフルオロプロパン、１，４－ビス（４－アミノフェニル）オクタフルオロブタン、１，５－ビス（４－アミノフェニル）デカフルオロペンタン、１，７－ビス（４－アミノフェニル）テトラデカフルオロヘプタン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（２－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ジメチルフェニル］ヘキサフルオロプロパン、２，２－ビス［４－（４－アミノフェノキシ）－３，５－ビス（トリフルオロメチル）フェニル］ヘキサフルオロプロパン、パラビス（４－アミノ－２－トリフルオロメチルフェノキシ）ベンゼン、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－３－トリフルオロメチルフェノキシ）ビフェニル、４，４’－ビス（４－アミノ－２－トリフルオロメチルフェノキシ）ジフェニルスルホン、４，４’－ビス（３－アミノ－５－トリフルオロメチルフェノキシ）ジフェニルスルホン、２，２－ビス［４－（４－アミノ－３－トリフルオロメチルフェノキシ）フェニル］ヘキサフルオロプロパン、３，３’，５，５’－テトラメチル－４，４’－ジアミノビフェニル、４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニル、２，２’，５，５’，６，６’－ヘキサフルオロトリジンおよび４，４’－ジアミノクアテルフェニルから選ばれる少なくとも１種のジアミンが挙げられる。 Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4- Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; meta and paraphenylenediamine, diaminotoluene, 4,4'- and 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether 4,4'- and 3,3'-diaminodiphenylmethane, 4,4'- and 3,3'-diaminodiphenyl sulfone, 4,4'- and 3,3'-diaminodiphenyl sulfide, 4,4 ' -And 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl (4,4'-diamino-2,2 '-Dimethylbiphenyl), 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2 , 2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis 3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3) -Hydroxyphenyl) sulfone, 4,4′-diaminoparaterphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3 -Aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3, 3'-dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) ben Zen, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenyl) benzene, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 3,3′-dimethyl- 4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) Phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3 ′, 4,4′-tetraaminobiphenyl, 3,3 ′, 4,4′-tetraaminodiphenyl ether 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4′-diaminobiphenyl, 9 9′-bis (4-aminophenyl) fluorene, 4,4′-dimethyl-3,3′-diaminodiphenylsulfone, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 2 -(3 ', 5'-diaminobenzoyloxy) ethyl methacrylate, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-paraphenylenediamine, acetoguanamine, 2,3,5,6-tetramethyl -Paraphenylenediamine, 2,4,6-trimethyl-metaphenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4 -Aminophenyl) ethane, diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene Diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octafluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) Phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5 -Bis (trifluoromethyl) phenyl] hexafluoropropane, parabis (4-amino-2-trifluoromethyl) Phenoxy) benzene, 4,4′-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4′-bis (4-Amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4′-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2,2-bis [4- (4-amino-3 -Trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl ) Selected from biphenyl, 2,2 ', 5,5', 6,6'-hexafluorotolidine and 4,4'-diaminoquaterphenyl At least one diamine that.

　また、下記に示すジアミン（ＤＡ－１）～（ＤＡ－１８）も好ましい。 Further, diamines (DA-1) to (DA-18) shown below are also preferable.

Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021

　また、少なくとも２つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましい例として挙げられる。好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれか一方または両方を一分子中にあわせて２つ以上含むジアミン、より好ましくは芳香環を含まないジアミンである。具体例としては、ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６、Ｄ－２００、Ｄ－４００、Ｄ－２０００、Ｄ－４０００（以上商品名、ＨＵＮＴＳＭＡＮ社製）、１－（２－（２－（２－アミノプロポキシ）エトキシ）プロポキシ）プロパン－２－アミン、１－（１－（１－（２－アミノプロポキシ）プロパン－２－イル）オキシ）プロパン－２－アミンなどが挙げられるが、これらに限定されない。
　ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６の構造を以下に示す。 A diamine having at least two alkylene glycol units in the main chain is also a preferred example. Preferred is a diamine containing two or more ethylene glycol chains or propylene glycol chains in one molecule, and more preferred is a diamine containing no aromatic ring. Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark). ) EDR-148, Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (above trade names, manufactured by HUNTSMAN), 1- (2- (2- (2 -Aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like. Not.
Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022

　上記において、ｘ、ｙ、ｚは平均値である。 In the above, x, y, and z are average values.

　Ｒ１１１は、得られる硬化膜の柔軟性の観点から、－Ａｒ０－Ｌ０－Ａｒ０－で表されることが好ましい。但し、Ａｒ０は、それぞれ独立に、芳香族炭化水素基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）であり、フェニレン基が好ましい。Ｌ０は、単結合、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基を表す。好ましい範囲は、上述のＡと同義である。 R 111 is preferably represented by -Ar 0 -L 0 -Ar 0- from the viewpoint of the flexibility of the resulting cured film. However, Ar 0 is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and particularly preferably 6 to 10), and is preferably a phenylene group. L 0 represents a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (═O). 2 represents a group selected from —NHCO— and combinations thereof. A preferred range is synonymous with A described above.

　Ｒ１１１は、ｉ線透過率の観点から下記式（５１）または式（６１）で表される２価の有機基であることが好ましい。特に、ｉ線透過率、入手のし易さの観点から式（６１）で表される２価の有機基であることがより好ましい。

Figure JPOXMLDOC01-appb-C000023
　Ｒ５０～Ｒ５７は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ５０～Ｒ５７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　Ｒ５０～Ｒ５７の１価の有機基として、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。
Figure JPOXMLDOC01-appb-C000024
 　Ｒ５８およびＲ５９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　式（５１）または（６１）の構造を与えるジアミン化合物としては、ジメチル－４,４’－ジアミノビフェニル、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらの１種を用いるか、２種以上を組み合わせて用いてもよい。 R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
Figure JPOXMLDOC01-appb-C000023
 R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, a difluoromethyl group, or A trifluoromethyl group.
Examples of the monovalent organic group represented by R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
Figure JPOXMLDOC01-appb-C000024
 R 58 and R 59 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.

　式（１）におけるＲ１１５は、４価の有機基を表す。４価の有機基としては、芳香環を含む基であることが好ましく、下記式（５）または式（６）で表される基がより好ましい。

Figure JPOXMLDOC01-appb-C000025
　Ｒ１１２は、Ａと同義であり、好ましい範囲も同じである。 R 115 in formula (1) represents a tetravalent organic group. The tetravalent organic group is preferably a group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
Figure JPOXMLDOC01-appb-C000025
 R 112 has the same meaning as A, and the preferred range is also the same.

　式（１）におけるＲ１１５が表す４価の有機基は、具体的には、テトラカルボン酸二無水物から酸二無水物基を除去した後に残存するテトラカルボン酸残基などが挙げられる。テトラカルボン酸二無水物は、１種のみ用いてもよいし、２種以上用いてもよい。テトラカルボン酸二無水物は、下記式（７）で表される化合物が好ましい。

Figure JPOXMLDOC01-appb-C000026
　Ｒ１１５は、４価の有機基を表す。Ｒ１１５は式（１）のＲ１１５と同義である。 Specific examples of the tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
Figure JPOXMLDOC01-appb-C000026
 R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (1).

　テトラカルボン酸二無水物の具体例としては、ピロメリット酸、ピロメリット酸二無水物（ＰＭＤＡ）、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルフィドテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルメタンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルメタンテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ベンゾフェノンテトラカルボン酸二無水物、４，４’－オキシジフタル酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、１，４，５，７－ナフタレンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、１，３－ジフェニルヘキサフルオロプロパン－３，３，４，４－テトラカルボン酸二無水物、１，４，５，６－ナフタレンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、１，２，４，５－ナフタレンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、１，８，９，１０－フェナントレンテトラカルボン酸二無水物、１，１－ビス（２，３－ジカルボキシフェニル）エタン二無水物、１，１－ビス（３，４－ジカルボキシフェニル）エタン二無水物、１，２，３，４－ベンゼンテトラカルボン酸二無水物、ならびに、これらの炭素数１～６のアルキル誘導体および炭素数１～６のアルコキシ誘導体から選ばれる少なくとも１種が例示される。 Specific examples of tetracarboxylic dianhydrides include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4 , 4′-diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 1,4,5,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) Propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1, -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride And at least one selected from alkyl derivatives having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

　また、下記に示すテトラカルボン酸二無水物（ＤＡＡ－１）～（ＤＡＡ－５）も好ましい例として挙げられる。

Figure JPOXMLDOC01-appb-C000027
Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
Figure JPOXMLDOC01-appb-C000027

　式（１）におけるＲ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す。Ｒ１１３およびＲ１１４の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことがより好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を有する基が挙げられる。
　エチレン性不飽和結合を有する基としては、ビニル基、アリル基、（メタ）アクリロイル基、下記式（ＩＩＩ）で表される基などが挙げられる。 R 113 and R 114 in Formula (1) each independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radical polymerizable group, and more preferably both contain a radical polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, a group represented by the following formula (III), and the like.

Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028

　式（ＩＩＩ）において、Ｒ２００は、水素原子またはメチル基を表し、メチル基がより好ましい。
　式（ＩＩＩ）において、Ｒ２０１は、炭素数２～１２のアルキレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－または炭素数４～３０の（ポリ）オキシアルキレン基（アルキレン基としては炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい；繰り返し数は１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）を表す。なお、（ポリ）オキシアルキレン基とは、オキシアルキレン基またはポリオキシアルキレン基を意味する。
　好適なＲ２０１の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、１，２－ブタンジイル基、１，３－ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－が挙げられ、エチレン基、プロピレン基、トリメチレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－がより好ましい。
　特に好ましくは、Ｒ２００がメチル基で、Ｒ２０１がエチレン基である。 In the formula (III), R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom) To 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3. The (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH 2 CH (OH) CH 2 —, and ethylene group, propylene group, trimethylene group, and —CH 2 CH (OH) CH 2 — are more preferable.
Particularly preferably, R 200 is a methyl group and R 201 is an ethylene group.

　本発明におけるポリイミド前駆体の好ましい実施形態として、Ｒ１１３またはＲ１１４の１価の有機基として、１、２または３つの、好ましくは１つの酸基を有する、脂肪族基、芳香族基およびアリールアルキル基などが挙げられる。具体的には、酸基を有する炭素数６～２０の芳香族基、酸基を有する炭素数７～２５のアリールアルキル基が挙げられる。より具体的には、酸基を有するフェニル基および酸基を有するベンジル基が挙げられる。酸基は、ヒドロキシル基が好ましい。すなわち、Ｒ１１３またはＲ１１４はヒドロキシル基を有する基であることが好ましい。
　Ｒ１１３またはＲ１１４が表す１価の有機基としては、現像液の溶解度を向上させる置換基が好ましく用いられる。
　Ｒ１１３またはＲ１１４が、水素原子、２－ヒドロキシベンジル、３－ヒドロキシベンジルおよび４－ヒドロキシベンジルであることが、水性現像液に対する溶解性の点からは、より好ましい。 As a preferable embodiment of the polyimide precursor in the present invention, an aliphatic group, an aromatic group and an aryl group having 1, 2, or 3, preferably one acid group, as the monovalent organic group of R 113 or R 114 An alkyl group etc. are mentioned. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acid group and an arylalkyl group having 7 to 25 carbon atoms having an acid group. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned. The acid group is preferably a hydroxyl group. That is, R 113 or R 114 is preferably a group having a hydroxyl group.
As the monovalent organic group represented by R113 or R114, a substituent that improves the solubility of the developer is preferably used.
R 113 or R 114 is more preferably a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl or 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.

　有機溶剤への溶解度の観点からは、Ｒ１１３またはＲ１１４は、１価の有機基であることが好ましい。１価の有機基としては、直鎖または分岐のアルキル基、環状アルキル基、芳香族基を含むことが好ましく、芳香族基で置換されたアルキル基がより好ましい。
　アルキル基の炭素数は１～３０が好ましい（環状の場合は３以上）。アルキル基は直鎖、分岐、環状のいずれであってもよい。直鎖または分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、１－エチルペンチル基、および２－エチルヘキシル基が挙げられる。環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状のアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基およびシクロオクチル基が挙げられる。多環の環状のアルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基およびピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が最も好ましい。また、芳香族基で置換されたアルキル基としては、後述する芳香族基で置換された直鎖アルキル基が好ましい。（ここで例示されたアルキル基をＡｌｋと称する）
　芳香族基としては、芳香族炭化水素基または芳香族複素環基が挙げられる。
　芳香族炭化水素基としては、具体的には、置換または無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環等の芳香族炭化水素環を有する基が挙げられる。（ここで例示された芳香族炭化水素環を環Ａｒｏと称する）
　芳香族複素環基としては、置換または無置換のピロール環、フラン環、チオフェン環、ピラゾール環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、トリアジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環またはフェナジン環等の芳香族複素環を有する基が挙げられる。（ここで例示された芳香族複素環を環Ａｒｈと称する） From the viewpoint of solubility in an organic solvent, R 113 or R 114 is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group). The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, and an octadecyl group. Isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a camphenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group, and a pinenyl group. Is mentioned. Among these, a cyclohexyl group is most preferable from the viewpoint of achieving high sensitivity. Moreover, as an alkyl group substituted by the aromatic group, the linear alkyl group substituted by the aromatic group mentioned later is preferable. (The alkyl group exemplified here is called Alk)
Examples of the aromatic group include an aromatic hydrocarbon group and an aromatic heterocyclic group.
Specific examples of the aromatic hydrocarbon group include a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring. , Groups having an aromatic hydrocarbon ring such as anthracene ring, naphthacene ring, chrysene ring, triphenylene ring, fluorene ring and biphenyl ring. (The aromatic hydrocarbon ring exemplified here is referred to as ring Aro)
Aromatic heterocyclic groups include substituted or unsubstituted pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, India Lysine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, phenanthroline And a group having an aromatic heterocycle such as a ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. (The aromatic heterocycle exemplified here is referred to as ring Arh)

　また、ポリイミド前駆体は、構成単位中にフッ素原子を有することも好ましい。ポリイミド前駆体中のフッ素原子含有量は１０質量％以上が好ましく、２０質量％以上がより好ましい。上限は特にないが５０質量％以下が実際的である。 Also, the polyimide precursor preferably has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.

　また、基板との密着性を向上させる目的で、シロキサン構造を有する脂肪族基を式（１）で表される構成単位に共重合してもよい。具体的には、ジアミン成分として、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（パラアミノフェニル）オクタメチルペンタシロキサンなどが挙げられる。 Further, for the purpose of improving the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with the structural unit represented by the formula (1). Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.

　式（１）で表される構成単位は、式（１－Ａ）で表される構成単位であることが好ましい。

Figure JPOXMLDOC01-appb-C000029
　Ａ１、Ａ２、Ｒ１１１、Ｒ１１３およびＲ１１４は、それぞれ、独立に、式（１）におけるＡ１、Ａ２、Ｒ１１１、Ｒ１１３およびＲ１１４と同義であり、好ましい範囲も同様である。Ｒ１１２は、式（５）におけるＲ１１２と同義であり、好ましい範囲も同様である。 The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (1-A).
Figure JPOXMLDOC01-appb-C000029
 A 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. is there. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.

　ポリイミド前駆体において、式（１）で表される構成単位は１種であってもよいが、２種以上であってもよい。また、式（１）で表される構成単位の構造異性体を含んでいてもよい。また、ポリイミド前駆体は、上記の式（１）の構成単位のほかに、他の種類の構成単位も含んでもよい。 In the polyimide precursor, the structural unit represented by the formula (1) may be one type, but may be two or more types. Moreover, the structural isomer of the structural unit represented by Formula (1) may be included. The polyimide precursor may also contain other types of structural units in addition to the structural unit of the above formula (1).

　本発明におけるポリイミド前駆体の一実施形態として、全構成単位の５０モル％以上、さらには７０モル％以上、特には９０モル％以上が式（１）で表される構成単位であるポリイミド前駆体が例示される。上限としては１００モル％以下が実際的である。 As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all the structural units is the structural unit represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.

　ポリイミド前駆体の重量平均分子量（Ｍｗ）は、好ましくは２０００～５０００００であり、より好ましくは５０００～１０００００であり、さらに好ましくは１００００～５００００である。また、数平均分子量（Ｍｎ）は、好ましくは８００～２５００００であり、より好ましくは、２０００～５００００であり、さらに好ましくは、４０００～２５０００である。
　ポリイミド前駆体の分子量の分散度は、１．５～３．５が好ましく、２～３がより好ましい。 The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The molecular weight dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

　ポリイミド前駆体は、ジカルボン酸またはジカルボン酸誘導体とジアミンを反応させて得られうる。好ましくは、ジカルボン酸またはジカルボン酸誘導体を、ハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られる。
　ポリイミド前駆体の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は１種でもよいし、２種以上でもよい。
　有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル（ジグリム）、Ｎ－メチルピロリドンおよびＮ－エチルピロリドンが例示される。 The polyimide precursor can be obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used for the reaction. One or more organic solvents may be used.
The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.

　ポリイミド前駆体の製造に際し、固体を析出する工程を含んでいることが好ましい。具体的には、反応液中のポリイミド前駆体を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体が可溶な溶剤に溶解させることによって、固体析出することができる。 In producing the polyimide precursor, it is preferable to include a step of depositing a solid. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble.

＜＜ポリベンゾオキサゾール前駆体＞＞
　ポリベンゾオキサゾール前駆体は、下記式（２）で表される構成単位を含むことが好ましい。

Figure JPOXMLDOC01-appb-C000030
　Ｒ１２１は、２価の有機基を表し、Ｒ１２２は、４価の有機基を表し、Ｒ１２３およびＲ１２４は、それぞれ独立に、水素原子または１価の有機基を表す。 << Polybenzoxazole precursor >>
The polybenzoxazole precursor preferably includes a structural unit represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000030
 R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group.

　Ｒ１２１は、２価の有機基を表す。２価の有機基としては、脂肪族基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）および芳香族基（炭素数６～２２が好ましく、６～１４がより好ましく、６～１２が特に好ましい）の少なくとも一方を含む基が好ましい。Ｒ１２１を構成する芳香族基としては、上記式（１）のＲ１１１の例が挙げられる。上記脂肪族基としては、直鎖の脂肪族基が好ましい。Ｒ１２１は、４，４’－オキシジベンゾイルクロリドに由来することが好ましい。
　式（２）において、Ｒ１２２は、４価の有機基を表す。４価の有機基としては、上記式（１）におけるＲ１１５と同義であり、好ましい範囲も同様である。Ｒ１２２は、２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンに由来することが好ましい。
　Ｒ１２３およびＲ１２４は、それぞれ独立に、水素原子または１価の有機基を表し、上記式（１）におけるＲ１１３およびＲ１１４と同義であり、好ましい範囲も同様である。 R 121 represents a divalent organic group. Examples of the divalent organic group include aliphatic groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and aromatic groups (preferably having 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable. Examples of the aromatic group constituting R 121 include R 111 in the above formula (1). As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably derived from 4,4′-oxydibenzoyl chloride.
In the formula (2), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the formula (1), and preferred ranges are also the same. R 122 is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferred range is also the same.

　ポリベンゾオキサゾール前駆体は上記の式（２）の構成単位のほかに、他の種類の構成単位も含んでよい。
　閉環に伴う硬化膜の反りの発生を抑制できる点で、前駆体は、下記式（ＳＬ）で表されるジアミン残基を他の種類の構成単位として含むことが好ましい。 The polybenzoxazole precursor may contain other types of structural units in addition to the structural unit of the above formula (2).
It is preferable that a precursor contains the diamine residue represented by a following formula (SL) as another kind of structural unit at the point which can suppress generation | occurrence | production of the curvature of the cured film accompanying ring closure.

Figure JPOXMLDOC01-appb-C000031
　Ｚは、ａ構造とｂ構造を有し、Ｒ１ｓは水素原子または炭素数１～１０の炭化水素基（好ましくは炭素数１～６、より好ましくは炭素数１～３）であり、Ｒ２ｓは炭素数１～１０の炭化水素基（好ましくは炭素数１～６、より好ましくは炭素数１～３）であり、Ｒ３ｓ、Ｒ４ｓ、Ｒ５ｓ、Ｒ６ｓのうち少なくとも１つは芳香族基（好ましくは炭素数６～２２、より好ましくは炭素数６～１８、特に好ましくは炭素数６～１０）で、残りは水素原子または炭素数１～３０（好ましくは炭素数１～１８、より好ましくは炭素数１～１２、特に好ましくは炭素数１～６）の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分において、好ましくは、ａ構造は５～９５モル％、ｂ構造は９５～５モル％であり、ａ＋ｂは１００モル％である。
Figure JPOXMLDOC01-appb-C000031
 Z has an a structure and a b structure, R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R 2s Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R 3s , R 4s , R 5s and R 6s is aromatic. A group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), the rest being a hydrogen atom or 1 to 30 carbon atoms (preferably having 1 to 18 carbon atoms, more Preferably, it is an organic group having 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

　式（ＳＬ）において、好ましいＺとしては、ｂ構造中のＲ５ｓおよびＲ６ｓがフェニル基であるものが挙げられる。また、式（ＳＬ）で示される構造の分子量は、４００～４，０００であることが好ましく、５００～３，０００がより好ましい。分子量は、一般的に用いられるゲル浸透クロマトグラフィによって求めることができる。上記分子量を上記範囲とすることで、ポリベンゾオキサゾール前駆体の脱水閉環後の弾性率を下げ、反りを抑制できる効果と溶解性を向上させる効果を両立することができる。 In the formula (SL), preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. The molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight within the above range, it is possible to reduce both the elastic modulus after dehydration and ring closure of the polybenzoxazole precursor and to suppress the warp and to improve the solubility.

　前駆体が、他の種類の構成単位として式（ＳＬ）で表されるジアミン残基を含む場合、アルカリ可溶性を向上させる点で、さらに、テトラカルボン酸二無水物から酸二無水物基の除去後に残存するテトラカルボン酸残基を構成単位として含むことが好ましい。このようなテトラカルボン酸残基の例としては、式（１）中のＲ１１５の例が挙げられる。 When the precursor includes a diamine residue represented by the formula (SL) as another type of structural unit, the acid dianhydride group is further removed from the tetracarboxylic dianhydride in terms of improving alkali solubility. It is preferable that a tetracarboxylic acid residue remaining later is included as a structural unit. Examples of such tetracarboxylic acid residue, and examples of R 115 in formula (1).

　ポリベンゾオキサゾール前駆体の重量平均分子量（Ｍｗ）は、好ましくは２０００～５０００００であり、より好ましくは５０００～１０００００であり、さらに好ましくは１００００～５００００である。また、数平均分子量（Ｍｎ）は、好ましくは８００～２５００００であり、より好ましくは、２０００～５００００であり、さらに好ましくは、４０００～２５０００である。
　ポリベンゾオキサゾール前駆体の分子量の分散度（数平均分子量／重量平均分子量）は、１．５～３．５が好ましく、２～３がより好ましい。 The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and still more preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The molecular weight dispersity (number average molecular weight / weight average molecular weight) of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.

　本発明の感光性樹脂組成物における、ポリマー前駆体の含有量は、組成物の全固形分に対し２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることがさらに好ましく、５０質量％以上であることが一層好ましく、６０質量％以上であることがより一層好ましく、７０質量％以上であることがさらに一層好ましい。また、本発明の感光性樹脂組成物における、ポリマー前駆体の含有量は、組成物の全固形分に対し、９９．５質量％以下であることが好ましく、９９質量％以下であることがより好ましく、９８質量％以下であることがさらに好ましく、９５質量％以下であることが一層好ましく、９５質量％以下であることがより一層好ましい。
　本発明の感光性樹脂組成物は、ポリマー前駆体を１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 In the photosensitive resin composition of the present invention, the content of the polymer precursor is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass with respect to the total solid content of the composition. More preferably, it is more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably 70% by mass or more. The content of the polymer precursor in the photosensitive resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, based on the total solid content of the composition. Preferably, it is 98 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 95 mass% or less.
The photosensitive resin composition of this invention may contain only 1 type of polymer precursors, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.

＜溶剤＞
　本発明の感光性樹脂組成物は、溶剤を含有することが好ましい。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類、アミド類などの化合物が挙げられる。
　エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例えば、３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例えば、２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチルおよび２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等が好適なものとして挙げられる。
　エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が好適なものとして挙げられる。
　ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン等が好適なものとして挙げられる。
　芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が好適なものとして挙げられる。
　スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。
　アミド類として、Ｎ－メチル－２－ピロリドン、Ｎ －エチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド等が好適なものとして挙げられる。 <Solvent>
The photosensitive resin composition of the present invention preferably contains a solvent. A known solvent can be arbitrarily used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, and ε-caprolactone , Δ-valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Chill, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like as preferred.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
Preferred examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.

　溶剤は、塗布面性状の改良などの観点から、２種以上を混合する形態も好ましい。
　本発明では、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、Ｎ－メチル－２－ピロリドン、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートから選択される１種の溶剤、または、２種以上で構成される混合溶剤が好ましい。ジメチルスルホキシドとγ－ブチロラクトンとの併用が特に好ましい。 A form in which two or more kinds of solvents are mixed is also preferable from the viewpoint of improving the coated surface properties.
In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- One solvent selected from butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or composed of two or more The mixed solvent is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.

　溶剤の含有量は、塗布性の観点から、本発明の感光性樹脂組成物の全固形分濃度が５～８０質量％になる量とすることが好ましく、５～７５質量％となる量にすることがより好ましく、１０～７０質量％となる量にすることがさらに好ましく、４０～７０質量％となるようにすることが一層好ましい。溶剤含有量は、所望の厚さと塗布方法に応じて調節すればよい。
　溶剤は１種のみ含有していてもよいし、２種以上含有していてもよい。溶剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the solvent is preferably an amount such that the total solid content concentration of the photosensitive resin composition of the present invention is 5 to 80% by mass from the viewpoint of applicability, and is an amount such that 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, still more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.
The solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.

＜光重合開始剤＞
　光重合開始剤は、光ラジカル重合開始剤であることが好ましい。
　本発明で用いることができる光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
　光ラジカル重合開始剤は、約３００～８００ｎｍ（好ましくは３３０～５００ｎｍ）の範囲内で少なくとも約５０のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶剤を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 <Photopolymerization initiator>
The photopolymerization initiator is preferably a radical photopolymerization initiator.
There is no restriction | limiting in particular as radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators. For example, a radical photopolymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

　感光性樹脂組成物が光ラジカル重合開始剤を含むことにより、本発明の感光性樹脂組成物を半導体ウェハなどの基板に適用して感光性樹脂組成物層を形成した後、光を照射することで、発生するラジカルに起因する硬化が起こり、光照射部における溶解性を低下させることができる。このため、例えば、電極部のみをマスクするパターンを持つフォトマスクを介して感光性樹脂組成物層を露光することで、電極のパターンにしたがって、溶解性の異なる領域を簡便に作製できるという利点がある。 When the photosensitive resin composition contains a photo radical polymerization initiator, the photosensitive resin composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light. Thus, curing due to the generated radicals occurs, and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the electrode pattern. is there.

　光ラジカル重合開始剤としては、公知の化合物を任意に使用できる。例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物、トリハロメチル基を有する化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノン、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。これらの詳細については、特開２０１６－０２７３５７号公報の段落０１６５～０１８２の記載を参酌でき、この内容は本明細書に組み込まれる。 As the photo radical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Can be mentioned. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, the contents of which are incorporated herein.

　ケトン化合物としては、例えば、特開２０１５－０８７６１１号公報の段落００８７に記載の化合物が例示され、この内容は本明細書に組み込まれる。市販品では、カヤキュアーＤＥＴＸ（日本化薬（株）製）も好適に用いられる。 Examples of ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

　光ラジカル重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、および、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ　１８４（ＩＲＧＡＣＵＲＥは登録商標）、ＤＡＲＯＣＵＲ　１１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ　１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ９０７、ＩＲＧＡＣＵＲＥ　３６９、および、ＩＲＧＡＣＵＲＥ　３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の波長光源に吸収極大波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができる。
　アシルホスフィン系開始剤としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドなどが挙げられる。また、市販品であるＩＲＧＡＣＵＲＥ－８１９やＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　メタロセン化合物としては、ＩＲＧＡＣＵＲＥ－７８４（ＢＡＳＦ社製）などが例示される。 As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

　光ラジカル重合開始剤として、より好ましくはオキシム化合物が挙げられる。オキシム化合物を用いることにより、露光ラチチュードをより効果的に向上させることが可能になる。オキシム化合物は、露光ラチチュード（露光マージン）が広く、かつ、光塩基発生剤としても働くため、特に好ましい。
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－０８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物を用いることができる。
　好ましいオキシム化合物としては、例えば、下記の構造の化合物や、３－ベンゾオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。本発明の感光性樹脂組成物においては、特に光ラジカル重合開始剤としてオキシム化合物（オキシム系の光重合開始剤）を用いることが好ましい。オキシム系の光重合開始剤は、分子内に　＞Ｃ＝Ｎ－Ｏ－Ｃ（＝Ｏ）－　の連結基を有する。

Figure JPOXMLDOC01-appb-C000032
　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０３、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－０１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１およびアデカアークルズＮＣＩ－９３０（（株）ＡＤＥＫＡ製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス株式会社製）を用いることができる。
　さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の段落０３４５に記載されている化合物２４、３６～４０、特開２０１３－１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ－３）などが挙げられる。
　最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。 As the photo radical polymerization initiator, an oxime compound is more preferable. By using the oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photobase generator.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, and compounds described in JP-A No. 2006-342166.
Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. In the photosensitive resin composition of the present invention, it is particularly preferable to use an oxime compound (an oxime photopolymerization initiator) as a radical photopolymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C═N—O—C (═O) — in the molecule.
Figure JPOXMLDOC01-appb-C000032
 Commercially available products include IRGACURE OXE 01, IRGACURE OXE02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF Corp.), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, JP 2012-014052) A polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daitokemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in paragraph 0345 of JP 2014-500852 A, and JP 2013. And the compound (C-3) described in paragraph 0101 of JP-A No. 164471.
As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.

　光ラジカル重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物およびその誘導体、シクロペンタジエン－ベンゼン－鉄錯体およびその塩、ハロメチルオキサジアゾール化合物、３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。
　さらに好ましい光ラジカル重合開始剤は、トリハロメチルトリアジン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α－アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物からなる群より選ばれる少なくとも１種の化合物が一層好ましく、メタロセン化合物またはオキシム化合物を用いるのがより一層好ましく、オキシム化合物がさらに一層好ましい。
　また、光ラジカル重合開始剤は、ベンゾフェノン、Ｎ，Ｎ’－テトラメチル－４，４’－ジアミノベンゾフェノン（ミヒラーケトン）等のＮ，Ｎ’－テトラアルキル－４，４’－ジアミノベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１，２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパノン－１等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。また、下記式（Ｉ）で表される化合物を用いることもできる。

Figure JPOXMLDOC01-appb-C000033
　式（Ｉ）中、ＲＩ００は、炭素数１～２０のアルキル基、１個以上の酸素原子によって中断された炭素数２～２０のアルキル基、炭素数１～１２のアルコキシル基、フェニル基、炭素数１～２０のアルキル基、炭素数１～１２のアルコキシル基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基および炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基、またはビフェニルであり、ＲＩ０１は、式（ＩＩ）で表される基であるか、ＲＩ００と同じ基であり、ＲＩ０２～ＲＩ０４は各々独立に炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基またはハロゲン原子である。
Figure JPOXMLDOC01-appb-C000034
 式中、ＲＩ０５～ＲＩ０７は、上記式（Ｉ）のＲＩ０２～ＲＩ０４と同じである。 Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.
More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is even more preferable.
In addition, photo radical polymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc. It is also possible to use quinones fused with the aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal. A compound represented by the following formula (I) can also be used.
Figure JPOXMLDOC01-appb-C000033
 In formula (I), R I00 represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, An alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms or a biphenyl,, R I01 is a group represented by formula (II), the same as R I00 R I02 to R I04 each independently represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.
Figure JPOXMLDOC01-appb-C000034
 In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).

　また、光ラジカル重合開始剤は、国際公開第２０１５／１２５４６９号の段落００４８～００５５に記載の化合物を用いることもできる。 Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469 can be used.

　光重合開始剤を含む場合、その含有量は、本発明の感光性樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは０．５～１５質量％であり、一層好ましくは１．０～１０質量％である。光重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。光重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the photopolymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the photosensitive resin composition of the present invention. More preferably, it is 0.5 to 15% by mass, and more preferably 1.0 to 10% by mass. The photoinitiator may contain only 1 type and may contain 2 or more types. When two or more photopolymerization initiators are contained, the total is preferably in the above range.

＜重合性化合物＞
＜＜ラジカル重合性化合物＞＞
　本発明の感光性樹脂組成物はラジカル重合性化合物を含むことが好ましい。
　ラジカル重合性化合物は、ラジカル重合性基を有する化合物を用いることができる。ラジカル重合性基としては、ビニルフェニル基、ビニル基、（メタ）アクリロイル基およびアリル基などのエチレン性不飽和結合を有する基が挙げられる。ラジカル重合性基は、（メタ）アクリロイル基が好ましい。 <Polymerizable compound>
<< Radically polymerizable compound >>
The photosensitive resin composition of the present invention preferably contains a radical polymerizable compound.
As the radical polymerizable compound, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as vinylphenyl group, vinyl group, (meth) acryloyl group, and allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.

　ラジカル重合性化合物が有するラジカル重合性基の数は、１個でもよく、２個以上でもよいが、ラジカル重合性化合物はラジカル重合性基を２個以上有することが好ましく、３個以上有することがより好ましい。上限は、１５個以下が好ましく、１０個以下がより好ましく、８個以下がさらに好ましい。 The number of radical polymerizable groups contained in the radical polymerizable compound may be one or two or more. However, the radical polymerizable compound preferably has two or more radical polymerizable groups, and preferably has three or more radical polymerizable groups. More preferred. The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.

　ラジカル重合性化合物の分子量は、２０００以下が好ましく、１５００以下がより好ましく、９００以下がさらに好ましい。ラジカル重合性化合物の分子量の下限は、１００以上が好ましい。 The molecular weight of the radical polymerizable compound is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical polymerizable compound is preferably 100 or more.

　本発明の感光性樹脂組成物は、現像性の観点から、重合性基を２個以上含む２官能以上のラジカル重合性化合物を少なくとも１種含むことが好ましく、３官能以上のラジカル重合性化合物を少なくとも１種含むことがより好ましい。また、２官能のラジカル重合性化合物と３官能以上のラジカル重合性化合物との混合物であってもよい。なお、ラジカル重合性化合物の官能基数は、１分子中におけるラジカル重合性基の数を意味する。 From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one bifunctional or higher radical polymerizable compound containing two or more polymerizable groups, and preferably contains a trifunctional or higher functional radical polymerizable compound. More preferably, at least one kind is included. Further, it may be a mixture of a bifunctional radically polymerizable compound and a trifunctional or higher functional radically polymerizable compound. In addition, the number of functional groups of the radical polymerizable compound means the number of radical polymerizable groups in one molecule.

　ラジカル重合性化合物の具体例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、および不飽和カルボン酸と多価アミン化合物とのアミド類である。また、ヒドロキシル基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステルあるいはアミド類と、単官能若しくは多官能イソシアネート類あるいはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステルあるいはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、さらに、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステルあるいはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。具体例としては、特開２０１６－０２７３５７号公報の段落０１１３～０１２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the radical polymerizable compound include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substituted reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as thiol or tosyloxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid. As specific examples, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.

　また、ラジカル重合性化合物は、常圧下で１００℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後、（メタ）アクリレート化した化合物、特公昭４８－０４１７０８号公報、特公昭５０－００６０３４号公報、特開昭５１－０３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－０６４１８３号、特公昭４９－０４３１９１号、特公昭５２－０３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレートおよびこれらの混合物を挙げることができる。また、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物も好適である。また、多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和結合を有する化合物を反応させて得られる多官能（メタ）アクリレートなども挙げることができる。
　また、上述以外の好ましいラジカル重合性化合物として、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号公報等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を２個以上有する化合物や、カルド樹脂も使用することが可能である。
　さらに、その他の例としては、特公昭４６－０４３９４６号公報、特公平１－０４０３３７号公報、特公平１－０４０３３６号公報に記載の特定の不飽和化合物や、特開平０２－０２５４９３号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭６１－０２２０４８号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。さらに日本接着協会誌　ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光重合性モノマーおよびオリゴマーとして紹介されているものも使用することができる。 The radical polymerizable compound is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Many such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, JP-B-48-0417 No. 8, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, urethane (meth) acrylates, Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof described in JP-B-52-030490 Can do. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. In addition, polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be exemplified.
Further, as other preferable radical polymerizable compounds other than those described above, there are fluorene rings described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having a carbonic acid or a cardo resin.
Other examples include specific unsaturated compounds described in JP-B-46-043946, JP-B-1-040337, JP-B-1-040336, and JP-A-02-025493. And vinyl phosphonic acid compounds. Further, compounds containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.

　上記のほか、特開２０１５－０３４９６４号公報の段落００４８～００５１に記載の化合物も好ましく用いることができ、これらの内容は本明細書に組み込まれる。 In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A No. 2015-034964 can also be preferably used, and the contents thereof are incorporated in the present specification.

　また、特開平１０－０６２９８６号公報において式（１）および式（２）としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、ラジカル重合性化合物として用いることができる。 Further, compounds described in JP-A-10-062986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a radically polymerizable compound.

　さらに、特開２０１５－１８７２１１号公報の段落０１０４～０１３１に記載の化合物も他のラジカル重合性化合物として用いることができ、これらの内容は本明細書に組み込まれる。 Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as other radical polymerizable compounds, the contents of which are incorporated herein.

　ラジカル重合性化合物としては、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製、Ａ－ＴＭＭＴ：新中村化学工業社製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、Ａ－ＤＰＨ；新中村化学工業社製）、およびこれらの（メタ）アクリロイル基がエチレングリコール残基またはプロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。 Examples of the radical polymerizable compound include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, as KAYARAD D-320; Nippon Kayaku ( A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl group via an ethylene glycol residue or a propylene glycol residue A bonded structure is preferred. These oligomer types can also be used.

　ラジカル重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、エチレンオキシ鎖を４個有する２官能メタクリレートであるサートマー社製のＳＲ－２０９、２３１、２３９、日本化薬（株）製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（日本製紙社製）、ＮＫエステルＭ－４０Ｇ、ＮＫエステル４Ｇ、ＮＫエステルＭ－９３００、ＮＫエステルＡ－９３００、ＵＡ－７２００（新中村化学工業社製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学社製）、ブレンマーＰＭＥ４００（日油（株）製）などが挙げられる。 Examples of commercially available radical polymerizable compounds include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60 which is a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- manufactured by Nippon Kayaku Co., Ltd. 10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306 , AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF Corporation) and the like.

　ラジカル重合性化合物としては、特公昭４８－０４１７０８号公報、特開昭５１－０３７１９３号公報、特公平０２－０３２２９３号公報、特公平０２－０１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－０４９８６０号公報、特公昭５６－０１７６５４号公報、特公昭６２－０３９４１７号公報、特公昭６２－０３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。さらに、ラジカル重合性化合物として、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する化合物を用いることもできる。 Examples of the radical polymerizable compound include urethane acrylates described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, and the like. Also suitable are urethane compounds having an ethylene oxide skeleton as described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418. Further, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as radically polymerizable compounds. It can also be used.

　ラジカル重合性化合物は、カルボキシル基、リン酸基等の酸基を有するラジカル重合性化合物であってもよい。酸基を有するラジカル重合性化合物は、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル重合性化合物がより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を持たせたラジカル重合性化合物において、脂肪族ポリヒドロキシ化合物がペンタエリスリトールまたはジペンタエリスリトールである化合物である。市販品としては、例えば、東亞合成株式会社製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。
　酸基を有するラジカル重合性化合物の好ましい酸価は、０．１～４０ｍｇＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇＫＯＨ／ｇである。ラジカル重合性化合物の酸価が上記範囲であれば、製造や取扱性に優れ、さらには、現像性に優れる。また、重合性が良好である。 The radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxyl group or a phosphate group. The radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A radically polymerizable compound having a group is more preferable. Particularly preferably, in the radical polymerizable compound in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentayl. A compound that is erythritol. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
A preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radically polymerizable compound is in the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.

　本発明の感光性樹脂組成物は、硬化膜の弾性率制御に伴う反り抑制の観点から、ラジカル重合性化合物として、単官能ラジカル重合性化合物を好ましく用いることができる。単官能ラジカル重合性化合物としては、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸誘導体、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等のＮ－ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能ラジカル重合性化合物としては、露光前の揮発を抑制するため、常圧下で１００℃以上の沸点を持つ化合物も好ましい。 In the photosensitive resin composition of the present invention, a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film. Monofunctional radically polymerizable compounds include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. ) Acrylic acid derivatives, N-vinyl pyrrolidone, N-vinyl compounds such as N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Le compounds are preferably used. As the monofunctional radically polymerizable compound, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

＜＜上述したラジカル重合性化合物以外の重合性化合物＞＞
　本発明の感光性樹脂組成物は、上述したラジカル重合性化合物以外の重合性化合物をさらに含むことができる。上述したラジカル重合性化合物以外の重合性化合物としては、ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物；エポキシ化合物；オキセタン化合物；ベンゾオキサジン化合物が挙げられる。 << Polymerizable compound other than the above-mentioned radical polymerizable compound >>
The photosensitive resin composition of this invention can further contain polymeric compounds other than the radically polymerizable compound mentioned above. Examples of polymerizable compounds other than the above-mentioned radical polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.

（ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物）
　ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物としては、下記式（ＡＭ１）、（ＡＭ４）または（ＡＭ５）で示される化合物が好ましい。 (Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1), (AM4) or (AM5) is preferable.

Figure JPOXMLDOC01-appb-C000035
（式中、ｔは、１～２０の整数を示し、Ｒ１０４は炭素数１～２００のｔ価の有機基を示し、Ｒ１０５は、－ＯＲ１０６または、－ＯＣＯ－Ｒ１０７で示される基を示し、Ｒ１０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ１０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000035
 (Wherein t represents an integer of 1 to 20, R 104 represents a t-valent organic group having 1 to 200 carbon atoms, and R 105 represents a group represented by —OR 106 or —OCO—R 107. R 106 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 107 represents an organic group having 1 to 10 carbon atoms.)

Figure JPOXMLDOC01-appb-C000036
（式中、Ｒ４０４は炭素数１～２００の２価の有機基を示し、Ｒ４０５は、－ＯＲ４０６または、－ＯＣＯ－Ｒ４０７で示される基を示し、Ｒ４０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ４０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000036
 (Wherein R 404 represents a divalent organic group having 1 to 200 carbon atoms, R 405 represents a group represented by —OR 406 or —OCO—R 407 , and R 406 represents a hydrogen atom or a carbon atom. An organic group having 1 to 10 carbon atoms, and R 407 represents an organic group having 1 to 10 carbon atoms.)

Figure JPOXMLDOC01-appb-C000037
（式中ｕは３～８の整数を示し、Ｒ５０４は炭素数１～２００のｕ価の有機基を示し、Ｒ５０５は、－ＯＲ５０６または、－ＯＣＯ－Ｒ５０７で示される基を示し、Ｒ５０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ５０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000037
 (Wherein u represents an integer of 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, and R 505 represents a group represented by —OR 506 or —OCO—R 507. R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 507 represents an organic group having 1 to 10 carbon atoms.)

　式（ＡＭ４）で示される化合物の具体例としては、４６ＤＭＯＣ、４６ＤＭＯＥＰ（以上、商品名、旭有機材工業（株）製）、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＥＰ、ＤＭＬ－ＰＯＰ、ｄｉｍｅｔｈｙｌｏｌＢｉｓＯＣ－Ｐ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＭＴｒｉｓＰＣ（以上、商品名、本州化学工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２９０（商品名、（株）三和ケミカル製）、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－４－ｔ－ｂｕｔｙｌｐｈｅｎｏｌ、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌ、２，６－ｄｉａｃｅｔｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌなどが挙げられる。 Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC Examples include MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diacetylmethyl-p-cresol, and the like. It is done.

　また、式（ＡＭ５）で示される化合物の具体例としては、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＨＱ、ＴＭＬ－ＢＰ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＡ、ＴＭＯＭ－ＢＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ、ＨＭＯＭ－ＴＰＰＨＢＡ、ＨＭＯＭ－ＴＰＨＡＰ（以上、商品名、本州化学工業（株）製）、ＴＭ－ＢＩＰ－Ａ（商品名、旭有機材工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２８０、ＮＩＫＡＬＡＣ　ＭＸ－２７０、ＮＩＫＡＬＡＣ　ＭＷ－１００ＬＭ（以上、商品名、（株）三和ケミカル製）が挙げられる。 Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).

（エポキシ化合物（エポキシ基を有する化合物））
　エポキシ化合物としては、一分子中にエポキシ基を２以上有する化合物であることが好ましい。エポキシ基は、２００℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、組成物の低温硬化および反りの抑制に効果的である。 (Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.

　エポキシ化合物は、ポリエチレンオキサイド基を含有することが好ましい。これにより、より弾性率が低下し、また反りを抑制することができる。ポリエチレンオキサイド基は、エチレンオキサイドの構成単位数が２以上のものを意味し、構成単位数が２～１５であることが好ましい。 The epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed. The polyethylene oxide group means that the number of structural units of ethylene oxide is 2 or more, and the number of structural units is preferably 2 to 15.

　エポキシ化合物の例としては、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；プロピレングリコールジグリシジルエーテル等のアルキレングリコール型エポキシ樹脂；ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコール型エポキシ樹脂；ポリメチル（グリシジロキシプロピル）シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン（登録商標）８５０－Ｓ、エピクロン（登録商標）ＨＰ－４０３２、エピクロン（登録商標）ＨＰ－７２００、エピクロン（登録商標）ＨＰ－８２０、エピクロン（登録商標）ＨＰ－４７００、エピクロン（登録商標）ＥＸＡ－４７１０、エピクロン（登録商標）ＨＰ－４７７０、エピクロン（登録商標）ＥＸＡ－８５９ＣＲＰ、エピクロン（登録商標）ＥＸＡ－１５１４、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８５０－１５０、エピクロンＥＸＡ－４８５０－１０００、エピクロン（登録商標）ＥＸＡ－４８１６、エピクロン（登録商標）ＥＸＡ－４８２２（以上商品名、大日本インキ化学工業（株）製）、リカレジン（登録商標）ＢＥＯ－６０Ｅ（商品名、新日本理化（株））、ＥＰ－４００３Ｓ、ＥＰ－４０００Ｓ（以上商品名、（株）ＡＤＥＫＡ製）などが挙げられる。この中でも、ポリエチレンオキサイド基を含有するエポキシ樹脂が、反りの抑制および耐熱性に優れる点で好ましい。例えば、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８２２、リカレジン（登録商標）ＢＥＯ－６０Ｅは、ポリエチレンオキサイド基を含有するので好ましい。 Examples of the epoxy compound include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( )), EP-4003S, EP-4000S (trade names, and the like (Ltd.) ADEKA). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

（オキセタン化合物（オキセタニル基を有する化合物））
　オキセタン化合物としては、一分子中にオキセタン環を２つ以上有する化合物、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、３－エチル－３－（２－エチルヘキシルメチル）オキセタン、１，４－ベンゼンジカルボン酸－ビス［（３－エチル－３－オキセタニル）メチル］エステル等を挙げることができる。具体的な例としては、東亞合成株式会社製のアロンオキセタンシリーズ（例えば、ＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸＴ－１９１、ＯＸＴ－２２３）が好適に使用することができ、これらは単独で、あるいは２種以上混合してもよい。 (Oxetane compound (compound having oxetanyl group))
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester. As specific examples, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be preferably used. Two or more kinds may be mixed.

（ベンゾオキサジン化合物（ベンゾオキサゾリル基を有する化合物））
　ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、さらに熱収縮を小さくして反りの発生が抑えられることから好ましい。 (Benzoxazine compound (compound having benzoxazolyl group))
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.

　ベンゾオキサジン化合物の好ましい例としては、Ｂ－ａ型ベンゾオキサジン、Ｂ－ｍ型ベンゾオキサジン（以上、商品名、四国化成工業社製）、ポリヒドロキシスチレン樹脂のベンゾオキサジン付加物、フェノールノボラック型ジヒドロベンゾオキサジン化合物が挙げられる。これらは単独で用いるか、あるいは２種以上混合してもよい。 Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo An oxazine compound is mentioned. These may be used alone or in combination of two or more.

　重合性化合物を含有する場合、その含有量は、本発明の感光性樹脂組成物の全固形分に対して、０質量％超６０質量％以下であることが好ましい。下限は５質量％以上がより好ましい。上限は、５０質量％以下であることがより好ましく、３０質量％以下であることがさらに好ましい。
　重合性化合物は１種を単独で用いてもよいが、２種以上を混合して用いてもよい。２種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 When the polymerizable compound is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the photosensitive resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
As the polymerizable compound, one kind may be used alone, or two or more kinds may be mixed and used. When using 2 or more types together, it is preferable that the total amount becomes said range.

＜マイグレーション抑制剤＞
　本発明の感光性樹脂組成物は、さらにマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層（金属配線）由来の金属イオンが感光性樹脂組成物層内へ移動することを効果的に抑制可能となる。
　マイグレーション抑制剤としては、特に制限はないが、複素環（ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、２Ｈ－ピラン環および６Ｈ－ピラン環、トリアジン環）を有する化合物、チオ尿素類およびメルカプト基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、１，２，４－トリアゾール、ベンゾトリアゾール等のトリアゾール系化合物、１Ｈ－テトラゾール、５－フェニルテトラゾール等のテトラゾール系化合物が好ましく使用できる。 <Migration inhibitor>
The photosensitive resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Salicylic acid derivative compounds and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

　また、ハロゲンイオンなどの陰イオンを捕捉するイオントラップ剤を使用することもできる。 Also, an ion trapping agent that traps anions such as halogen ions can be used.

　その他のマイグレーション抑制剤としては、特開２０１３－０１５７０１号公報の段落００９４に記載の防錆剤、特開２００９－２８３７１１号公報の段落００７３～００７６に記載の化合物、特開２０１１－０５９６５６号公報の段落００５２に記載の化合物、特開２０１２－１９４５２０号公報の段落０１１４、０１１６および０１１８に記載の化合物などを使用することができる。 Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-015701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656A. The compounds described in paragraph 0052 and the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.

　マイグレーション抑制剤の具体例としては、下記化合物を挙げることができる。

Figure JPOXMLDOC01-appb-C000038
Specific examples of the migration inhibitor include the following compounds.
Figure JPOXMLDOC01-appb-C000038

　感光性樹脂組成物がマイグレーション抑制剤を有する場合、マイグレーション抑制剤の含有量は、感光性樹脂組成物の全固形分に対して、０．０１～５．０質量％であることが好ましく、０．０５～２．０質量％であることがより好ましく、０．１～１．０質量％であることがさらに好ましい。
　マイグレーション抑制剤は１種のみでもよいし、２種以上であってもよい。マイグレーション抑制剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition. More preferably, the content is 0.05 to 2.0% by mass, and still more preferably 0.1 to 1.0% by mass.
Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.

＜重合禁止剤＞
　本発明の感光性樹脂組成物は、重合禁止剤を含むことが好ましい。
　重合禁止剤としては、例えば、ヒドロキノン、４－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｐ－ｔｅｒｔ－ブチルカテコール、１，４－ベンゾキノン、ジフェニル－ｐ－ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、Ｎ－ニトロソジフェニルアミン、Ｎ－フェニルナフチルアミン、エチレンジアミン四酢酸、１，２－シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、５－ニトロソ－８－ヒドロキシキノリン、１－ニトロソ－２－ナフトール、２－ニトロソ－１－ナフトール、２－ニトロソ－５－（Ｎ－エチル－Ｎ－スルホプロピルアミノ）フェノール、Ｎ－ニトロソ－Ｎ－（１－ナフチル）ヒドロキシアミンアンモニウム塩、ビス（４－ヒドロキシ－３，５－ｔｅｒｔ－ブチル）フェニルメタンなどが好適に用いられる。また、特開２０１５－１２７８１７号公報の段落００６０に記載の重合禁止剤、および、国際公開第２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもできる。
　また、下記化合物を用いることができる（Ｍｅはメチル基である）。

Figure JPOXMLDOC01-appb-C000039
　本発明の感光性樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０．０１～５質量％であることが好ましく、０．０２～３質量％であることがより好ましく、０．０５～２．５質量％であることがさらに好ましい。
　重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 <Polymerization inhibitor>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, 4-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4 ′. -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso 2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4 -Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. In addition, a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of WO2015 / 125469 can also be used.
Moreover, the following compound can be used (Me is a methyl group).
Figure JPOXMLDOC01-appb-C000039
 When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferably 0.02 to 3% by mass, more preferably 0.05 to 2.5% by mass.
Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.

＜金属接着性改良剤＞
　本発明の感光性樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、シランカップリング剤などが挙げられる。 <Metal adhesion improver>
The photosensitive resin composition of the present invention preferably contains a metal adhesion improver for improving the adhesion with a metal material used for electrodes and wirings. Examples of metal adhesion improvers include silane coupling agents.

　シランカップリング剤の例としては、特開２０１４－１９１００２号公報の段落００６２～００７３に記載の化合物、国際公開第２０１１／０８０９９２号の段落００６３～００７１に記載の化合物、特開２０１４－１９１２５２号公報の段落００６０～００６１に記載の化合物、特開２０１４－０４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開第２０１４／０９７５９４号の段落００５５に記載の化合物が挙げられる。また、特開２０１１－１２８３５８号公報の段落００５０～００５８に記載のように異なる２種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Ｅｔはエチル基を表す。

Figure JPOXMLDOC01-appb-C000040
Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP-A No. 2014-191002, compounds described in paragraphs 0063 to 0071 of WO 2011/080992, and JP-A No. 2014-191252. The compounds described in paragraphs [0060] to [0061], the compounds described in paragraphs [0045] to [0052] of JP-A No. 2014-041264, and the compounds described in paragraph [0055] of WO2014 / 097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000040

　また、金属接着性改良剤は、特開２０１４－１８６１８６号公報の段落００４６～００４９に記載の化合物、特開２０１３－０７２９３５号公報の段落００３２～００４３に記載のスルフィド系化合物を用いることもできる。 As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

　金属接着性改良剤の含有量はポリマー前駆体１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは０．５～１５質量部の範囲であり、さらに好ましくは０．５～５質量部の範囲である。上記下限値以上とすることで硬化工程後の硬化膜と金属層との接着性が良好となり、上記上限値以下とすることで硬化工程後の硬化膜の耐熱性、機械特性が良好となる。金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 0 to 100 parts by mass of the polymer precursor. The range is from 5 to 5 parts by mass. Adhesion between the cured film and the metal layer after the curing step is improved by setting it to the above lower limit or more, and heat resistance and mechanical properties of the cured film after the curing step are improved by setting the upper limit or less. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.

＜熱塩基発生剤＞
　本発明の感光性樹脂組成物は、熱塩基発生剤を含んでいてもよい。熱光塩基発生剤は、熱により塩基を発生するものであることが好ましい。
　熱塩基発生剤は第四級アンモニウムカチオンとカルボン酸アニオンとの塩が好ましい。この第四級アンモニウムカチオンは、下記式（Ｙ１－１）～式（Ｙ１－４）のいずれかで表されることが好ましい。

Figure JPOXMLDOC01-appb-C000041
<Heat base generator>
The photosensitive resin composition of the present invention may contain a thermal base generator. The thermophotobase generator is preferably one that generates a base by heat.
The thermal base generator is preferably a salt of a quaternary ammonium cation and a carboxylic acid anion. The quaternary ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-4).
Figure JPOXMLDOC01-appb-C000041

　ＲＹ１は、ｎＹ価（ｎＹは、１～１２の整数）の有機基を表し、ｎＹ価の炭化水素基であることが好ましい。炭化水素基としては、アルカンを含むｎＹ価の基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケンを含むｎＹ価の基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、芳香族炭化水素を含むｎＹ価の基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、またはそれらの組み合わせが挙げられる。ＲＹ１は中でも芳香族炭化水素基であることが好ましい。ＲＹ１は本発明の効果を損ねない範囲で、前述の置換基Ｔを有していてもよい。
　ＲＹ２～ＲＹ５は、それぞれ独立に、水素原子または炭化水素基（炭素数１～３６が好ましく、１～２４がより好ましく、１～１２がさらに好ましい）を表し、アルキル基（炭素数１～３６が好ましく、１～２４がより好ましく、１～２３がさらに好ましい）、アルケニル基（炭素数２～３６が好ましく、２～２４がより好ましく、２～２３がさらに好ましい）、アルキニル基（炭素数１～３６が好ましく、１～２４がより好ましく、１～２３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）が好ましい。このアルキル基、アルケニル基、アルキニル基は、環状でも鎖状でもよく、鎖状の場合は、直鎖状でも分岐状でもよく、置換基Ｔを有していてもよい。
　ＲＹ６はアルキル基（炭素数１～３６が好ましく、２～２４がより好ましく、４～１８がさらに好ましい）、アルケニル基（炭素数２～３６が好ましく、２～２４がより好ましく、４～１８がさらに好ましい）、アルキニル基（炭素数２～３６が好ましく、２～２４がより好ましく、４～１８がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）である。アルキル基、アルケニル基、アルキニル基は環状でも鎖状でもよく、鎖状の場合は、直鎖状でも分岐状でもよい。アルキル基、アルケニル基、アルキニル基、アリール基には、基の途中に、ヘテロ原子を含む連結基（例えば連結基Ｌのうちヘテロ原子を有するもの）が介在していてもよい。例えば、オリゴアルキレン基（構成単位中の炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい。繰り返し数は２～１００が好ましく、２～６０がより好ましく、２～３０がさらに好ましい）が挙げられる。
　ｎＹは、１～１２の整数を表し、１～６の整数がより好ましく、１～３の整数がさらに好ましい。
　ｎＸは１～１２の整数を表し、１～６の整数が好ましく、１～３の整数がさらに好ましい。
　ＲＹ２～ＲＹ６はそれぞれその２つ以上が互いに結合して環を形成してもよい。 R Y1 is n Y-valent (n Y is an integer of 1 to 12) represents an organic group is preferably a n Y-valent hydrocarbon group. Examples of the hydrocarbon group include an n Y valent group containing an alkane (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3), and an n Y valent group containing an alkene (2 carbon atoms). To 12, preferably 2 to 6, more preferably 2 to 3, and an n Y- valent group containing an aromatic hydrocarbon (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 carbon atoms). Are more preferable), or a combination thereof. R Y1 is preferably an aromatic hydrocarbon group. R Y1 may have the above-described substituent T as long as the effects of the present invention are not impaired.
R Y2 to R Y5 each independently represents a hydrogen atom or a hydrocarbon group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and still more preferably 1 to 12), and an alkyl group (having a carbon number of 1 to 36). 36 is preferred, 1 to 24 is more preferred, 1 to 23 is more preferred, an alkenyl group (preferably having 2 to 36 carbon atoms, more preferred is 2 to 24, still more preferred being 2 to 23), and an alkynyl group (having carbon numbers). 1 to 36 are preferred, 1 to 24 are more preferred, 1 to 23 are more preferred, and an aryl group (preferably having 6 to 22 carbon atoms, more preferred is 6 to 18 and even more preferred is 6 to 10). The alkyl group, alkenyl group and alkynyl group may be cyclic or chain-like, and in the case of a chain, may be linear or branched and may have a substituent T.
R Y6 represents an alkyl group (preferably having a carbon number of 1 to 36, preferably 2 to 24, more preferably 4 to 18), or an alkenyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, and 4 to 18). Is more preferable), an alkynyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24, more preferably 4 to 18), and an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms). To 10 is more preferable). The alkyl group, alkenyl group and alkynyl group may be cyclic or chain-like, and in the case of a chain, it may be linear or branched. In the alkyl group, alkenyl group, alkynyl group, and aryl group, a linking group containing a hetero atom (for example, one having a hetero atom in the linking group L) may be interposed in the middle of the group. For example, an oligoalkylene group (the number of carbon atoms in the structural unit is preferably 1 to 12, more preferably 1 to 6, more preferably 1 to 3, the number of repetitions is preferably 2 to 100, more preferably 2 to 60, and more preferably 2 to 30 is more preferable).
n Y represents an integer of 1 to 12, more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 3.
n X represents an integer of 1 to 12, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
Two or more of R Y2 to R Y6 may be bonded to each other to form a ring.

　ＲＹ７～ＲＹ１６はＲＮと同義である（ＲＮは置換基Ｔを有していてもよい）。ただし、ＲＹ７～ＲＹ９がすべて水素原子であることはない。式（Ｙ１－２）において、ＲＹ７およびＲＹ８はカルボキシアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい；カルボキシル基の数は１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）が好ましい。ＲＹ９は芳香族基が好ましく、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）が好ましい。あるいは、芳香族基が置換したアルコキシカルボニル基が好ましい（アルコキシル基は炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい、芳香族基は炭素数６～２２が好ましく、６～１８がより好ましく、６～１４がさらに好ましい）。式（Ｙ１－３）において、ＲＹ１１およびＲＹ１３は水素原子であることが好ましい。ＲＹ１４およびＲＹ１５は２つが組み合わさって、＝Ｃ（ＮＲＮ ２）２の形の置換基になっていてもよい（　＝　は二重結合で窒素原子に結合することを意味する）。式（Ｙ１－４）において、ＲＹ１３は水素原子であることが好ましく、ＲＹ１０、ＲＹ１１、ＲＹ１２、ＲＹ１６はアルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）であることが好ましい。このとき、ＲＹ１１とＲＹ１６、ＲＹ１０とＲＹ１２が結合して環を形成しビシクロ化合物となっていることが好ましい。具体的には、ジアザビシクロノネン、ジアザビシクロウンデセンが挙げられる。 R Y7 to R Y16 have the same meaning as R N (R N may have a substituent T). However, R Y7 to R Y9 are not all hydrogen atoms. In the formula (Y1-2), R Y7 and R Y8 are carboxyalkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms; preferably 1 to 12 carboxyl groups). 1 to 6 are more preferable, and 1 to 3 are more preferable. R Y9 is preferably an aromatic group, and is preferably an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and even more preferably 6 to 10). Alternatively, an alkoxycarbonyl group substituted with an aromatic group is preferred (the alkoxyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms, and the aromatic group preferably has 6 to 22 carbon atoms). 6 to 18 are more preferable, and 6 to 14 are more preferable. In the formula (Y1-3), R Y11 and R Y13 are preferably hydrogen atoms. R Y14 and R Y15 may be combined together to form a substituent of the form ═C (NR N 2 ) 2 (= means that it is bonded to the nitrogen atom with a double bond). In the formula (Y1-4), R Y13 is preferably a hydrogen atom, and R Y10 , R Y11 , R Y12 and R Y16 are alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms). ~ 3 are more preferred). At this time, R Y11 and R Y16 , R Y10 and R Y12 are preferably bonded to form a ring to form a bicyclo compound. Specific examples include diazabicyclononene and diazabicycloundecene.

　本実施形態において、上記式（Ｙ１－１）、式（Ｙ１－３）および式（Ｙ１－４）の第四級アンモニウムカチオンと対になるカルボン酸アニオンは、下記式（Ｘ１）で表されることが好ましい。

Figure JPOXMLDOC01-appb-C000042
　式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。 In the present embodiment, the carboxylate anion paired with the quaternary ammonium cation of the above formula (Y1-1), formula (Y1-3) and formula (Y1-4) is represented by the following formula (X1). It is preferable.
Figure JPOXMLDOC01-appb-C000042
 In the formula (X1), EWG represents an electron withdrawing group.

　本実施形態において電子求引性基とは、ハメットの置換基定数σｍが正の値を示すものを意味する。ここでσｍは、都野雄甫総説、有機合成化学協会誌第２３巻第８号（１９６５）ｐ．６３１－６４２に詳しく説明されている。なお、本実施形態における電子求引性基は、上記文献に記載された置換基に限定されるものではない。
　σｍが正の値を示す置換基の例としては、ＣＦ３基（σｍ＝０．４３）、ＣＦ３ＣＯ基（σｍ＝０．６３）、ＨＣ≡Ｃ基（σｍ＝０．２１）、ＣＨ２＝ＣＨ基（σｍ＝０．０６）、Ａｃ基（σｍ＝０．３８）、ＭｅＯＣＯ基（σｍ＝０．３７）、ＭｅＣＯＣＨ＝ＣＨ基（σｍ＝０．２１）、ＰｈＣＯ基（σｍ＝０．３４）、Ｈ２ＮＣＯＣＨ２基（σｍ＝０．０６）などが挙げられる。なお、Ｍｅはメチル基を表し、Ａｃはアセチル基を表し、Ｐｈはフェニル基を表す（以下、同じ）。 In the present embodiment, the electron-withdrawing group means a group in which Hammett's substituent constant σm exhibits a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965) p. 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include CF 3 group (σm = 0.43), CF 3 CO group (σm = 0.63), HC≡C group (σm = 0.21), CH 2 = CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0 .34), H 2 NCOCH 2 group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

　ＥＷＧは、下記式（ＥＷＧ－１）～（ＥＷＧ－６）で表される基であることが好ましい。

Figure JPOXMLDOC01-appb-C000043
　式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒｘ１～Ｒｘ３は、それぞれ独立に、水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３がさらに好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３がさらに好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）、ヒドロキシル基、またはカルボキシル基を表す。Ａｒは芳香族基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０がさらに好ましい）を表す。Ｒｘ１～Ｒｘ３がアルキル基、アルケニル基、アリール基のとき、環を形成してもよく、環を形成する際にはその途中に上記連結基Ｌを介在していてもよい。これらのアルキル基、アルケニル基、アリール基、ならびに、Ａｒは、本発明の効果を損ねない範囲で、置換基Ｔを有していてもよい。なかでも、Ａｒは特にカルボキシル基（好ましくは１～３個）を有することが好ましい。＊は結合位置を表す。
　Ｎｐは１～６の整数を表し、１～３の整数が好ましく、１または２がより好ましい。 EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
Figure JPOXMLDOC01-appb-C000043
 In formulas (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3). More preferably), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and 6 to 6 carbon atoms). 10 is more preferable), and represents a hydroxyl group or a carboxyl group. Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms). When R x1 to R x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed, and when the ring is formed, the linking group L may be interposed in the middle. These alkyl group, alkenyl group, aryl group, and Ar may have a substituent T as long as the effects of the present invention are not impaired. Among these, Ar preferably has a carboxyl group (preferably 1 to 3). * Represents a bonding position.
Np represents an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably 1 or 2.

　本発明における熱塩基発生剤の分子量は、好ましくは、１００以上２０００未満であり、より好ましくは２００～１０００である。
　本発明における熱塩基発生剤の具体例としては、後述する実施例で用いる化合物の他、国際公開第２０１５／１９９２１９号に記載の４０℃以上に加熱すると塩基を発生する酸性化合物およびｐＫａ１が０～４のアニオンとアンモニウムカチオンを有するアンモニウム塩が例示され、これらの内容は本明細書に組み込まれる。 The molecular weight of the thermal base generator in the present invention is preferably 100 or more and less than 2000, and more preferably 200 to 1000.
Specific examples of the thermal base generator in the present invention include, in addition to the compounds used in the examples described later, an acidic compound that generates a base when heated to 40 ° C. or higher described in International Publication No. 2015/199219 and pKa1 of 0 to Illustrative are ammonium salts having four anions and an ammonium cation, the contents of which are incorporated herein.

　熱塩基発生剤を用いる場合、組成物における熱塩基発生剤の含有量は、組成物の全固形分に対し、０．０１～５０質量％であることが好ましい。下限は、０．０５質量％以上がより好ましく、０．１質量％以上がさらに好ましい。上限は、１０質量％以下がより好ましく、５質量％以下がさらに好ましい。
　熱塩基発生剤は、１種または２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。また、本発明の組成物は、熱塩基発生剤を実質的に含まない構成とすることもできる。実質的に含まないとは、組成物の全固形分に対し、０．０１質量％未満であることをいい、０．００５質量％未満であることがより好ましい。 When a thermal base generator is used, the content of the thermal base generator in the composition is preferably 0.01 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. The upper limit is more preferably 10% by mass or less, and further preferably 5% by mass or less.
1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range. Moreover, the composition of this invention can also be set as the structure which does not contain a thermal base generator substantially. “Substantially free” means less than 0.01% by mass, more preferably less than 0.005% by mass, based on the total solid content of the composition.

＜その他の添加剤＞
　本発明の感光性樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、熱ラジカル重合開始剤、熱酸発生剤、増感色素、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を添加することができる。これらの添加剤を添加する場合、その合計添加量は組成物の固形分の３質量％以下とすることが好ましい。 <Other additives>
The photosensitive resin composition of the present invention has various additives, for example, a thermal radical polymerization initiator, a thermal acid generator, a sensitizing dye, and a chain transfer agent, as necessary, as long as the effects of the present invention are not impaired. , Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, aggregation inhibitors, and the like can be added. When these additives are added, the total addition amount is preferably 3% by mass or less based on the solid content of the composition.

＜＜光酸発生剤＞＞
本発明の組成物は、光酸発生剤を含有していてもよい。光酸発生剤を含有することにより、露光部に酸が発生し、露光部のアルカリ水溶液に対する溶解性が増大するため、ポジ型感光性樹脂組成物として用いることができる。
　光酸発生剤としては、キノンジアジド化合物、スルホニウム塩、ホスホニウム塩、ジアゾニウム塩、ヨードニウム塩などが挙げられる。中でも優れた溶解抑止効果を発現し、高感度かつ低膜減りのポジ型組成物を得られるという点から、キノンジアジド化合物が好ましく用いられる。また、光酸発生剤を２種以上含有してもよい。これにより、露光部と未露光部の溶解速度の比をより大きくすることができ、高感度なポジ型感光性樹脂組成物を得ることができる。 
　具体的には、国際公開第２０１７／１１０９８２号の段落０２０９～０２１５の記載を参酌でき、これらの内容は本明細書に組み込まれる。 << Photoacid generator >>
The composition of the present invention may contain a photoacid generator. By containing the photoacid generator, an acid is generated in the exposed area, and the solubility of the exposed area in the alkaline aqueous solution is increased. Therefore, it can be used as a positive photosensitive resin composition.
Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, a quinonediazide compound is preferably used because it exhibits an excellent dissolution inhibiting effect and a positive composition with high sensitivity and low film thickness can be obtained. Moreover, you may contain 2 or more types of photo-acid generators. Thereby, the ratio of the dissolution rate of an exposed part and an unexposed part can be enlarged more, and a highly sensitive positive type photosensitive resin composition can be obtained.
Specifically, the description in paragraphs 0209 to 0215 of International Publication No. 2017/110982 can be referred to, and the contents thereof are incorporated in the present specification.

　光酸発生剤の含有量は、ポリマー前駆体１００質量部に対して、好ましくは３～４０質量部である。光酸発生剤の含有量をこの範囲とすることにより、より高感度化を図ることができる。さらに増感剤などを必要に応じて含有してもよい。
光酸発生剤は、１種のみ用いても、２種以上用いてもよい。２種以上用いる場合は、合計量が上記範囲となることが好ましい。   The content of the photoacid generator is preferably 3 to 40 parts by mass with respect to 100 parts by mass of the polymer precursor. By setting the content of the photoacid generator within this range, higher sensitivity can be achieved. Furthermore, you may contain a sensitizer etc. as needed.
Only one type of photoacid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

＜＜光塩基発生剤＞＞
　本発明で用いる感光性樹脂組成物は、光塩基発生剤を含んでいてもよい。本発明における光硬化促進剤とは、露光により塩基を発生するもの（光塩基発生剤）が好ましく、常温常圧の通常の条件下では活性を示さないが、外部刺激として電磁波の照射と加熱が行なわれると、塩基（塩基性物質）を発生するものが特に好ましい。露光により発生した塩基はポリマー前駆体を加熱により硬化させる際の触媒として働くため、好適に用いることができる。
　本発明においては、光硬化促進剤として公知のものを用いることができる。例えば遷移金属化合物錯体や、アンモニウム塩などの構造を有するものや、アミジン部分がカルボン酸と塩を形成することで潜在化されたもののように、塩基成分が塩を形成することにより中和されたイオン性の化合物や、カルバメート誘導体、オキシムエステル誘導体、アシル化合物などのウレタン結合やオキシム結合などにより塩基成分が潜在化された非イオン性の化合物を挙げることができる。 << Photobase generator >>
The photosensitive resin composition used in the present invention may contain a photobase generator. The photocuring accelerator in the present invention is preferably one that generates a base upon exposure (photobase generator), and does not exhibit activity under normal conditions of room temperature and normal pressure. Particularly preferably, those which generate a base (basic substance) when carried out. Since the base generated by exposure works as a catalyst for curing the polymer precursor by heating, it can be suitably used.
In the present invention, known photocuring accelerators can be used. For example, the base component was neutralized by forming a salt, such as a transition metal compound complex, a compound having an ammonium salt structure, or an amidine moiety made latent by forming a salt with a carboxylic acid. Examples include ionic compounds, and nonionic compounds in which a base component is made latent by urethane bonds or oxime bonds such as carbamate derivatives, oxime ester derivatives, and acyl compounds.

　本発明に係る光硬化促進剤としては、例えば、特開２００９－０８０４５２号公報および国際公開第２００９／１２３１２２号で開示されたような桂皮酸アミド構造を有する光硬化促進剤、特開２００６－１８９５９１号公報および特開２００８－２４７７４７号公報で開示されたようなカルバメート構造を有する光硬化促進剤、特開２００７－２４９０１３号公報および特開２００８－００３５８１号公報で開示されたようなオキシム構造、カルバモイルオキシム構造を有する光硬化促進剤等が挙げられるが、これらに限定されず、その他にも公知の光硬化促進剤の構造を用いることができる。 Examples of the photocuring accelerator according to the present invention include a photocuring accelerator having a cinnamic acid amide structure as disclosed in JP2009-080452A and WO2009 / 123122, and JP2006-188951A. Photocuring accelerator having a carbamate structure as disclosed in Japanese Patent Application Laid-Open No. 2008-247747, and an oxime structure as disclosed in Japanese Patent Application Laid-Open No. 2007-249013 and Japanese Patent Application Laid-Open No. 2008-003581, carbamoyl Examples of the photocuring accelerator having an oxime structure include, but are not limited to, and other known photocuring accelerator structures can be used.

　その他、光硬化促進剤としては、特開２０１２－０９３７４６号公報の段落０１８５～０１８８、０１９９～０２００および０２０２に記載の化合物、特開２０１３－１９４２０５号公報の段落００２２～００６９に記載の化合物、特開２０１３－２０４０１９号公報の段落００２６～００７４に記載の化合物、ならびに国際公開第２０１０／０６４６３１号の段落００５２に記載の化合物が例として挙げられる。 Other examples of the photocuring accelerator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-093746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205A, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019A and the compound described in paragraph 0052 of WO2010 / 064631.

　光硬化促進剤の市販品としては、ＷＰＢＧ－２６６、ＷＰＢＧ－３００、ＷＰＧＢ－３４５、ＷＰＧＢ－１４０、ＷＰＢＧ－１６５、ＷＰＢＧ－０２７、ＰＢＧ－０１８、ＷＰＧＢ－０１５、ＷＰＢＧ－０４１、ＷＰＧＢ－１７２、ＷＰＧＢ－１７４、ＷＰＢＧ－１６６、ＷＰＧＢ－１５８、ＷＰＧＢ－０２５、ＷＰＧＢ－１６８、ＷＰＧＢ－１６７およびＷＰＢＧ－０８２（和光純薬工業社製）を用いることもできる。 Commercially available photocuring accelerators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167 and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.

　光硬化促進剤を用いる場合、組成物における光硬化促進剤の含有量は、組成物の全固形分に対し、０．１～５０質量％であることが好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上がさらに好ましい。上限は、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。
　光硬化促進剤は、１種または２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the photocuring accelerator is used, the content of the photocuring accelerator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a photocuring accelerator. When using 2 or more types, it is preferable that a total amount is the said range.

＜＜熱ラジカル重合開始剤＞＞
　本発明の感光性樹脂組成物は、本発明の趣旨を逸脱しない範囲で熱ラジカル重合開始剤を含んでいてもよい。
　熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤を添加することによって、ポリマー前駆体の環化と共に、ポリマー前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。
　熱ラジカル重合開始剤として、具体的には、特開２００８－０６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられる。 << Thermal radical polymerization initiator >>
The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator without departing from the gist of the present invention.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be promoted together with the cyclization of the polymer precursor, so that higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

　熱ラジカル重合開始剤を含む場合、その含有量は、本発明の感光性樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは５～１５質量％である。熱ラジカル重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。熱ラジカル重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the thermal radical polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. %, And more preferably 5 to 15% by mass. The thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.

＜＜熱酸発生剤＞＞
　本発明の感光性樹脂組成物は、熱酸発生剤を含んでいてもよい。熱酸発生剤は、加熱により酸を発生し、ポリマー前駆体の環化を促進し硬化膜の機械特性をより向上させる。熱酸発生剤は、特開２０１３－１６７７４２号公報の段落００５９に記載の化合物などが挙げられる。 << thermal acid generator >>
The photosensitive resin composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the polymer precursor, and further improves the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.

　熱酸発生剤の含有量は、ポリマー前駆体１００質量部に対して０．０１質量部以上が好ましく、０．１質量部以上がより好ましい。熱酸発生剤を０．０１質量部以上含有することで、架橋反応およびポリマー前駆体の環化が促進されるため、硬化膜の機械特性および耐薬品性をより向上させることができる。また、熱酸発生剤の含有量は、硬化膜の電気絶縁性の観点から、２０質量部以下が好ましく、１５質量部以下がより好ましく、１０質量部以下がさらに好ましい。
　熱酸発生剤は、１種のみ用いても、２種以上用いてもよい。２種以上用いる場合は、合計量が上記範囲となることが好ましい。 0.01 mass part or more is preferable with respect to 100 mass parts of polymer precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 parts by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the polymer precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less, from the viewpoint of electrical insulation of the cured film.
The thermal acid generator may be used alone or in combination of two or more. When using 2 or more types, it is preferable that a total amount becomes the said range.

＜＜増感色素＞＞
　本発明の感光性樹脂組成物は、増感色素を含んでいてもよい。増感色素は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感色素は、熱塩基発生剤、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱塩基発生剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸あるいは塩基を生成する。増感色素の詳細については、特開２０１６－０２７３５７号公報の段落０１６１～０１６３の記載を参酌でき、この内容は本明細書に組み込まれる。 << Sensitizing dye >>
The photosensitive resin composition of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a photo radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a thermal base generator, a thermal radical polymerization initiator, and a photo radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.

　本発明の感光性樹脂組成物が増感色素を含む場合、増感色素の含有量は、本発明の感光性樹脂組成物の全固形分に対し、０．０１～２０質量％であることが好ましく、０．１～１５質量％であることがより好ましく、０．５～１０質量％であることがさらに好ましい。増感色素は、１種単独で用いてもよいし、２種以上を併用してもよい。 When the photosensitive resin composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Preferably, the content is 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

＜＜連鎖移動剤＞＞
　本発明の感光性樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版（高分子学会編、２００５年）６８３－６８４頁に定義されている。連鎖移動剤としては、例えば、分子内にＳＨ、ＰＨ、ＳｉＨ、およびＧｅＨを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、もしくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物（例えば、２－メルカプトベンズイミダゾール類、２－メルカプトベンズチアゾール類、２－メルカプトベンズオキサゾール類、３－メルカプトトリアゾール類、５－メルカプトテトラゾール類等）を好ましく用いることができる。 << Chain transfer agent >>
The photosensitive resin composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, and GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.

　本発明の感光性樹脂組成物が連鎖移動剤を有する場合、連鎖移動剤の含有量は、本発明の感光性樹脂組成物の全固形分に対し、０．０１～２０質量％であることが好ましく、１～１０質量％であることがより好ましく、１～５質量％であることがさらに好ましい。連鎖移動剤は１種のみでもよいし、２種以上であってもよい。連鎖移動剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Preferably, it is 1 to 10% by mass, more preferably 1 to 5% by mass. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.

＜＜界面活性剤＞＞
　本発明の感光性樹脂組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。

Figure JPOXMLDOC01-appb-C000044
<< Surfactant >>
From the viewpoint of further improving coatability, various types of surfactants may be added to the photosensitive resin composition of the present invention. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.
Figure JPOXMLDOC01-appb-C000044

　本発明の感光性樹脂組成物が界面活性剤を有する場合、界面活性剤の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０．００１～２．０質量％であることが好ましく、より好ましくは０．００５～１．０質量％である。界面活性剤は１種のみでもよいし、２種以上であってもよい。界面活性剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. It is preferable that the content is 0.005 to 1.0% by mass. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.

＜＜高級脂肪酸誘導体＞＞
　本発明の感光性樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で組成物の表面に偏在させてもよい。
　本発明の感光性樹脂組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０．１～１０質量％であることが好ましい。高級脂肪酸誘導体は１種のみでもよいし、２種以上であってもよい。高級脂肪酸誘導体が２種以上の場合は、その合計が上記範囲であることが好ましい。 << Higher fatty acid derivative >>
In order to prevent polymerization inhibition caused by oxygen, the photosensitive resin composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and the surface of the composition is dried during the coating process. May be unevenly distributed.
When the photosensitive resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is preferred. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.

＜その他の含有物質についての制限＞
　本発明の感光性樹脂組成物の水分含有量は、塗布面性状の観点から、５質量％未満が好ましく、１質量％未満がより好ましく、０．６質量％未満がさらに好ましい。 <Restrictions on other contained substances>
The water content of the photosensitive resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of the coated surface properties.

　本発明の感光性樹脂組成物の金属含有量は、絶縁性の観点から、５質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満がさらに好ましい。金属としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、クロム、ニッケルなどが挙げられる。金属を複数含む場合は、これらの金属の合計が上記範囲であることが好ましい。
　また、本発明の感光性樹脂組成物に意図せずに含まれる金属不純物を低減する方法としては、本発明の感光性樹脂組成物を構成する原料として金属含有量が少ない原料を選択する、本発明の感光性樹脂組成物を構成する原料に対してフィルターろ過を行う、装置内をポリテトラフロロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 The metal content of the photosensitive resin composition of the present invention is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and even more preferably less than 0.5 ppm by weight from the viewpoint of insulation. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
In addition, as a method for reducing metal impurities unintentionally contained in the photosensitive resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the photosensitive resin composition of the present invention. Examples include a method in which the raw material constituting the photosensitive resin composition of the invention is subjected to filter filtration, the inside of the apparatus is lined with polytetrafluoroethylene or the like, and distillation is performed under the conditions in which contamination is suppressed as much as possible. be able to.

　本発明の感光性樹脂組成物は、半導体材料としての用途を考慮すると、ハロゲン原子の含有量が、配線腐食性の観点から、５００質量ｐｐｍ未満が好ましく、３００質量ｐｐｍ未満がより好ましく、２００質量ｐｐｍ未満がさらに好ましい。中でも、ハロゲンイオンの状態で存在するものは、５質量ｐｐｍ未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満がさらに好ましい。ハロゲン原子としては、塩素原子および臭素原子が挙げられる。塩素原子および臭素原子、あるいは塩素イオンおよび臭素イオンの合計がそれぞれ上記範囲であることが好ましい。 In consideration of the use as a semiconductor material, the photosensitive resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, from the viewpoint of wiring corrosion. More preferably less than ppm. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.

　本発明の感光性樹脂組成物の収納容器としては従来公知の収納容器を用いることができる。また、収納容器としては、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 A conventionally known storage container can be used as the storage container for the photosensitive resin composition of the present invention. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into raw materials and compositions, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and the 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.

＜組成物の調製＞
　本発明の感光性樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。本発明は、また、ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体に、酸を添加することを含み、上記酸が、窒素と硫黄の単結合を有し、波長３６５ｎｍの光に対して安定である、感光性樹脂組成物の製造方法を提供する。上記酸は、上記ポリマー前駆体の合成中に添加することが好ましい。
　また、組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、１μｍ以下が好ましく、０．５μｍ以下がより好ましく、０．１μｍ以下がさらに好ましい。フィルターの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルターろ過工程では、複数種のフィルターを直列または並列に接続して用いてもよい。複数種のフィルターを使用する場合は、孔径または材質が異なるフィルターを組み合わせて使用してもよい。また、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であってもよい。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は０．０５ＭＰａ以上０．３ＭＰａ以下が好ましい。
　フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 <Preparation of composition>
The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method. The present invention also includes adding an acid to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, wherein the acid has a single bond of nitrogen and sulfur. A method for producing a photosensitive resin composition, which is stable with respect to light having a wavelength of 365 nm, is provided. The acid is preferably added during the synthesis of the polymer precursor.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore sizes or materials may be used in combination. Various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and filter. When the pressure is applied for filtration, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

＜硬化膜、積層体、半導体デバイス、およびそれらの製造方法＞
　次に、硬化膜、積層体、半導体デバイス、およびそれらの製造方法について説明する。
　本発明の硬化膜は、本発明の感光性樹脂組成物を硬化してなる。本発明の硬化膜の膜厚は、例えば、０．５μｍ以上とすることができ、１μｍ以上とすることができる。また、上限値としては、１００μｍ以下とすることができ、３０μｍ以下とすることもできる。 <Hardened film, laminate, semiconductor device, and production method thereof>
Next, a cured film, a laminated body, a semiconductor device, and a manufacturing method thereof will be described.
The cured film of the present invention is formed by curing the photosensitive resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.

　本発明の硬化膜を２層以上、さらには、３～７層積層して積層体としてもよい。本発明の硬化膜を２層以上有する積層体は、硬化膜の間に金属層を有する態様が好ましい。このような金属層は、再配線層などの金属配線として好ましく用いられる。 The laminate of the cured film of the present invention may be formed by laminating two or more layers, further 3 to 7 layers. The laminate having two or more cured films of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.

　本発明の硬化膜の適用可能な分野としては、半導体デバイスの絶縁膜、再配線層用層間絶縁膜、ストレスバッファ膜などが挙げられる。そのほか、封止フィルム、基板材料（フレキシブルプリント基板のベースフィルムやカバーレイ、層間絶縁膜）、あるいは上記のような実装用途の絶縁膜をエッチングでパターン形成することなどが挙げられる。これらの用途については、例えば、サイエンス＆テクノロジー株式会社「ポリイミドの高機能化と応用技術」２００８年４月、柿本雅明／監修、ＣＭＣテクニカルライブラリー「ポリイミド材料の基礎と開発」２０１１年１１月発行、日本ポリイミド・芳香族系高分子研究会／編「最新ポリイミド　基礎と応用」エヌ・ティー・エス，２０１０年８月等を参照することができる。 The fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. In addition, patterning may be performed by etching a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above. Regarding these uses, for example, Science & Technology Co., Ltd. “Polyimide high performance and applied technology” April 2008, Masaaki Enomoto / supervision, CMC technical library “Basics and Development of Polyimide Materials” issued November 2011 Reference can be made to Japan Polyimide / Aromatic Polymer Study Group / edition, “Latest Polyimide Basics and Applications”, NTS, August 2010, etc.

　また、本発明における硬化膜は、オフセット版面またはスクリーン版面などの版面の製造、成形部品のエッチングへの使用、エレクトロニクス、特に、マイクロエレクトロニクスにおける保護ラッカーおよび誘電層の製造などにも用いることもできる。 Further, the cured film in the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, the use for etching of molded parts, and the production of protective lacquers and dielectric layers in electronics, in particular, microelectronics.

　本発明の硬化膜の製造方法は、本発明の感光性樹脂組成物を用いることを含む。具体的には、本発明の感光性樹脂組成物を基板に適用して膜を形成する膜形成工程（層状にする層形成工程）と、層状にした感光性樹脂組成物を８０～４５０℃で加熱する加熱工程とを含む。好ましくは、硬化膜の製造方法は、上記の膜形成工程（層形成工程）の後、膜を露光する露光工程と、上記露光された感光性樹脂組成物層（膜、すなわち、樹脂層）に対して、現像を行う現像工程とを有する製造方法が挙げられる。この現像の後、加熱（好ましくは８０～４５０℃で加熱）する加熱工程を含むことで露光された樹脂層をさらに硬化させることができる。なお、上記のとおり、感光性樹脂組成物を用いる場合には、あらかじめ露光により組成物を硬化しておき、その後に必要により所望の加工（例えば下記の積層）を施して、さらに加熱により硬化させることができる。 The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Specifically, the photosensitive resin composition of the present invention is applied to a substrate to form a film (layer forming step), and the layered photosensitive resin composition is heated at 80 to 450 ° C. A heating step of heating. Preferably, in the method for producing a cured film, the film forming step (layer forming step) is followed by an exposure step of exposing the film, and the exposed photosensitive resin composition layer (film, ie, resin layer). On the other hand, the manufacturing method which has the image development process which develops is mentioned. After the development, the exposed resin layer can be further cured by including a heating step of heating (preferably heating at 80 to 450 ° C.). As described above, when the photosensitive resin composition is used, the composition is cured in advance by exposure, and then subjected to desired processing (for example, the following lamination) if necessary, and further cured by heating. be able to.

　本発明の積層体の製造方法は、本発明の硬化膜の製造方法を含む。本発明の積層体の製造方法は、上記の硬化膜の製造方法に従って、硬化膜を形成後、さらに、再度、感光性樹脂組成物の膜形成工程（層形成工程）および加熱工程、あるいは、感光性を付した場合には、膜形成工程（層形成工程）、露光工程、および現像工程（必要によりさらに加熱工程）を、上記順に行うことが好ましい。特に、上記各工程を順に、複数回、例えば、２～５回（すなわち、合計で３～６回）行うことが好ましい。このように硬化膜を積層することにより、積層体とすることができる。本発明では特に硬化膜を設けた部分の上または硬化膜の間、あるいはその両者に金属層を設けることが好ましい。
　以下これらの詳細を説明する。 The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. According to the method for producing a laminate of the present invention, after forming a cured film according to the above-described method for producing a cured film, a film forming step (layer forming step) and a heating step of a photosensitive resin composition, or In the case of imparting properties, it is preferable to perform the film formation step (layer formation step), the exposure step, and the development step (further, if necessary) in the above order. In particular, it is preferable to perform each of the above steps in order several times, for example, 2 to 5 times (that is, 3 to 6 times in total). Thus, a laminated body can be obtained by laminating a cured film. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both.
These details will be described below.

＜＜膜形成工程（層形成工程）＞＞
　本発明の好ましい実施形態に係る製造方法は、感光性樹脂組成物を基板に適用して膜（層状）にする、膜形成工程（層形成工程）を含む。
　基板の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基板、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ｎｉ、Ｃｕ、Ｃｒ、Ｆｅなどの金属基板、紙、ＳＯＧ（Ｓｐｉｎ　Ｏｎ　Ｇｌａｓｓ）、ＴＦＴ（薄膜トランジスタ）アレイ基板、プラズマディスプレイパネル（ＰＤＰ）の電極板など特に制約されない。本発明では、特に、半導体作製基板が好ましく、シリコン基板がより好ましい。
　また、樹脂層の表面や金属層の表面に感光性樹脂組成物層を形成する場合は、樹脂層や金属層が基板となる。
　感光性樹脂組成物を基板に適用する手段としては、塗布が好ましい。
　具体的には、適用する手段としては、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、およびインクジェット法などが例示される。感光性樹脂組成物層の厚さの均一性の観点から、より好ましくはスピンコート法、スリットコート法、スプレーコート法、インクジェット法である。方法に応じて適切な固形分濃度や塗布条件を調整することで、所望の厚さの樹脂層を得ることができる。また、基板の形状によっても塗布方法を適宜選択でき、ウェハ等の円形基板であればスピンコート法やスプレーコート法、インクジェット法等が好ましく、矩形基板であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、５００～２０００ｒｐｍの回転数で、１０秒～１分程度適用することができる。 << Film formation process (layer formation process) >>
The manufacturing method which concerns on preferable embodiment of this invention includes the film | membrane formation process (layer formation process) which applies the photosensitive resin composition to a board | substrate, and makes it a film | membrane (layer form).
The type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor manufacturing substrate is particularly preferable, and a silicon substrate is more preferable.
Moreover, when forming the photosensitive resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board | substrate.
As a means for applying the photosensitive resin composition to the substrate, coating is preferable.
Specifically, as a means to apply, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And an inkjet method. From the viewpoint of uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Also, the coating method can be appropriately selected depending on the shape of the substrate, and a spin coat method, a spray coat method, an ink jet method or the like is preferable for a circular substrate such as a wafer, and a slit coat method, a spray coat method, an ink jet method or the like for a rectangular substrate. The method is preferred. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.

＜＜乾燥工程＞＞
　本発明の製造方法は、感光性樹脂組成物層を形成後、膜形成工程（層形成工程）の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は５０～１５０℃で、７０℃～１３０℃がより好ましく、９０℃～１１０℃がさらに好ましい。乾燥時間としては、３０秒～２０分が例示され、１分～１０分が好ましく、３分～７分がより好ましい。 << Drying process >>
The manufacturing method of this invention may include the process of drying in order to remove a solvent after forming a photosensitive resin composition layer and after a film | membrane formation process (layer formation process). A preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

＜＜露光工程＞＞
　本発明の製造方法は、上記感光性樹脂組成物層を露光する露光工程を含んでもよい。露光量は、感光性樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長３６５ｎｍでの露光エネルギー換算で１００～１００００ｍＪ／ｃｍ２照射することが好ましく、２００～８０００ｍＪ／ｃｍ２照射することがより好ましい。
　露光波長は、１９０～１０００ｎｍの範囲で適宜定めることができ、２４０～５５０ｎｍが好ましい。
　露光波長は、光源との関係でいうと、（１）半導体レーザー（波長　８３０ｎｍ、５３２ｎｍ、４８８ｎｍ、４０５ｎｍ　ｅｔｃ．）、（２）メタルハライドランプ、（３）高圧水銀灯、ｇ線（波長　４３６ｎｍ）、ｈ線（波長　４０５ｎｍ）、ｉ線（波長　３６５ｎｍ）、ブロード（ｇ，ｈ，ｉ線の３波長）、（４）エキシマレーザー、ＫｒＦエキシマレーザー（波長　２４８ｎｍ）、ＡｒＦエキシマレーザー（波長　１９３ｎｍ）、Ｆ２エキシマレーザー（波長　１５７ｎｍ）、（５）極端紫外線；ＥＵＶ（波長　１３．６ｎｍ）、（６）電子線等が挙げられる。本発明の感光性樹脂組成物については、特に高圧水銀灯による露光が好ましく、なかでも、ｉ線による露光が好ましい。これにより、特に高い露光感度が得られうる。 << Exposure process >>
The manufacturing method of this invention may also include the exposure process which exposes the said photosensitive resin composition layer. The amount of exposure is not particularly defined as long as the photosensitive resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and to irradiate 200 to 8000 mJ / cm 2 . It is more preferable.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and is preferably 240 to 550 nm.
The exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h. Line (wavelength 405 nm), i line (wavelength 365 nm), broad (3 wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, and the like. About the photosensitive resin composition of this invention, the exposure by a high pressure mercury lamp is especially preferable, and the exposure by i line | wire is especially preferable. Thereby, particularly high exposure sensitivity can be obtained.

＜＜現像工程＞＞
　本発明の製造方法は、露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程を含んでもよい。現像を行うことにより、露光されていない部分（非露光部）が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えば、パドル、スプレー、浸漬、超音波等の現像方法が採用可能である。
　現像は現像液を用いて行う。現像液は、露光されていない部分（非露光部）が除去されるのであれば、特に制限なく使用できる。現像液は、有機溶剤を含むことが好ましく、現像液が有機溶剤を９０質量％以上含むことがより好ましい。本発明では、現像液は、ＣｌｏｇＰ値が－１～５の有機溶剤を含むことが好ましく、ＣｌｏｇＰ値が０～３の有機溶剤を含むことがより好ましい。
　有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチルおよび２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、ならびに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、ならびに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、ならびに、芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等、スルホキシド類としてジメチルスルホキシドが好適に挙げられる。
　本発明では、特にシクロペンタノン、γ－ブチロラクトンが好ましく、シクロペンタノンがより好ましい。
　現像液は、全成分の５０質量％以上が有機溶剤であることが好ましく、７０質量％以上が有機溶剤であることがより好ましく、９０質量％以上が有機溶剤であることがさらに好ましい。また、現像液は、１００質量％が有機溶剤であってもよい。 << Development process >>
The production method of the present invention may include a development processing step of performing development processing on the exposed photosensitive resin composition layer. By performing development, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as paddle, spray, immersion, and ultrasonic wave can be employed.
Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed. The developer preferably contains an organic solvent, and more preferably the developer contains 90% by mass or more of the organic solvent. In the present invention, the developer preferably contains an organic solvent having a ClogP value of −1 to 5, more preferably an organic solvent having a ClogP value of 0 to 3.
Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropyl) Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Cyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like As ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. A preferred example of the sulfoxide is dimethyl sulfoxide.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
In the developer, 50% by mass or more of all components is preferably an organic solvent, more preferably 70% by mass or more is an organic solvent, and further preferably 90% by mass or more is an organic solvent. Further, 100% by mass of the developer may be an organic solvent.

　現像時間としては、１０秒～５分が好ましい。現像時の現像液の温度は、特に定めるものではないが、通常、２０～４０℃で行うことができる。
　現像液を用いた処理の後、さらに、リンスを行ってもよい。リンスは、現像液とは異なる溶剤で行うことが好ましい。例えば、感光性樹脂組成物に含まれる溶剤を用いてリンスすることができる。リンス時間は、５秒～１分が好ましい。 The development time is preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly defined, but it can be usually 20 to 40 ° C.
After treatment with a developer, rinsing may be further performed. The rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.

＜＜加熱工程＞＞
　本発明の製造方法は、膜形成工程（層形成工程）、乾燥工程、または現像工程の後に加熱する工程を含むことが好ましい。特に、現像工程後に膜を加熱する工程を含むことが好ましい。加熱工程では、ポリマー前駆体の環化反応が進行する。また、本発明の組成物はポリマー前駆体以外のラジカル重合性化合物を含ませてもよいが、未反応のポリマー前駆体以外のラジカル重合性化合物の硬化などもこの工程で進行させることができる。加熱工程における層の加熱温度（最高加熱温度）としては、５０～５００℃が好ましく、８０～４５０℃がより好ましく、１４０～３５０℃がさらに好ましく、１６０～２５０℃が一層好ましく、１７０～２２０度が最も好ましい。
　加熱は、加熱開始時の温度から最高加熱温度まで１～１２℃／分の昇温速度で行うことが好ましく、２～１０℃／分がより好ましく、３～１０℃／分がさらに好ましい。昇温速度を１℃／分以上とすることにより、生産性を確保しつつ、アミンの過剰な揮発を防止することができ、昇温速度を１２℃／分以下とすることにより、硬化膜の残存応力を緩和することができる。
　加熱開始時の温度は、２０℃～１５０℃が好ましく、２０℃～１３０℃がより好ましく、２５℃～１２０℃がさらに好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の温度のことをいう。例えば、感光性樹脂組成物を基板の上に適用した後、乾燥させる場合、この乾燥後の膜（層）の温度であり、例えば、感光性樹脂組成物に含まれる溶剤の沸点よりも、３０～２００℃低い温度から徐々に昇温させることが好ましい。
　加熱時間（最高加熱温度での加熱時間）は、１０～３６０分であることが好ましく、２０～３００分であることがより好ましく、３０～２４０分であることがさらに好ましい。
　特に多層の積層体を形成する場合、硬化膜の層間の密着性の観点から、加熱温度は１８０℃～３２０℃で加熱することが好ましく、１８０℃～２６０℃で加熱することがより好ましい。その理由は定かではないが、この温度とすることで、層間のポリマー前駆体のエチニル基同士が架橋反応を進行しているためと考えられる。 << Heating process >>
The production method of the present invention preferably includes a heating step after the film forming step (layer forming step), the drying step, or the developing step. In particular, it is preferable to include a step of heating the film after the development step. In the heating step, the cyclization reaction of the polymer precursor proceeds. Moreover, although the composition of this invention may contain radically polymerizable compounds other than a polymer precursor, hardening of radically polymerizable compounds other than an unreacted polymer precursor can also be advanced at this process. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 to 500 ° C., more preferably 80 to 450 ° C., further preferably 140 to 350 ° C., still more preferably 160 to 250 ° C., and 170 to 220 ° C. Is most preferred.
Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the heating rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the heating rate to 12 ° C./min or less, the cured film Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto the substrate and then dried, the temperature of the dried film (layer) is, for example, 30% higher than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable to gradually raise the temperature from a temperature as low as ˜200 ° C.
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason is not certain, it is considered that the ethynyl groups of the polymer precursors between layers proceed with a crosslinking reaction at this temperature.

　加熱は段階的に行ってもよい。例として、２５℃から１８０℃まで３℃／分で昇温し、１８０℃にて６０分保持し、１８０℃から２００℃まで２℃／分で昇温し、２００℃にて１２０分保持する、といった前処理工程を行ってもよい。前処理工程としての加熱温度は１００～２００℃が好ましく、１１０～１９０℃であることがより好ましく、１２０～１８５℃であることがさらに好ましい。この前処理工程においては、米国特許９１５９５４７号公報に記載のように紫外線を照射しながら処理することも好ましい。このような前処理工程により膜の特性を向上させることが可能である。前処理工程は１０秒間～２時間程度の短い時間で行うとよく、１５秒～３０分間がより好ましい。前処理は２段階以上のステップとしてもよく、例えば１００～１５０℃の範囲で前処理工程１を行い、その後に１５０～２００℃の範囲で前処理工程２を行ってもよい。
　さらに、加熱後冷却してもよく、この場合の冷却速度としては、１～５℃／分であることが好ましい。 Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. You may perform the pre-processing process of these. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

　加熱工程は、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことがポリマー前駆体の分解を防ぐ点で好ましい。酸素濃度は、５０ｐｐｍ（体積比）以下が好ましく、２０ｐｐｍ（体積比）以下がより好ましい。 The heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the polymer precursor. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.

＜＜金属層形成工程＞＞
　本発明の製造方法は、現像処理後の感光性樹脂組成物層の表面に金属層を形成する金属層形成工程を含んでいることが好ましい。
　金属層としては、特に限定なく、既存の金属種を使用することができ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金およびタングステンが例示され、銅およびアルミニウムがより好ましく、銅がさらに好ましい。
　金属層の形成方法は、特に限定なく、既存の方法を適用することができる。例えば、特開２００７－１５７８７９号公報、特表２００１－５２１２８８号公報、特開２００４－２１４５０１号公報、特開２００４－１０１８５０号公報に記載された方法を使用することができる。例えば、フォトリソグラフィ、リフトオフ、電解めっき、無電解めっき、エッチング、印刷、およびこれらを組み合わせた方法などが考えられる。より具体的には、スパッタリング、フォトリソグラフィおよびエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解めっきを組み合わせたパターニング方法が挙げられる。
　金属層の厚さとしては、最も厚肉部で、０．１～５０μｍが好ましく、１～１０μｍがより好ましい。 << Metal layer formation process >>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer after the development treatment.
There are no particular limitations on the metal layer, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest part.

＜＜積層工程＞＞
　本発明の製造方法は、さらに、積層工程を含むことが好ましい。
　積層工程とは、硬化膜（樹脂層）または金属層の表面に、再度、上記膜形成工程（層形成工程）および加熱工程、あるいは、上記膜形成工程（層形成工程）、上記露光工程、および上記現像処理工程を、上記順に行うことを含む一連の工程である。積層工程には、さらに、上記乾燥工程や加熱工程等を含んでいてもよいことは言うまでもない。
　積層工程後、さらに積層工程を行う場合には、上記加熱工程後、上記露光工程後、または、上記金属層形成工程後に、さらに、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。
　上記積層工程は、２～５回行うことが好ましく、３～５回行うことがより好ましい。
　例えば、樹脂層／金属層／樹脂層／金属層／樹脂層／金属層のような、樹脂層が３層以上７層以下の構成が好ましく、３層以上５層以下がさらに好ましい。
　すなわち、本発明では特に、金属層を設けた後、さらに、上記金属層を覆うように、上記感光性樹脂組成物の膜形成工程（層形成工程）および加熱工程、あるいは、上記膜形成工程（層形成工程）、上記露光工程、および、上記現像処理工程（必要によりさらに加熱工程）を、上記順に行うことが好ましい。感光性樹脂組成物層（樹脂）を積層する積層工程と、金属層形成工程を交互に行うことにより、感光性樹脂組成物層（樹脂層）と金属層を交互に積層することができる。 << Lamination process >>
The production method of the present invention preferably further includes a lamination step.
The lamination step refers to the film formation step (layer formation step) and the heating step again on the surface of the cured film (resin layer) or metal layer, or the film formation step (layer formation step), the exposure step, and It is a series of steps including performing the development processing steps in the order described above. It goes without saying that the laminating step may further include the drying step and the heating step.
When a lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the heating process, the exposure process, or the metal layer formation process. An example of the surface activation treatment is plasma treatment.
The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers.
That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition film formation step (layer formation step) and the heating step, or the film formation step ( It is preferable to perform the layer forming step), the exposure step, and the development processing step (further, if necessary) in the order described above. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.

　本発明は、本発明の硬化膜または積層体を有する半導体デバイスも開示する。本発明の感光性樹脂組成物を再配線層用層間絶縁膜の形成に用いた半導体デバイスの具体例としては、特開２０１６－０２７３５７号公報の段落０２１３～０２１８の記載および図１の記載を参酌でき、これらの内容は本明細書に組み込まれる。 The present invention also discloses a semiconductor device having the cured film or laminate of the present invention. As specific examples of the semiconductor device using the photosensitive resin composition of the present invention for the formation of the interlayer insulating film for the rewiring layer, refer to the description in paragraphs 0213 to 0218 and the description in FIG. The contents of which are incorporated herein.

　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。「部」、「％」は特に述べない限り、質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. “Parts” and “%” are based on mass unless otherwise specified.

＜ポリマー前駆体（樹脂）の合成＞
（合成例１）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよび下記に示すジアミン（ａ）からのポリイミド前駆体組成物Ａ－１の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに７６．０ｇのジアミン（ａ）を溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２５６００、数平均分子量８６００であった。
ジアミン（ａ）

Figure JPOXMLDOC01-appb-C000045
<Synthesis of polymer precursor (resin)>
(Synthesis Example 1)
[Synthesis of polyimide precursor composition A-1 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 0 g saccharin (B-1), 20 mL ethyl alcohol and 200 mL γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 25600 and a number average molecular weight of 8600.
Diamine (a)
Figure JPOXMLDOC01-appb-C000045

（合成例２）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよびジアミン（ａ）からのポリイミド前駆体組成物Ａ－２の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに７６．０ｇのジアミン（ａ）を溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのＮ－シクロヘキシルスルファミン酸（Ｂ－２）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２３６００、数平均分子量８２００であった。 (Synthesis Example 2)
[Synthesis of polyimide precursor composition A-2 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a)]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 0 g of N-cyclohexylsulfamic acid (B-2), 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 23600 and a number average molecular weight of 8200.

（合成例３）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよびジアミン（ａ）からのポリイミド前駆体組成物Ａ－３の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに７６．０ｇのジアミン（ａ）を溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのエタンスルホン酸（Ｂ－ｃ１）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液を１４Ｌの水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２５１００、数平均分子量８４００であった。 (Synthesis Example 3)
[Synthesis of polyimide precursor composition A-3 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a)]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 0 g ethanesulfonic acid (B-c1), 20 mL ethyl alcohol and 200 mL γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was filtered by precipitating a polyimide precursor in 14 L of water, and dried under reduced pressure at 45 ° C. for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 25,100 and a number average molecular weight of 8,400.

（合成例４）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよびジアミン（ａ）からのポリイミド前駆体組成物Ａ－４の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに７６．０ｇのジアミン（ａ）を溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２２５００、数平均分子量８２００であった。 (Synthesis Example 4)
[Synthesis of polyimide precursor composition A-4 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a)]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution of 76.0 g of diamine (a) dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C., and the mixture was stirred for 1 hour, and then 20 mL of Ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 22500 and a number average molecular weight of 8200.

（合成例５）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－５の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジイソプロピルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２３８００、数平均分子量８７００であった。 (Synthesis Example 5)
[Synthesis of polyimide precursor composition A-5 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. The reaction mixture was then cooled to −10 ° C., and a solution of 34.35 g diisopropylcarbodiimide in 80 mL γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 3.0 g of saccharin (B-1), 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 23,800 and a number average molecular weight of 8,700.

（合成例６）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－６の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジイソプロピルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのＮ－シクロヘキシルスルファミン酸（Ｂ－２）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２３８００、数平均分子量８７００であった。 (Synthesis Example 6)
[Synthesis of polyimide precursor composition A-6 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. The reaction mixture was then cooled to −10 ° C., and a solution of 34.35 g diisopropylcarbodiimide in 80 mL γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 3.0 g of N-cyclohexylsulfamic acid (B-2), 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 23,800 and a number average molecular weight of 8,700.

（合成例７）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－７の合成］
　４２．４ｇの４，４’－オキシジフタル酸無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジイソプロピルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２５４００、数平均分子量８５００であった。 (Synthesis Example 7)
[Synthesis of polyimide precursor composition A-7 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
42.4 g of 4,4′-oxydiphthalic anhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. The reaction mixture was then cooled to −10 ° C., and a solution of 34.35 g diisopropylcarbodiimide in 80 mL γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution obtained by dissolving 25.1 g of 4,4′-diaminodiphenyl ether in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C., and the mixture was stirred for 1 hour. 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8500.

（合成例８）
［４，４’－オキシジフタル酸ニ無水物、２－ヒドロキシエチルメタクリレートおよびジアミン（ａ）からのポリイミド前駆体組成物Ａ－８の合成］
　２１．２ｇの４，４’－オキシジフタル酸ニ無水物と、１８．０ｇの２－ヒドロキシエチルメタクリレートと、２３．９ｇのピリジンと、と、２５０ｍＬのジグリムと混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±５℃に保ちながら１７．０ｇのＳＯＣｌ２を６０分かけて加えた。５０ｍＬのＮ－メチルピロリドンで希釈した後、１００ｍＬのＮ－メチルピロリドンに３８．０ｇのジアミン（ａ）を溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）とエチルアルコール２０ｍＬを加えた。得られた反応液を６Ｌの水の中でポリイミド前駆体を沈殿させ、固体を濾過してテトラヒドロフラン３８０ｇに溶解させた。得られた反応液に６Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させ、固体を再び濾過して減圧下で、４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２３９００、数平均分子量８０００であった。 (Synthesis Example 8)
[Synthesis of polyimide precursor composition A-8 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a)]
21.2 g of 4,4′-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme are mixed at a temperature of 60 ° C. for 4 hours. Stir. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 38.0 g of diamine (a) dissolved in 100 mL of N-methylpyrrolidone is added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. After stirring for 1 hour, 3.0 g of saccharin (B-1) and 20 mL of ethyl alcohol were added. From the obtained reaction solution, a polyimide precursor was precipitated in 6 L of water, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor in water, and the solid was filtered again and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 23,900 and a number average molecular weight of 8,000.

（合成例９）
［３，３’４，４’－ビフェニルテトラカルボン酸二無水物、２－ヒドロキシエチルメタクリレートおよびジアミン（ａ）からのポリイミド前駆体組成物Ａ－９の合成］
　４０．２ｇの３，３’４，４’－ビフェニルテトラカルボン酸二無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに７６．０ｇのジアミン（ａ）を溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２４６００、数平均分子量８３００であった。 (Synthesis Example 9)
[Synthesis of Polyimide Precursor Composition A-9 from 3,3′4,4′-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and diamine (a)]
40.2 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine and 100 mL of tetrahydrofuran were mixed, and 60 ° C. Stir at temperature for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution prepared by dissolving 76.0 g of diamine (a) in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 0 g saccharin (B-1), 20 mL ethyl alcohol and 200 mL γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 24,600 and a number average molecular weight of 8,300.

（合成例１０）
［３，３’４，４’－ビフェニルテトラカルボン酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－１０の合成］
　４０．２ｇの３，３’４，４’－ビフェニルテトラカルボン酸二無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２２５００、数平均分子量８０００であった。 (Synthesis Example 10)
[Synthesis of Polyimide Precursor Composition A-10 from 3,3′4,4′-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
40.2 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine and 100 mL of tetrahydrofuran were mixed, and 60 ° C. Stir at temperature for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 3.0 g of saccharin (B-1), 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 22500 and a number average molecular weight of 8,000.

（合成例１１）
［３，３’４，４’－ビフェニルテトラカルボン酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－１１の合成］
　４０．２ｇの３，３’４，４’－ビフェニルテトラカルボン酸二無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２５４００、数平均分子量８５００であった。 (Synthesis Example 11)
[Synthesis of Polyimide Precursor Composition A-11 from 3,3′4,4′-biphenyltetracarboxylic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
40.2 g of 3,3′4,4′-biphenyltetracarboxylic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine and 100 mL of tetrahydrofuran were mixed, and 60 ° C. Stir at temperature for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution obtained by dissolving 25.1 g of 4,4′-diaminodiphenyl ether in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C., and the mixture was stirred for 1 hour. 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8500.

（合成例１２）
［ピロメリット酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－１２の合成］
　２９．８ｇのピロメリット酸二無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２５２００、数平均分子量８８００であった。 (Synthesis Example 12)
[Synthesis of polyimide precursor composition A-12 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 3.0 g of saccharin (B-1), 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 25200 and a number average molecular weight of 8800.

（合成例１３）
［ピロメリット酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体組成物Ａ－１３の合成］
　２９．８ｇのピロメリット酸二無水物と、３６．４ｇの２－ヒドロキシエチルメタクリレートと、２２．０７ｇのピリジンと、１００ｍＬのテトラヒドロフランを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、８０ｍＬのγ－ブチロラクトンに３４．３５ｇのジシクロヘキシルカルボジイミドを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を３０分撹拌した。続いて、２００ｍＬのγ－ブチロラクトンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのＮ－シクロヘキシルスルファミン酸（Ｂ－２）と２０ｍＬのエチルアルコールと２００ｍＬのγ－ブチロラクトンを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。得られた反応液に１４Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させて濾過して、減圧下４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２５４００、数平均分子量８４００であった。 (Synthesis Example 13)
[Synthesis of polyimide precursor composition A-13 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
29.8 g of pyromellitic dianhydride, 36.4 g of 2-hydroxyethyl methacrylate, 22.07 g of pyridine, and 100 mL of tetrahydrofuran were mixed and stirred at a temperature of 60 ° C. for 4 hours. Next, the reaction mixture was cooled to −10 ° C., and a solution of 34.35 g dicyclohexylcarbodiimide dissolved in 80 mL of γ-butyrolactone was added dropwise to the reaction mixture over 60 minutes at −10 ± 5 ° C. Stir for minutes. Subsequently, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 200 mL of γ-butyrolactone was added dropwise to the reaction mixture at −10 ± 5 ° C. over 60 minutes, and the mixture was stirred for 1 hour. 3.0 g of N-cyclohexylsulfamic acid (B-2), 20 mL of ethyl alcohol and 200 mL of γ-butyrolactone were added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. 14 L of water was added to the obtained reaction solution, a polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 25400 and a number average molecular weight of 8400.

（合成例１４）
［ピロメリット酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニルからのポリイミド前駆体組成物Ａ－１４の合成］
　１４．９ｇのピロメリット酸二無水物と、１８．０ｇの２－ヒドロキシエチルメタクリレートと、２３．９ｇのピリジンと、２５０ｍＬのジグリムとを混合し、６０℃の温度で４時間撹拌した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±５℃に保ちながら１７．０ｇのＳＯＣｌ２を６０分かけて加えた。５０ｍＬのＮ－メチルピロリドンで希釈した後、１００ｍＬのＮ－メチルピロリドンに４０．２ｇの４，４’－ジアミノ－２，２’－ビス（トリフルオロメチル）ビフェニルを溶解させた溶液を－１０±５℃で６０分かけて反応混合物に滴下して、混合物を１時間撹拌した後、３．０ｇのサッカリン（Ｂ－１）とエチルアルコール２０ｍＬを加えた。得られた反応液を６Ｌの水の中でポリイミド前駆体を沈殿させ、固体を濾過してテトラヒドロフラン３８０ｇに溶解させた。得られた反応液に６Ｌの水を投入し、水の中でポリイミド前駆体を沈殿させ、固体を再び濾過して減圧下で、４５℃で２日間乾燥した。得られた粉末状のポリイミド前駆体は、重量平均分子量２３８００、数平均分子量８８００であった。 (Synthesis Example 14)
[Synthesis of polyimide precursor composition A-14 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl]
14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme were mixed and stirred at a temperature of 60 ° C. for 4 hours. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at −10 ± 5 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 40.2 g of 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl dissolved in 100 mL of N-methylpyrrolidone is −10 ± The mixture was added dropwise to the reaction mixture over 60 minutes at 5 ° C., and the mixture was stirred for 1 hour, and then 3.0 g of saccharin (B-1) and 20 mL of ethyl alcohol were added. From the obtained reaction solution, a polyimide precursor was precipitated in 6 L of water, and the solid was filtered and dissolved in 380 g of tetrahydrofuran. 6 L of water was added to the obtained reaction solution to precipitate a polyimide precursor in water, and the solid was filtered again and dried at 45 ° C. under reduced pressure for 2 days. The obtained powdery polyimide precursor had a weight average molecular weight of 23800 and a number average molecular weight of 8800.

（合成例１５）
［２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンおよび４，４’－オキシジベンゾイルクロリドからのポリベンゾオキサゾール前駆体組成物Ａ－１５の合成］
　２８．０ｇの２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンを２００ｍＬのＮ－メチルピロリドンに撹拌溶解した。続いて、温度を０～５℃に保ちながら、２５．０ｇの４，４’－オキシジベンゾイルクロリドを１０分間で滴下した後、６０分間撹拌を続け、３．０ｇのサッカリン（Ｂ－１）を加えた。得られた反応液に６Ｌの水を投入してポリベンゾオキサゾール前駆体を沈殿させ、固体をろ過して減圧下で、４５℃で２日間乾燥した。得られた粉末状のポリベンゾオキサゾール前駆体は、重量平均分子量２５０００、数平均分子量８５００であった。 (Synthesis Example 15)
[Synthesis of Polybenzoxazole Precursor Composition A-15 from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4′-oxydibenzoyl chloride]
28.0 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved by stirring in 200 mL of N-methylpyrrolidone. Subsequently, 25.0 g of 4,4′-oxydibenzoyl chloride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 60 minutes to obtain 3.0 g of saccharin (B-1). Was added. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45 ° C. for 2 days under reduced pressure. The obtained powdery polybenzoxazole precursor had a weight average molecular weight of 25000 and a number average molecular weight of 8500.

＜感光性樹脂組成物の調製＞
　樹脂を下記表１、２に記載の成分と混合し、均一な溶液として、感光性樹脂組成物の塗布液を調製した。各感光性樹脂組成物を、細孔の幅が０．８μｍのＡＤＶＡＮＴＥＣ製のフィルターを通して加圧濾過した。 <Preparation of photosensitive resin composition>
The resin was mixed with the components described in Tables 1 and 2 below to prepare a coating solution for the photosensitive resin composition as a uniform solution. Each photosensitive resin composition was pressure filtered through an ADVANTEC filter having a pore width of 0.8 μm.

＜基板処理工程＞
　シリコンウェハ上にＣｕをめっきしたウェハ（以下、「Ｃｕウェハ」という）に対し、酸化膜エッチャー（Ｕ６２１、株式会社 日立ハイテクノロジーズ）によってＯ２プラズマ処理をＯ２ガス流量５００ｍＬ／分で６０秒実施した。
＜感光性樹脂組成物層形成工程＞
　その後、各感光性樹脂組成物をＣｕウェハ上にスピンコート法により塗布して層状にし、感光性樹脂組成物層を形成した。
＜乾燥工程＞
　得られた感光性樹脂組成物層を有するＣｕウェハをホットプレート上で、１００℃で４分間乾燥し、シリコンウェハ上に２０μｍの厚さの均一な感光性樹脂組成物層を得た。
＜露光工程＞
　次いで、Ｃｕウェハ上の感光性樹脂組成物層を、ステッパー（Ｎｉｋｏｎ　ＮＳＲ　２００５　ｉ９Ｃ）を用いて、３６５ｎｍ（ｉ線）の露光波長で、バイナリ型フォトマスク（正方配列のホールパターン、２００μｍピッチ、マスクサイズ１００μｍ）を使用して４００ｍＪ／ｃｍ２の露光エネルギーで露光した。
　感光性樹脂組成物層をパターン化する場合の方が、パターン化しない場合よりも多くの界面が生じ、基板と硬化膜と金属層を積層した場合の層間に接触面積が少ない箇所が生じる。この場合、より層間剥離が生じやすくなり、本発明の効果がより顕著に示される。
＜現像工程＞
　全面露光された感光性樹脂組成物層を、シクロペンタノンに６０秒間浸漬して、現像処理した。
＜硬化工程＞
　次いで、現像処理後の感光性樹脂組成物層を５℃／分の昇温速度で昇温し、２３０℃に達した後３時間温度を維持した。 <Substrate processing process>
O 2 plasma treatment is performed for 60 seconds at an O 2 gas flow rate of 500 mL / min on an oxide film etcher (U621, Hitachi High-Technologies Corporation) on a wafer in which Cu is plated on a silicon wafer (hereinafter referred to as “Cu wafer”). did.
<Photosensitive resin composition layer forming step>
Then, each photosensitive resin composition was apply | coated by the spin coat method on Cu wafer, and was layered, and the photosensitive resin composition layer was formed.
<Drying process>
The obtained Cu wafer having the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 4 minutes to obtain a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer.
<Exposure process>
Next, the photosensitive resin composition layer on the Cu wafer was subjected to a binary photomask (square pattern hole pattern, 200 μm pitch, mask) at an exposure wavelength of 365 nm (i-line) using a stepper (Nikon NSR 2005 i9C). And an exposure energy of 400 mJ / cm 2 .
When the photosensitive resin composition layer is patterned, more interfaces are generated than when the patterning is not performed, and a portion having a small contact area is formed between the layers when the substrate, the cured film, and the metal layer are laminated. In this case, delamination is more likely to occur, and the effects of the present invention are more markedly exhibited.
<Development process>
The exposed photosensitive resin composition layer was immersed in cyclopentanone for 60 seconds and developed.
<Curing process>
Next, the photosensitive resin composition layer after the development treatment was heated at a temperature rising rate of 5 ° C./min, and after reaching 230 ° C., the temperature was maintained for 3 hours.

＜保存安定性評価＞
　上記感光性樹脂組成物１０ｇを容器（容器の材質：遮光ガラス、容量：１００ｍＬ）に密閉し、２５℃、相対湿度６５％の環境下で２週間静置した。放置前後での粘度をＥ型粘度計（ＴＶ－２５、東機産業）にて測定し、静置前後での粘度変動率（｜試験後の粘度－試験前の粘度｜／試験前の粘度）を算出した。
Ａ：８％未満
Ｂ：８％以上１０％未満
Ｃ：１０以上１５％未満
Ｄ：１５％以上 <Storage stability evaluation>
10 g of the photosensitive resin composition was sealed in a container (container material: light-shielding glass, capacity: 100 mL), and allowed to stand in an environment of 25 ° C. and a relative humidity of 65% for 2 weeks. Viscosity before and after standing was measured with an E-type viscometer (TV-25, Toki Sangyo), and the viscosity fluctuation rate before and after standing (| viscosity after test-viscosity before test // viscosity before test) Was calculated.
A: Less than 8% B: 8% or more and less than 10% C: 10 or more and less than 15% D: 15% or more

＜密着性評価＞
　上記硬化膜を、高加速寿命試験装置（ＰＣ－４２２Ｒ８Ｄ、平山製作所）を用いて、１２１℃、１００％ＲＨの条件下で１０００時間静置した。試験前後の銅（Ｃｕ）ウェハ上に１００μｍパターン角の硬化膜をボンドテスター（Ｃｏｎｄｏｒ　Ｓｉｇｍａ、ＸＹＺＴＥＣ）を用いて基板と硬化膜の剥離力測定を実施した。測定条件としては、室温下で２００μｍ針を使用して剥離速度１０μｍ／ｓ、基板と針の距離２μｍで実施した。試験前の密着力は５０ｇｆ（１Ｎは１０２．０ｇｆである）であり、前後での密着力減少率（（試験後の剥離力－試験前の剥離力）／試験前の剥離力）を算出した。
Ａ：３０％未満
Ｂ：３０％以上３５％未満
Ｃ：３５％以上４０％未満
Ｄ：４０％以上 <Adhesion evaluation>
The cured film was allowed to stand for 1000 hours under conditions of 121 ° C. and 100% RH using a high accelerated life test apparatus (PC-422R8D, Hirayama Seisakusho). The peel strength between the substrate and the cured film was measured using a bond tester (Condor Sigma, XYZTEC) on a cured film having a pattern angle of 100 μm on copper (Cu) wafers before and after the test. As measurement conditions, a 200 μm needle was used at room temperature and the peeling rate was 10 μm / s, and the distance between the substrate and the needle was 2 μm. The adhesion before the test was 50 gf (1N is 102.0 gf), and the rate of decrease in adhesion before and after ((peeling force after test−peeling force before test) / peeling force before test) was calculated. .
A: Less than 30% B: 30% or more and less than 35% C: 35% or more and less than 40% D: 40% or more

＜銅腐食性＞
　硬化膜を塗布していない銅基板（ブランク）と上記装置で評価した銅基板上のパターン周辺部を光学顕微鏡（Ｎｉｋｏｎ製）と断面ＳＥＭ（日立製）にて観察を行った。目視による変色・腐食の確認と基板界面の膜厚変動・凹凸の確認をして、下記の判別をした。
Ａ：ブランクに比べて変色がみられなかった。
Ｂ：ブランクに比べて変色が発生しており、膜厚には変化がみられなかった。
Ｃ：ブランクに比べて変色が発生しており、膜厚の減少がみられたが、表面に凹凸はみられなかった。
Ｄ：ブランクに比べて変色が発生しており、膜厚の減少がみられた。また、表面に凹凸がみられた。 <Copper corrosion>
The copper substrate (blank) to which the cured film was not applied and the peripheral portion of the pattern on the copper substrate evaluated by the above apparatus were observed with an optical microscope (Nikon) and a cross-sectional SEM (Hitachi). The following distinctions were made by visually confirming discoloration / corrosion and confirming film thickness variation / unevenness at the substrate interface.
A: Discoloration was not seen compared with the blank.
B: Discoloration occurred compared to the blank, and no change was observed in the film thickness.
C: Discoloration occurred compared to the blank, and the film thickness decreased, but no irregularities were observed on the surface.
D: Discoloration occurred compared to the blank, and a decrease in film thickness was observed. In addition, irregularities were observed on the surface.

 

Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
    
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000047
  

感光性樹脂組成物の配合表

Figure JPOXMLDOC01-appb-T000048
表１、２で「－」とされたものは添加していないこと（０質量部）を
意味する特定の酸（添加剤）
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-C000050
 Composition table of photosensitive resin composition
Figure JPOXMLDOC01-appb-T000048
 Specific acids (additives) meaning that “-” in Tables 1 and 2 is not added (0 parts by mass)
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-C000050

重合開始剤

Figure JPOXMLDOC01-appb-T000051
Polymerization initiator
Figure JPOXMLDOC01-appb-T000051

ラジカル重合性化合物（重合性化合物）

Figure JPOXMLDOC01-appb-T000052
Radical polymerizable compound (polymerizable compound)
Figure JPOXMLDOC01-appb-T000052

溶剤

Figure JPOXMLDOC01-appb-T000053
DMSO:ジメチルスルホキシド
N-メチルピロリドン/乳酸エチルは128.80/32.20、γ-ブチロラクトン/DMSO（ジメチルスルホキシド）は128.80/32.20で配合したことを意味する。 solvent
Figure JPOXMLDOC01-appb-T000053
 DMSO: Dimethyl sulfoxide
It means that N-methylpyrrolidone / ethyl lactate was blended at 128.80 / 32.20, and γ-butyrolactone / DMSO (dimethyl sulfoxide) was blended at 128.80 / 32.20.

熱塩基発生剤

Figure JPOXMLDOC01-appb-C000054
Thermal base generator
Figure JPOXMLDOC01-appb-C000054

金属接着性改良剤（シランカップリング剤）

Figure JPOXMLDOC01-appb-C000055
　Ｅｔ：エチル基 Metal adhesion improver (silane coupling agent)
Figure JPOXMLDOC01-appb-C000055
 Et: ethyl group

重合禁止剤
　Ｈ－１：１，４－ベンゾキノン
　Ｈ－２：４－メトキシフェノール Polymerization inhibitor H-1: 1,4-benzoquinone H-2: 4-methoxyphenol

マイグレーション抑制剤（銅腐食防止剤）
Ｉ－１：１，２，４－トリアゾール
Ｉ－２：１Ｈ－テトラゾール Migration inhibitor (copper corrosion inhibitor)
I-1: 1,2,4-triazole I-2: 1H-tetrazole

　上記の結果から分かるとおり、本発明においてポリマー前駆体と特定の酸とを組み合わせて用いた感光性樹脂組成物では、十分な密着性を示し、かつ高い保存安定性を実現していた。一方、酸自体を用いていない比較例２、３では、保存安定性に劣り（Ｄ）、密着性も不十分（Ｄ）であった。酸は用いているが特定の要件を満たさないものであった場合（比較例１）、保存安定性は低めで（Ｃ）、密着性については不十分（Ｄ）の結果であった。これらの結果から、本発明の感光性樹脂組成物は、半導体デバイスの製造およびその製品等において優れた性能を発揮しうることが分かった。 As can be seen from the above results, the photosensitive resin composition used in the present invention in combination with the polymer precursor and the specific acid showed sufficient adhesion and realized high storage stability. On the other hand, in Comparative Examples 2 and 3 in which the acid itself was not used, the storage stability was inferior (D) and the adhesion was insufficient (D). When the acid was used but did not satisfy the specific requirements (Comparative Example 1), the storage stability was low (C), and the adhesion was insufficient (D). From these results, it was found that the photosensitive resin composition of the present invention can exhibit excellent performance in the production of semiconductor devices and their products.

＜実施例１００＞
　感光性樹脂組成物Ａ－１を、細孔の幅が１．０μｍのＡＤＶＡＮＴＥＣ製フィルターを通して加圧濾過した後、銅薄層が形成された樹脂基板の表面にスピニング（３５００ｒｐｍ、３０秒）して適用した。樹脂基板に適用した感光性樹脂組成物を、１００℃で２分間乾燥した後、ステッパー（ニコン製、ＮＳＲ１５０５ｉ６）を用いて露光した。露光はマスクを介して、波長３６５ｎｍで２００ｍＪ／ｃｍ２の露光量で露光した。露光の後、ベークを行い、シクロペンタノンで３０秒間現像し、ＰＧＭＥＡで２０秒間リンスし、パターンを得た。
　次いで、２３０℃で３時間加熱し、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。 <Example 100>
The photosensitive resin composition A-1 was pressure filtered through an ADVANTEC filter having a pore width of 1.0 μm, and then spun onto the surface of the resin substrate on which the copper thin layer was formed (3500 rpm, 30 seconds). Applied. The photosensitive resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (Nikon NSR1505i6). The exposure was performed through a mask at an exposure amount of 200 mJ / cm 2 at a wavelength of 365 nm. After exposure, it was baked, developed with cyclopentanone for 30 seconds, and rinsed with PGMEA for 20 seconds to obtain a pattern.
Subsequently, it heated at 230 degreeC for 3 hours, and formed the interlayer insulation film for rewiring layers. This interlayer insulation film for rewiring layers was excellent in insulation.

Claims (26)

　ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体と、窒素と硫黄の単結合を有する酸とを含む、感光性樹脂組成物。 A photosensitive resin composition comprising at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and an acid having a single bond of nitrogen and sulfur. 　前記酸のｐｋａが０以上４．０以下である、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, wherein the acid has a pka of 0 or more and 4.0 or less. 　前記酸の水／オクタノール分配係数の対数であるＣｌｏｇＰが－２．１以上１．２以下である、請求項１または２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1 or 2, wherein ClogP, which is a logarithm of the water / octanol distribution coefficient of the acid, is from -2.1 to 1.2. 　前記酸の分子量が３００以下である、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 4. The photosensitive resin composition according to claim 1, wherein the molecular weight of the acid is 300 or less. 　前記酸が環状構造を有する、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid has a cyclic structure. 　前記酸がスルタム構造を有する、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid has a sultam structure. 　前記酸が下記式（Ｓ１）～（Ｓ４）のいずれかで表される、請求項１～４のいずれか１項に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000001
 　式（Ｓ１）～（Ｓ４）中、Ｌ１１は単結合または連結基を表し、Ｌ１２は連結基を表し、Ｒ１１は水素原子または置換基を表し、Ｒ２１は置換基を表し、Ｒ３１は置換基を表し、Ｒ４１は水素原子または置換基を表し、Ｒ４２は置換基を表し、Ｒ４３はＯＨ、ＮＨ２またはＮ３を表す。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid is represented by any one of the following formulas (S1) to (S4);
Figure JPOXMLDOC01-appb-C000001
 In the formulas (S1) to (S4), L 11 represents a single bond or a linking group, L 12 represents a linking group, R 11 represents a hydrogen atom or a substituent, R 21 represents a substituent, and R 31 Represents a substituent, R 41 represents a hydrogen atom or a substituent, R 42 represents a substituent, and R 43 represents OH, NH 2 or N 3 . 　前記酸が下記式（Ｓ１－１）で表される、請求項１～４のいずれか１項に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000002
 　式（Ｓ１－１）中、Ｒ１２は水素原子または置換基であり、Ｒ１３およびＲ１４はそれぞれ独立に水素原子または置換基である。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the acid is represented by the following formula (S1-1);
Figure JPOXMLDOC01-appb-C000002
 In formula (S1-1), R 12 is a hydrogen atom or a substituent, and R 13 and R 14 are each independently a hydrogen atom or a substituent. 　さらに、光重合開始剤、ラジカル重合性化合物および溶剤の少なくとも１種を含む、請求項１～８のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 1, further comprising at least one of a photopolymerization initiator, a radical polymerizable compound, and a solvent. 　再配線層用層間絶縁膜の形成に用いられる、請求項１～９のいずれか１項に記載の感光性樹脂組成物。 10. The photosensitive resin composition according to claim 1, which is used for forming an interlayer insulating film for a rewiring layer. 　ポリイミド前駆体およびポリベンゾオキサゾール前駆体からなる群より選ばれる少なくとも１つのポリマー前駆体に、窒素と硫黄の単結合を有する酸を添加することを含む、感光性樹脂組成物の製造方法。 A method for producing a photosensitive resin composition, comprising adding an acid having a single bond of nitrogen and sulfur to at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor. 　前記酸を、前記ポリマー前駆体の合成中に添加する、請求項１１に記載の感光性樹脂組成物の製造方法。 The method for producing a photosensitive resin composition according to claim 11, wherein the acid is added during the synthesis of the polymer precursor. 　前記酸のｐｋａが０以上４．０以下である、請求項１１または１２に記載の感光性樹脂組成物の製造方法。 The method for producing a photosensitive resin composition according to claim 11 or 12, wherein the acid has a pka of 0 or more and 4.0 or less. 　前記酸のＣｌｏｇＰが－２．１以上１．２以下である、請求項１１～１３のいずれか１項に記載の感光性樹脂組成物の製造方法。 The method for producing a photosensitive resin composition according to any one of claims 11 to 13, wherein ClogP of the acid is from -2.1 to 1.2. 　前記酸の分子量が３００以下である、請求項１１～１４のいずれか１項に記載の感光性樹脂組成物の製造方法。 The method for producing a photosensitive resin composition according to any one of claims 11 to 14, wherein the acid has a molecular weight of 300 or less. 　前記酸が下記式（Ｓ１）～（Ｓ４）のいずれかで表される、請求項１１～１５のいずれか１項に記載の感光性樹脂組成物の製造方法；
Figure JPOXMLDOC01-appb-C000003
 　式（Ｓ１）～（Ｓ４）中、Ｌ１１は単結合または連結基を表し、Ｌ１２は連結基を表し、Ｒ１１は水素原子または置換基を表し、Ｒ２１は置換基を表し、Ｒ３１は置換基を表し、Ｒ４１は水素原子または置換基を表し、Ｒ４２は置換基を表し、Ｒ４３はＯＨ、ＮＨ２またはＮ３を表す。 The method for producing a photosensitive resin composition according to any one of claims 11 to 15, wherein the acid is represented by any one of the following formulas (S1) to (S4);
Figure JPOXMLDOC01-appb-C000003
 In the formulas (S1) to (S4), L 11 represents a single bond or a linking group, L 12 represents a linking group, R 11 represents a hydrogen atom or a substituent, R 21 represents a substituent, and R 31 Represents a substituent, R 41 represents a hydrogen atom or a substituent, R 42 represents a substituent, and R 43 represents OH, NH 2 or N 3 . 　請求項１～１０のいずれか１項に記載の感光性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. 　膜厚が１～３０μｍである、請求項１７に記載の硬化膜。 The cured film according to claim 17, wherein the film thickness is 1 to 30 μm. 　請求項１７または１８に記載の硬化膜を２層以上有する、積層体。 A laminate having two or more cured films according to claim 17 or 18. 　前記硬化膜の間に金属層を有する、請求項１９に記載の積層体。 The laminate according to claim 19, further comprising a metal layer between the cured films. 　請求項１～１０のいずれか１項に記載の感光性樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。 A method for producing a cured film, comprising a film forming step of forming a film by applying the photosensitive resin composition according to any one of claims 1 to 10 to a substrate. 　前記膜を露光する露光工程および前記膜を現像する現像工程を有する、請求項２１に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 21, comprising an exposure step of exposing the film and a developing step of developing the film. 　前記現像に用いられる現像液が有機溶剤を９０質量％以上含む、請求項２２に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 22, wherein the developer used for the development contains 90% by mass or more of an organic solvent. 　前記現像工程後に膜を加熱する工程を含む、請求項２２または２３に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 22 or 23, comprising a step of heating the film after the developing step. 　請求項２１～２４のいずれか１項に記載の硬化膜の製造方法を複数回行なう、積層体の製造方法。 A method for producing a laminate, wherein the method for producing a cured film according to any one of claims 21 to 24 is performed a plurality of times. 　請求項１７もしくは１８に記載の硬化膜または請求項１９もしくは２０に記載の積層体を有する、半導体デバイス。 A semiconductor device comprising the cured film according to claim 17 or 18 or the laminate according to claim 19 or 20.
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