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WO2019189327A1 - Composition de résine photosensible, film durci, stratifié et application de ceux-ci - Google Patents

Composition de résine photosensible, film durci, stratifié et application de ceux-ci 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
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English (en)
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/ja
Publication of WO2019189327A1 publication Critical patent/WO2019189327A1/fr
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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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne : une composition de résine photosensible comprenant au moins un précurseur de polymère choisi parmi le groupe constitué de précurseurs de polyimide et de précurseurs de polybenzoxazole, et un acide ayant une liaison simple d'azote et de soufre ; un procédé de fabrication de la composition de résine photosensible ; un film durci ; un stratifié ; un procédé de fabrication du film durci ; un procédé de fabrication du stratifié ; un dispositif semi-conducteur ; et un stabilisateur de conservation.
PCT/JP2019/013121 2018-03-30 2019-03-27 Composition de résine photosensible, film durci, stratifié et application de ceux-ci Ceased WO2019189327A1 (fr)

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CN114524938A (zh) * 2021-10-28 2022-05-24 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件

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TWI878445B (zh) * 2020-02-03 2025-04-01 日商富士軟片股份有限公司 硬化性樹脂組成物、樹脂膜、硬化膜、積層體、硬化膜的製造方法及半導體元件

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JP2000241974A (ja) * 1999-02-17 2000-09-08 Toray Ind Inc ポジ型感光性組成物
JP2001181249A (ja) * 1999-10-14 2001-07-03 Asahi Kasei Corp アミドフェノール化合物
JP2002131906A (ja) * 2000-10-30 2002-05-09 Hitachi Chemical Dupont Microsystems Ltd 感光性ポリイミド前駆体組成物及びそれを用いたパターンの製造法並びに電子部品
JP2011164454A (ja) * 2010-02-12 2011-08-25 Hitachi Chemical Dupont Microsystems Ltd 感光性樹脂組成物及びこれを用いた回路形成用基板

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JPH0580514A (ja) * 1991-09-20 1993-04-02 Hitachi Ltd 感光性耐熱重合体組成物
JP2000241974A (ja) * 1999-02-17 2000-09-08 Toray Ind Inc ポジ型感光性組成物
JP2001181249A (ja) * 1999-10-14 2001-07-03 Asahi Kasei Corp アミドフェノール化合物
JP2002131906A (ja) * 2000-10-30 2002-05-09 Hitachi Chemical Dupont Microsystems Ltd 感光性ポリイミド前駆体組成物及びそれを用いたパターンの製造法並びに電子部品
JP2011164454A (ja) * 2010-02-12 2011-08-25 Hitachi Chemical Dupont Microsystems Ltd 感光性樹脂組成物及びこれを用いた回路形成用基板

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114524938A (zh) * 2021-10-28 2022-05-24 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
CN114524938B (zh) * 2021-10-28 2024-02-09 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件

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TW201942198A (zh) 2019-11-01
TWI797291B (zh) 2023-04-01

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