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WO2018225676A1 - Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et composé - Google Patents

Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et composé Download PDF

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Publication number
WO2018225676A1
WO2018225676A1 PCT/JP2018/021347 JP2018021347W WO2018225676A1 WO 2018225676 A1 WO2018225676 A1 WO 2018225676A1 JP 2018021347 W JP2018021347 W JP 2018021347W WO 2018225676 A1 WO2018225676 A1 WO 2018225676A1
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WIPO (PCT)
Prior art keywords
group
photosensitive resin
resin composition
formula
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
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PCT/JP2018/021347
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English (en)
Japanese (ja)
Inventor
健志 川端
健太 吉田
悠 岩井
渋谷　明規
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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 KR1020197035583A priority Critical patent/KR102279447B1/ko
Priority to JP2019523520A priority patent/JP6808831B2/ja
Priority to CN201880037130.9A priority patent/CN110741318B/zh
Publication of WO2018225676A1 publication Critical patent/WO2018225676A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

Definitions

  • the present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device, and a compound.
  • a photosensitive resin composition obtained by imparting photosensitivity to a polyimide resin itself has been used. It is because a pattern formation process can be simplified by using the photosensitive resin composition.
  • Patent Document 1 (a) a polyimide precursor having a predetermined structure, (b) a compound that generates radicals upon irradiation with actinic rays, and (c) the following formula (4a) or (4b) And a resin composition containing (d) a solvent.
  • na is an integer of 3 or less.
  • R 101 and R 102 are each independently a hydrogen atom or a monovalent group.
  • Mb is an integer of 9 or less. .
  • tripropylene glycol diacrylate, tripropylene glycol or the like is disclosed as a compound represented by the formula (4a) or (4b).
  • the composition described in Patent Document 1 is not necessarily highly sensitive to light. Moreover, when making a cured film after storing the photosensitive resin composition for a fixed time, the storage stability of the photosensitive resin composition is also required.
  • the present invention aims to solve the above-described problems, and is a photosensitive resin composition having excellent storage stability and high sensitivity, and a cured film, a laminate, and a cured film using the same.
  • An object is to provide a manufacturing method and a semiconductor device. Moreover, it aims at providing the compound for manufacturing the said photosensitive resin composition.
  • a photosensitive resin composition comprising a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a radical polymerizable compound having a sulfur atom, a radical photopolymerization initiator, and a solvent.
  • 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 represent a hydrogen atom or a monovalent organic group
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group.
  • the photosensitive resin composition according to ⁇ 4> wherein the formula (3-1) is represented by the following formula (3-2);
  • L 1 represents —S—, —SS—, —S ( ⁇ O) —, or —S ( ⁇ O) 2 —
  • X 1 and X 2 are Each independently a single bond, —O—, —C ( ⁇ O) —, —C ( ⁇ O) O—, —OC ( ⁇ O) —, —S—, —S ( ⁇ O) 2 — or —NR 3 represents CO—
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical polymerizable group
  • La 1 to La 4 each independently represent a single bond, Any one of a group consisting of one or more combinations of an alkylene group and a phenylene group and a group consisting of a combination of one or more of an alkylene group and
  • ⁇ 6> The photosensitive resin composition according to ⁇ 5>, wherein both of R 1 and R 2 are each independently a radical polymerizable group.
  • ⁇ 7> The photosensitive resin composition according to ⁇ 5> or ⁇ 6>, wherein X 1 and X 2 are —O—.
  • ⁇ 8> The photosensitive resin composition according to any one of ⁇ 5> to ⁇ 7>, wherein L 1 is —S ( ⁇ O) —.
  • R 1 and R 2 are each independently a monovalent organic group having an acryloyl group or a methacryloyl group.
  • ⁇ 13> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 12>, further comprising a base generator.
  • ⁇ 14> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 13>, which is used for development.
  • ⁇ 15> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 14>, which is used for a development using a developer containing an organic solvent.
  • ⁇ 16> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 15>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 17> A cured film formed from the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 18> A laminate having two or more cured films according to ⁇ 17>. ⁇ 19> The laminate according to ⁇ 18>, having a metal layer between the cured films.
  • ⁇ 20> A method for producing a cured film, comprising using the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 16>.
  • ⁇ 21> A photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer, an exposure step of exposing the photosensitive resin composition layer, and the exposed photosensitive resin The manufacturing method of the cured film as described in ⁇ 20> which has a development process process which performs a development process with respect to a composition layer.
  • ⁇ 22> A semiconductor device having the cured film according to ⁇ 17> or the laminate according to ⁇ 18> or ⁇ 19>.
  • ⁇ 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.
  • 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.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”
  • (meth) acryl” represents both “acryl” and “methacryl”
  • (Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
  • solid content is the mass percentage of the other component except a solvent with respect to the gross mass of a composition.
  • solid content concentration says the density
  • 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. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
  • the photosensitive resin composition of the present invention includes a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, and a radical having a sulfur atom. It contains a polymerizable compound, a radical photopolymerization initiator, and a solvent. By setting it as such a structure, the photosensitive resin composition excellent in storage stability and having a high sensitivity is obtained. The reason for this is presumed that the radically polymerizable compound having a sulfur atom hardly causes a polymerization reaction with heat at room temperature and is based on enhancing the radically polymerizable property of the composition.
  • the photosensitive resin composition of the present invention includes a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor.
  • the polymer precursor preferably includes a polyimide precursor or a polybenzoxazole precursor, more preferably includes a polyimide precursor, and is a polyimide precursor including a repeating unit represented by the formula (1) described below. More preferably.
  • the polyimide precursor preferably contains a repeating unit represented by the following formula (1).
  • 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 in Formula (1) is an oxygen atom or NH, preferably an oxygen atom.
  • R 111 in Formula (1) represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic group, a straight chain aliphatic group having 2 to 20 carbon atoms, A group consisting of 20 branched aliphatic groups, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferable, and an aromatic group having 6 to 20 carbon atoms More preferred is a group consisting of
  • R 111 is preferably derived from a diamine.
  • the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one type of diamine may be used, or two or more types may be used. Specifically, the diamine is a straight chain aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof. And a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. The following are mentioned as an example of an aromatic group.
  • 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 at least two ethylene glycol chains or propylene glycol chains in one molecule, more preferably 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-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 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L is substituted with a fluorine atom.
  • Ar 0 is preferably a phenylene group
  • L is an aliphatic hydrocarbon group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S— or — S ( ⁇ O) 2 — is more preferable.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • 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.
  • Formula (51) In the formula (51), 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.
  • Formula (61) In formula (61), 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.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • R 112 represents 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 It is preferably a group selected from —, —S ( ⁇ O) 2 —, —NHCO—, and combinations thereof, and is a single bond or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom More preferably a group selected from among —, —O—, —C ( ⁇ O) —, —S— and —S ( ⁇ O) 2 —, —CH 2 —, —C (CF 3 ) 2 — More preferred is a divalent group selected from the group consisting of, —C (CH 3 ) 2 —, —O—, —C ( ⁇ O) —, —S— and —S ( ⁇ O) 2 —.
  • 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 (O).
  • 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 the formula (1) each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 includes a radical polymerizable group, both of which are radical polymerization. It is more preferable that a sex group is included.
  • 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.
  • the (meth) acryloyl group is a general term for an acryloyl group and a methacryloyl group.
  • 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 polyoxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 to 12 carbon atoms). 1 to 6 is more preferable, 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.
  • 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.
  • R 200 is a methyl group and R 201 is an ethylene group.
  • 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 a monovalent organic group
  • aromatic groups, aralkyl groups, and the like having 1, 2 or 3, preferably one acidic group, bonded to the carbon constituting the aryl group are exemplified. It is done. Specific examples include an aromatic group having 6 to 20 carbon atoms having an acidic group and an aralkyl group having 7 to 25 carbon atoms having an acidic group. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
  • the acidic group is preferably an OH group.
  • 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.
  • aromatic group examples include 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, anthracene.
  • the polyimide precursor when R 113 is a hydrogen atom or R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
  • 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 preferably 20% by mass or less. 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 repeating unit represented by the formula (1).
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (1-A). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
  • a 11 and A 12 represent an oxygen atom or NH
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently Represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a radical polymerizable group, and preferably a radical polymerizable group.
  • a 11 , A 12 , 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 repeating structural unit represented by the formula (1) may be one type or two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (1) may be included.
  • the polyimide precursor may also contain other types of repeating structural units in addition to the repeating 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 repeating units is a repeating unit represented by the formula (1).
  • 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more of all repeating units is a repeating 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 degree of dispersion of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with 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 used in the present invention preferably contains a repeating 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 represents 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 10 is particularly preferable.
  • the aliphatic group a linear aliphatic group is preferable.
  • 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 repeating structural units in addition to the repeating unit of the above formula (2). It is preferable to contain the diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage of the cured film accompanying ring closure can be suppressed.
  • SL diamine residue represented by the following formula
  • Z has an a structure and a b structure, and R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms). ), and a hydrocarbon group (preferably having 1 to 6 carbon atoms R 2s is 1 to 10 carbon atoms, more preferably from 1 to 3 carbon atoms), R 3s, R 4s, R 5s, of R 6s At least one is an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the remainder is a hydrogen atom or 1 to 30 carbon atoms (preferably carbon atoms).
  • the polymerization of the a structure and the b structure may be block polymerization or random polymerization.
  • the a structure is preferably 5 to 95 mol%
  • the b structure is 95 to 5 mol%
  • 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 diamine residue represented by the formula (SL) When the diamine residue represented by the formula (SL) is included as another type of repeating structural unit, it remains after the removal of the acid dianhydride group from the tetracarboxylic dianhydride in terms of improving alkali solubility. It is preferable to include a tetracarboxylic acid residue as a repeating 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 degree of dispersion 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 to 100% by mass, more preferably 30 to 99% by mass, based on the total solid content of the composition. It is more preferably from -98% by mass, even more preferably from 50-95% by mass, even more preferably from 60-95% by mass, and even more preferably from 70-95% by mass.
  • the polymer precursor may contain only 1 type 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 contains a radically polymerizable compound having a sulfur atom.
  • a radically polymerizable compound having a sulfur atom is a radical having a sulfur atom having two or more (preferably 2 to 4, more preferably 2 to 3, more preferably 2) radically polymerizable groups. It is a polymerizable compound.
  • the radically polymerizable compound having a sulfur atom is preferably a compound represented by the following formula (3-1).
  • L 11 represents a divalent linking group containing a sulfur atom
  • X 11 and X 12 each independently represent a single bond or a divalent linking group
  • R 11 And R 12 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one of R 11 and R 12 represents a monovalent organic group containing at least one radical polymerizable group; R 11 And R 12 may be bonded to each other to form a ring.
  • L 11 represents a divalent linking group containing a sulfur atom.
  • a linking group having 1 or 2 sulfur atoms is preferable, and a linking group having 2 to 6 atoms having 1 or 2 sulfur atoms and an oxygen atom is more preferable. More preferably, it has the same meaning as L 1 in formula (3-2) described later, and the preferred range is also the same.
  • X 11 and X 12 each independently represent a single bond or a divalent linking group.
  • the divalent linking group include a linear or branched alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and particularly preferably 1 to 6), and an aromatic group (preferably having 6 to 22 carbon atoms). , 6-14 are more preferable, and 6-10 are particularly preferable), —O—, —S—, —C ( ⁇ O) —, —NR 3 —, —NR 3 CO—, and combinations thereof Groups.
  • R 3 has the same meaning as R 3 in formula (3-2) described later.
  • the linking group may be a hydrocarbon group.
  • the hydrocarbon group may be an oligohydrocarbon group, and the number of repetitions at that time is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6.
  • the hydrocarbon group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms.
  • the number of atoms of the linking group is preferably 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6 when it is other than an oligohydrocarbon group.
  • the number of atoms is preferably 2 to 64, more preferably 2 to 32, and particularly preferably 2 to 18.
  • the divalent linking group represented by X 11 and X 12 is a divalent linking group containing an oxygen atom, sulfur atom or nitrogen atom (preferably having 1 to 12 atoms, more preferably 1 to 6 and more preferably 1 to 3 Is particularly preferable), and a divalent linking group containing an oxygen atom is more preferable.
  • R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group include a monovalent organic group containing a radical polymerizable group and a substituent T described later.
  • the radical polymerizable group include a group having a carbon-carbon unsaturated double bond.
  • the radically polymerizable group is preferably a group having a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group, and more preferably a group having an acryloyl group or a methacryloyl group.
  • acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, vinyl group, vinylphenyl group (o, m, p), vinylphenyloxy group (o, m , P) and vinylphenylmethyl groups (o, m, p) are preferred, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group are more preferred, acryloyloxy group, methacryloyloxy group Is more preferable.
  • the monovalent organic group containing a radical polymerizable group may be a group having only one radical polymerizable group or a group having two or more radical polymerizable groups.
  • the plurality of radical polymerizable groups may be the same as or different from each other.
  • the monovalent organic group containing a radically polymerizable group may further have a substituent described later as long as the effects of the present invention are not impaired. Examples of the substituent include a substituent T described later.
  • the number of radically polymerizable groups contained in one monovalent organic group is preferably 3 or less, and more preferably 2 or less. In this invention, the aspect in which the monovalent organic group containing a radically polymerizable group does not have a substituent is illustrated preferably.
  • R 11 and R 12 represents a monovalent organic group containing at least one radical polymerizable group. Among these, it is preferable that R 11 and R 12 are each independently a monovalent organic group containing a radical polymerizable group.
  • the number of radically polymerizable groups in one molecule is preferably 2 or more, more preferably 4 or less, and more preferably 3 or less. Two is more preferable.
  • R 11 and R 12 may be bonded to each other to form a ring.
  • R 11 and R 12 may be directly connected or may be connected via a connecting group L described later.
  • the ring formed may be condensed.
  • the linking group L is a linear or branched alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and particularly preferably 1 to 6), —O—, —S—, —C ( ⁇ O ) —, —NR 3 —, —NR 3 CO—, and combinations thereof.
  • R 3 has the same meaning as R 3 in formula (3-2) described later, and the preferred range is also the same.
  • the radically polymerizable compound having a sulfur atom is more preferably represented by the following formula (3-2).
  • L 1 represents —S—, —SS—, —S ( ⁇ O) —, or —S ( ⁇ O) 2 —
  • X 1 and X 2 are Each independently a single bond, —O—, —C ( ⁇ O) —, —C ( ⁇ O) O—, —OC ( ⁇ O) —, —S—, —S ( ⁇ O) 2 — or —NR 3 represents CO—
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a radical polymerizable group
  • La 1 to La 4 each independently represent a single bond, Any one of a group consisting of one or more combinations of an alkylene group and a phenylene group and a group consisting of a combination of one or more of an alkylene group and a phenylene group
  • R 3 is a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), or an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms). 2 to 3 are particularly preferable), an alkynyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, and 6 to 18 carbon atoms). More preferably, 6 to 10 is particularly preferable, and a hydrogen atom or an alkyl group having the above carbon number is preferable.
  • R 1 and R 2 are each independently a radically polymerizable group, a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms), a cycloalkyl group (carbon number 3 to 24 are preferable, 3 to 12 are more preferable, and 3 to 6 are particularly preferable.)
  • An aryl group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms is represented.
  • R 1 and R 2 are an alkyl group, a cycloalkyl group, or an aryl group, they may have an arbitrary substituent T as long as the effects of the present invention are not impaired.
  • the optional substituent T includes a branched or straight chain alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 and particularly preferably 1 to 6), and a cycloalkyl group (preferably having 3 to 24 carbon atoms).
  • 3 to 12 are more preferable, 3 to 6 are particularly preferable), a hydroxyl group, and a hydroxylalkyl group (1 to 24 carbon atoms are preferable, 1 to 12 are more preferable, and 1 to 6 are particularly preferable; the number of hydroxyl groups is 1 to 6 are preferable, 1 to 3 are more preferable, an amino group (preferably having a carbon number of 0 to 24, more preferably 0 to 12, and particularly preferably 0 to 6), and an aminoalkyl group (having 1 to 24 carbon atoms).
  • 1 to 12 is more preferable, and 1 to 6 is particularly preferable; the number of amino groups is preferably 1 to 6, more preferably 1 to 3, and a thiol group or thiolalkyl group (having 1 to 2 carbon atoms).
  • 1 to 12 is more preferable, and 1 to 6 is particularly preferable; the number of thiol groups is preferably 1 to 6, more preferably 1 to 3, and a carboxyl group or a carboxyalkyl group (preferably having 1 to 24 carbon atoms).
  • 1 to 12 is more preferable, and 1 to 6 is particularly preferable; the number of carboxyl groups is preferably 1 to 6, more preferably 1 to 3, and acyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms).
  • acyloxy groups preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms
  • R 1 and R 2 represents a radical polymerizable group.
  • R 1 and R 2 examples include the same groups as those exemplified in the above formula (3-1).
  • R 1 and R 2 are preferably each independently a radical polymerizable group, and more preferably the same radical polymerizable group.
  • La 1 to La 4 each independently represents a single bond, a group consisting of one or a combination of two or more of an alkylene group and a phenylene group, and one of an alkylene group and a phenylene group. Alternatively, it represents one of a group consisting of a combination of two or more and —O—.
  • La 1 to La 4 each independently represents a single bond, an alkylene group (preferably having a carbon number of 1 to 24, more preferably 1 to 12, and particularly preferably 1 to 6), a phenylene group, an (oligo) oxyalkylene group ( The alkylene group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6.
  • the repeating number is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • (Oligo) alkyleneoxy group (the alkylene group preferably has 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms, preferably 1 to 12 repeating units, more preferably 1 to 6 carbon atoms, 1 to 6 carbon atoms). 3 is particularly preferred.) Or a combination thereof may be present.
  • the (oligo) oxyalkylene group means an oxyalkylene group or an oligooxyalkylene group. The same applies to other groups containing the description “(oligo)”.
  • the alkylene group, phenylene group, (oligo) oxyalkylene group, and (oligo) alkyleneoxy group may further have the optional substituent T as long as the effects of the present invention are not impaired.
  • La 1 to La 4 are more preferably each independently a single bond or an alkylene group, more preferably La 2 and La 3 are a single bond, and La 1 and La 4 are alkylene groups. .
  • R 1 and R 2 may be bonded to each other to form a ring.
  • R 1 and R 2 may be directly connected or connected via the connecting group L.
  • the ring formed may be condensed.
  • the radically polymerizable compound having a sulfur atom used in the present invention may be a low molecule (for example, a molecular weight of less than 2000 or even less than 1000) or a polymer, but is preferably a low molecule.
  • radical polymerizable compound having a sulfur atom examples include the following exemplary compounds, but the present invention is not construed as being limited thereto.
  • the following compounds 301, 302, 303, 304, 312, and 322 are preferable, 301 and 302 (compounds represented by formula (4)) are more preferable, and 302 is particularly preferable.
  • m is 1 to 30, and n is 1 to 30.
  • the content of the radically polymerizable compound having a sulfur atom in the photosensitive resin composition of the present invention is preferably 0.001% by mass or more as a lower limit with respect to the total solid content of the composition, and is 0.005% by mass. % Or more, more preferably 0.01% by weight or more, still more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, and 0% More preferably, the content is 3% by mass or more.
  • the blending amount of the radically polymerizable compound having a sulfur atom with respect to 100 parts by mass of the polymer precursor is the sum of the other polymerizable compounds to be described later, and is preferably 70 parts by mass or less, and 60 parts by mass or less as the polymerizable compound. Is more preferably 55 parts by mass or less, still more preferably 50 parts by mass or less, and particularly preferably 45 parts by mass or less.
  • the polymerizable compound is preferably 0.1 part by mass or more, and may be 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, and 10 parts by mass or more.
  • the ratio of the radical polymerizable compound having a sulfur atom in the total polymerizable compound including other polymerizable compounds described later is preferably 0.01% by mass or more, more preferably 0.02% by mass or more as a lower limit value. 0.1 mass% or more is further more preferable, 0.3 mass% or more is more preferable, and 0.5 mass% or more is still more preferable.
  • 100 mass% or less is preferable, 50 mass% or less, 30 mass% or less, 20 mass% or less, 10 mass% or less, 7 mass% or less, 5 mass% or less, 2 mass% or less, 1 mass% or less. It may be.
  • a radically polymerizable compound having a sulfur atom in the composition in the above-described proportion, higher stability and higher exposure sensitivity can be achieved.
  • the radically polymerizable compound having a sulfur atom may contain only one kind or two or more kinds. When 2 or more types are included, the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention contains a radical photopolymerization initiator.
  • a radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators.
  • a photo radical polymerization 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 IRGACURE 907, 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).
  • the photo radical polymerization initiator include oxime compounds.
  • 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. 2000-80068, 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.
  • this oxime photopolymerization initiator it is particularly preferable to use this oxime photopolymerization initiator.
  • the oxime-based photopolymerization initiator has a linking group of> C ⁇ N—O—C ( ⁇ O) — in the molecule.
  • IRGACURE OXE 01, IRGACURE OXE 02 (manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA, photo radical polymerization initiator 2 described in JP 2012-14052 A) are also suitable as commercial products. Used for.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 can also be used.
  • DFI-091 (manufactured by Daitokemix Co., Ltd.) can be used. Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP2010-262028A, compounds 24 described in paragraph 0345 of JP-T-2014-500852, and paragraphs 0347-0348. And compounds (C-3) described in paragraph 0101 of JP2013-164471A, and the like. As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
  • 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 alkoxy group having 1 to 12 carbon atoms, a phenyl group, An alkyl group having 1 to 20 carbon atoms, an alkoxy 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 biphenylyl,
  • R I01 is a group represented by formula (II), the same as R I00 R I02 to R I04 are each independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
  • radical photopolymerization initiator compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can be used.
  • the content of the radical photopolymerization initiator 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, the content is 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass.
  • the radical photopolymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more kinds of radical photopolymerization initiators are contained, the total is preferably in the above 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-2008-63554.
  • 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 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 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 depending on 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 photosensitive resin composition of the present invention also contains a radical polymerizable compound not containing a sulfur atom (hereinafter also referred to as “a polymerizable monomer not containing a sulfur atom”) in addition to the radical polymerizable compound containing a sulfur atom. Is preferred. By setting it as such a structure, the cured film excellent in heat resistance can be formed.
  • a compound having a radical polymerizable group can be used as the polymerizable monomer not containing a sulfur atom.
  • the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and an allyl group.
  • the radical polymerizable group is preferably a (meth) acryloyl group.
  • the number of radical polymerizable groups contained in the polymerizable monomer not containing a sulfur atom may be one or two or more, but the polymerizable monomer not containing a sulfur atom may have two or more radical polymerizable groups. It is preferable to have three or more.
  • 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 polymerizable monomer containing no sulfur atom 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 polymerizable monomer is preferably 100 or more.
  • the photosensitive resin composition of the present invention preferably contains at least one polymerizable monomer that contains two or more polymerizable groups and does not contain a bifunctional or higher functional sulfur atom, and preferably has a trifunctional or higher functional sulfur. More preferably, it contains at least one polymerizable monomer containing no atoms. Moreover, the mixture of the polymerizable monomer which does not contain a bifunctional sulfur atom, and the polymerizable monomer which does not contain a trifunctional or more than trifunctional sulfur atom may be sufficient.
  • the functional group number of the polymerizable monomer which does not contain a sulfur atom means the number of radically polymerizable groups in one molecule.
  • the polymerizable monomer containing no sulfur atom include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group or an amino group with a monofunctional or polyfunctional isocyanate or epoxy, or a monofunctional or polyfunctional carboxylic acid.
  • a dehydration condensation reaction product with an acid or the like is also preferably used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate group or epoxy group with monofunctional or polyfunctional alcohols or amines, and removal of halogen groups or the like are also suitable.
  • a substitution reaction product of an unsaturated carboxylic acid ester or amide having a releasable substituent with a monofunctional or polyfunctional alcohol or amine is also suitable.
  • the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
  • the polymerizable monomer containing no sulfur atom 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.
  • polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490. it can. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970.
  • polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be exemplified.
  • a polymerizable monomer not containing a sulfur atom other than those described above it has a fluorene ring described in JP 2010-160418 A, JP 2010-129825 A, JP 4364216 A, and the like, and is ethylenic.
  • a compound having two or more groups having an unsaturated bond, or a cardo resin can also be used.
  • Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493.
  • vinyl phosphonic acid compounds Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used.
  • 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.
  • Examples of the polymerizable monomer containing no sulfur atom include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd., A-TMMT: Shin-Nakamura Chemical Co., Ltd., dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; Nippon Kayaku Co., Ltd.), di Pentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are ethylene glycol, propylene Structures linked via glycol residue
  • Examples of commercially available polymerizable monomers that do not contain sulfur atoms include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, and Sartomer, a bifunctional methacrylate having four ethyleneoxy chains.
  • SR-209 manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, TPA-330, a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA- 40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306 (Manufactured by Kyoeisha Chemical (Co.)) AH-600, T-600, AI-600, Blemmer PME400 (manufactured by NOF Corporation) and the like.
  • polymerizable monomers include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Also suitable are urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Further, as polymerizable monomers containing no sulfur atom, compounds having an amino structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 Can also be used.
  • the polymerizable monomer containing no sulfur atom may be a polymerizable monomer having an acid group such as a carboxyl group or a phosphoric acid group.
  • the polymerizable monomer 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. More preferred is a polymerizable monomer.
  • the aliphatic polyhydroxy compound is pentaerythritol and / or diester. It is a compound that is pentaerythritol.
  • examples of commercially available products include M-510, M-520 and the like as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the polymerizable monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used.
  • a preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
  • a monofunctional polymerizable monomer can be preferably used as a polymerizable monomer that does not contain a sulfur atom from the viewpoint of suppressing warpage accompanying the control of the elastic modulus of the cured film.
  • Monofunctional polymerizable monomers 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.
  • N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Goods and the like are preferably used.
  • the monofunctional polymerizable monomer 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 4 represents a t-valent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7.
  • R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 7 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.
  • the occurrence of cracks can be more effectively suppressed when the photosensitive resin composition is applied to a substrate having irregularities. Moreover, it is excellent in pattern workability and can form the cured film which has high heat resistance from which 5 mass% reduction temperature becomes 350 degreeC or more, More preferably, it is 380 degreeC or more.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML- PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC MX -290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diaxymethyl-p-cresol, etc. .
  • 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, NIKACALAC 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 repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane. However, it is not limited to these.
  • 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 DIC Corporation), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nippon Rika Co., Ltd.), EP- 003S, EP-4000S (trade names, Co., Ltd.
  • 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 suitably used, and these are used alone. Or you may mix 2 or more types.
  • a benzoxazine compound (compound having a 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 A dihydrobenzoxazine compound is mentioned. These may be used alone or in combination of two or more.
  • the content of the polymerizable compound other than the radically polymerizable compound having a sulfur atom is preferably 0 to 60% by mass 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 and even more preferably 30% by mass or less.
  • Other polymerizable compounds may be used alone or in combination of two or more. 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 JP2013-15701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711A, and JP2011-95956A.
  • 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, 1,4-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
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication 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 preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is particularly preferable. 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 JP2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252A. Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
  • the content of the metal adhesion improving agent is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and particularly 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 base generator.
  • the base generator may be a thermal base generator or a photobase generator.
  • thermal base generator The type of the thermal base generator is not particularly defined, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of the above.
  • pKa1 represents a logarithmic representation ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
  • the thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. It is preferable to contain. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can promote the cyclization reaction of the polymer precursor, thereby cyclizing the polymer precursor. Can be performed at low temperatures.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
  • the upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower.
  • the lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, so that a polymer precursor having excellent stability can be prepared.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polymer precursor can be lowered.
  • the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
  • the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine is highly basic, the cyclization temperature of the polymer precursor can be further lowered.
  • the base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 140 ° C. or higher.
  • the molecular weight of the generated base is preferably 80 to 2000.
  • the lower limit is more preferably 100 or more.
  • the upper limit is more preferably 500 or less.
  • the molecular weight value is a theoretical value obtained from the structural formula.
  • the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.
  • the ammonium salt (A2) is preferably an acidic compound.
  • the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
  • the ammonium salt used as the thermal base generator is preferably a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion.
  • the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R N1 to R N6 each independently represent a hydrogen atom or a hydrocarbon group (preferably having a carbon number of 1 to 36, more preferably 1 to 24, and particularly preferably 1 to 12), and an alkyl group (the number of carbon atoms) 1 to 36 are preferred, 1 to 24 are more preferred, 1 to 23 are particularly preferred, an alkenyl group (preferably having a carbon number of 2 to 36, more preferably 2 to 24, particularly preferably 2 to 23), an alkynyl group ( 1 to 36 carbon atoms are preferable, 1 to 24 are more preferable, and 1 to 23 are particularly preferable, and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms) are preferable.
  • RN7 represents a hydrocarbon group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12), and is preferably an alkylidene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12).
  • R N1 and R N2 , R N3 and R N4 , R N5 and R N6 , and R N5 and R N7 may be bonded to each other to form a ring.
  • the linking group L or a hetero linking group Lh described later may be interposed in the middle of the ring.
  • R N1 to R N7 may have the above-described substituent T as long as the effects of the present invention are not impaired.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-6).
  • R N101 is Nn number (Nn is an integer of 1 to 12) represents an organic group, Nn-valent group (C 1 - which are based on alkane 12 is preferable, 1 to 6 is more preferable, and 1 to 3 is particularly preferable.
  • RN101 is preferably an aromatic hydrocarbon group.
  • RN101 may have the above-described substituent T as long as the effects of the present invention are not impaired.
  • RN101 is an alkane-based group or an alkene-based group
  • the following hetero-linking group Lh may be interposed.
  • R N1 and R N7 are the same meaning as R N1 and R N7 in formula (101) or formula (102).
  • RN8 is an alkyl group (preferably having 1 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, particularly preferably 4 to 18 carbon atoms), and an alkenyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms).
  • an alkynyl group (preferably 2 to 36 carbon atoms, more preferably 2 to 24 carbon atoms, particularly preferably 4 to 18 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 To 10 is particularly preferred).
  • the alkyl group, the alkenyl group, the alkynyl group, and the aryl group may have a linking group Lh having a hetero atom in the middle of the chain or in connection with the mother nucleus.
  • Examples of the linking group Lh having a hetero atom include linking groups relating to —O—, —S—, —C ( ⁇ O) —, —NR 3 —, or a combination thereof.
  • the number of linking groups Lh having a hetero atom is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3.
  • R 3 is a hydrogen atom or an alkyl group (preferably a methyl group).
  • RN8 may further have the above-described substituent T as long as the effects of the present invention are not impaired.
  • R N9 is preferably a group having the same meaning as R N8 .
  • an aryl group-containing group is preferable, an aryloyl group-containing group is more preferable, and an aryloylalkyl group (the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms). preferable.
  • Ar N101 and Ar N102 each independently represent an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms).
  • Nn represents an integer of 1 to 12.
  • Nm represents an integer of 0 to 5. No is preferably an integer of 1 to 12, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 3.
  • R N1 , R N1 and R N8 , R N1 and R N7 , R N1 and R N9 , R N1 and Ar N101 , R N1 and Ar N102 , Ar N101 and Ar N102 are bonded to form a ring, respectively. Also good.
  • the linking group L or a hetero linking group Lh described later may be interposed in the middle of the ring.
  • the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the lower limit is preferably 0.5 or more, and more preferably 1.0 or more. If the pKa1 of the anion is in the above range, the polymer precursor can be cyclized at a lower temperature, and further the stability of the composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the composition is good.
  • the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less.
  • pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the stability of the composition can be further improved.
  • pKa1 indicates a logarithmic representation ( ⁇ Log10Ka) of the dissociation constant (Ka) of the first proton of a polyvalent acid, and is determined of Organic Structures by Physical Methods (author: Brown, HC, McDanel). , D. H., Hafliger, O., Nachod, F. C .; Compilation: Braude, E. A., Nachod, F. C .; Academic Press, New York, 1955), Data for Biochemical (Author). Dawson, RMC et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
  • the carboxylate anion is preferably represented by the following formula (X1).
  • 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. 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).
  • an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 3 carbon atoms
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6 carbon atoms
  • 10 represents a hydroxyl group or a carboxyl group.
  • R X1 of formula (EWG-1), is not R X1 of formula (EWG-4) is a carboxyl group.
  • Ar represents an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly 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 or the hetero linking group Lh described later is interposed in the middle of the ring. It may be.
  • R x1 to R x3 are an alkyl group, an alkenyl group, or an aryl group
  • 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).
  • Np is preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1 or 2.
  • the carboxylate anion is also preferably represented by the following formula (XA).
  • L 10 is a single bond or an alkylene group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) or an alkenylene group (having 2 to 12 carbon atoms).
  • an aromatic group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and particularly preferably 6 to 10
  • the carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion.
  • the thermal base generator can be referred to the descriptions in paragraphs 0021 to 0077 of JP-A-2016-027357, the contents of which are incorporated herein. Examples of the thermal base generator include the following compounds.
  • the content of the thermal base generator in the composition is preferably 0.1 to 50% by mass relative to the total solid content of the composition.
  • the lower limit is more preferably 0.25% by mass or more, and further preferably 0.5% by mass or more.
  • the upper limit is more preferably 20% by mass or less, and further preferably 10% 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.
  • a configuration that does not substantially contain a thermal base generator may be employed. “Substantially free” means that the total solid content of the composition is less than 0.1% by mass, further 0.01% by mass or less, and particularly 0.001% by mass or less. it can.
  • the photosensitive resin composition used in the present invention may contain a photobase generator.
  • a photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure.
  • the base (basic substance) ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst when the polymer precursor is cured by heating, it can be suitably used for development.
  • photobase generators can be used.
  • M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci.
  • An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or an oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound can be mentioned.
  • the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
  • the generated basic substance is preferably a compound having an amino group having a higher basicity. This is because such a compound has a strong catalytic effect on a dehydration condensation reaction or the like in imidation of a polymer precursor, and a catalytic effect in a dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. . That is, since the catalytic effect of the generated basic substance is large, the apparent sensitivity as the photosensitive resin composition is improved. From the viewpoint of the catalytic effect, the basic substance is preferably amidine or an aliphatic amine.
  • the photobase generator used in the present invention preferably contains an aromatic ring and the generated basic substance is a compound having an amino group.
  • Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open Nos. 2009-80452 and 2009/123122.
  • a photobase generator having a carbamate structure as disclosed in Japanese Patent No. 189591 and Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure as disclosed in Japanese Patent Application Laid-Open No. 2007-249013 and Japanese Patent Application Laid-Open No. 2008-003581 Examples include photobase generators having a carbamoyloxime structure, but are not limited thereto, and other known photobase generator structures can be used.
  • photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019, and the compound described in paragraph 0052 of WO2010 / 064631.
  • photobase generators 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. Moreover, the following compound is illustrated as a photobase generator. Et represents an ethyl group, and Me represents a methyl group.
  • the content of the photobase generator in the composition is preferably 0.1 to 50% by mass relative 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 photobase generator. When using 2 or more types, it is preferable that a total amount is the said range.
  • a configuration that does not substantially contain a photobase generator may be employed. “Substantially free” means that the total solid content of the composition is less than 0.1% by mass, further 0.01% by mass or less, and particularly 0.001% by mass or less. it can.
  • the photosensitive resin composition of the present invention is various additives, for example, a thermal acid generator, a sensitizing dye, a chain transfer agent, a surfactant, a high grade, as necessary, as long as the effects of the present invention are not impaired.
  • Fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • 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 particularly preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
  • One type of thermal acid 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 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, 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 for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention.
  • 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is more preferable.
  • 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 of surfactants may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability.
  • 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 particularly 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 particularly 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 content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • 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 filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more 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. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination.
  • Various materials may be filtered a plurality of times.
  • circulation filtration may be used.
  • 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.
  • the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the cured film of the present invention is formed by curing the photosensitive resin composition of the present invention.
  • the 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.
  • a laminate may be obtained by laminating two or more cured films of the present invention.
  • 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, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
  • 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 layer, a photosensitive resin composition layer forming step, an exposure step of exposing the photosensitive resin composition layer, and the exposed photosensitivity.
  • the manufacturing method of a cured film which has the image development process process which performs image development processing with respect to a conductive resin composition layer (resin layer) is mentioned.
  • the photosensitive resin composition of the present invention is preferably used when developing.
  • the manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention.
  • the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed again. It is preferable to repeat in order.
  • the photosensitive resin composition layer forming step, the exposure step, and the development processing step are preferably performed 2 to 5 times in the above order (that is, 3 to 6 times in total).
  • a laminated body can be obtained by laminating a cured film.
  • the manufacturing method which concerns on preferable embodiment of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies the photosensitive resin composition to a board
  • 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 the laminated body of this invention may include the process of drying in order to remove a solvent, after forming the photosensitive resin composition layer.
  • 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 the laminated body 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 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.
  • exposure with a high-pressure mercury lamp is particularly preferable, and i-line exposure is particularly preferable. Thereby, particularly high exposure sensitivity can be obtained.
  • the manufacturing method of the laminated body of this invention may also include the image development process process which performs image development processing with respect to 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.
  • the developer preferably contains an organic solvent having a ClogP of ⁇ 1 to 5, more preferably an organic solvent having a ClogP of 0 to 3.
  • ClogP can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
  • 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.
  • the developer is preferably 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and even more preferably 90% by mass or more of 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 at the time of development is not particularly defined, but it can usually be carried out at 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 manufacturing method of the laminated body of this invention includes the process heated after image development. In the heating step, the cyclization reaction of the polymer precursor proceeds. Moreover, although the composition of this invention contains radically polymerizable compounds other than a polymer precursor, hardening of radically polymerizable compounds other than an unreacted polymer precursor also advances.
  • the heating temperature is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and further preferably 160 to 350 ° C.
  • 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 after the drying is, for example, 30 to 200 ° C. lower than the boiling point of the solvent contained in the photosensitive resin composition. It is preferable that the temperature is gradually raised.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly 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 laminate 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 (cured film) after the development treatment.
  • a metal layer forming step of forming a metal layer on the surface of the photosensitive resin composition layer (cured film) 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.
  • a lamination process is a series of processes including performing the said photosensitive resin composition layer formation process, the said exposure process, and the said image development process again in the said order again. 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 exposure process or after 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 layer forming step, the exposure step, and the development processing step are performed in the above order so as to cover the metal layer. Is preferred. By alternately performing the lamination process of laminating the photosensitive resin composition layer (resin layer) and the metal layer forming process, 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 forming an interlayer insulating film for a rewiring layer refer to the description in paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein.
  • the polyimide precursor solid was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water, the polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 3 days.
  • This polyimide precursor had a weight average molecular weight of 27400 and a number average molecular weight of 10100.
  • the polyimide precursor solid was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water, the polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 3 days. This polyimide precursor had a weight average molecular weight of 23100 and a number average molecular weight of 9700.
  • reaction mixture was then cooled to ⁇ 10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at ⁇ 10 ° C.
  • SOCl 2 was added over 60 minutes while maintaining the temperature at ⁇ 10 ° C.
  • a solution of 20.1 g of 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl dissolved in 100 mL of N-methylpyrrolidone at ⁇ 10 ° C. was added dropwise to the reaction mixture over 60 minutes and the mixture was stirred for 2 hours before adding 20 mL of ethyl alcohol.
  • the polyimide precursor solid was filtered and dissolved in 380 g of tetrahydrofuran. The obtained solution was poured into 6 liters of water, the polyimide precursor was precipitated in water, filtered, and dried at 45 ° C. under reduced pressure for 3 days.
  • This polyimide precursor had a weight average molecular weight of 23200 and a number average molecular weight of 9600.
  • This polybenzoxazole precursor had a weight average molecular weight of 25800 and a number average molecular weight of 9300.
  • the obtained organic layer was washed 5 times with distilled water, and then the low boiling point solvent was removed with an evaporator to obtain 220.1 g of a radical polymerizable compound B1-1.
  • the obtained compound is the exemplary compound 302 of the above-mentioned radical polymerizable compound having a sulfur atom.
  • the obtained organic layer was washed 5 times with distilled water, and then the low boiling point solvent was removed with an evaporator to obtain 200.2 g of a radical polymerizable compound B1-2.
  • the obtained compound is an exemplary compound 312 of the above-mentioned radical polymerizable compound having a sulfur atom.
  • the obtained organic layer was washed 5 times with distilled water, and then the low boiling point solvent was removed with an evaporator to obtain 220.1 g of a radical polymerizable compound B1-3.
  • the obtained compound is an exemplary compound 322 of the above-mentioned radical polymerizable compound having a sulfur atom.
  • ⁇ Measurement method of molecular weight About the molecular weight (weight average molecular weight, number average molecular weight) of said polymer precursor, it defined as a polystyrene conversion value according to gel permeation chromatography (GPC method). Specifically, HLC-8220 (trade name: manufactured by Tosoh Corporation) is used, and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (trade names) are used as columns. : Manufactured by Tosoh Corporation). The eluent was measured using THF (tetrahydrofuran). For detection, a UV ray (ultraviolet) wavelength 254 nm detector was used. In addition, unless otherwise indicated, all the molecular weights prescribed
  • ⁇ Storage stability 10 g of the photosensitive resin composition was sealed in a container (container material: light-shielding glass, capacity: 100 mL), and allowed to stand in an environment of 25 ° C. and a relative humidity of 65%. Stability was evaluated by the time until a solid was precipitated from the photosensitive resin composition. The longer the time until precipitation, the higher the stability of the photosensitive resin composition, which is a favorable result. For solid precipitation, three samples stored in a container were prepared for one type of photosensitive resin composition, and one sample container was opened when 30 days, 60 days, and 120 days had elapsed.
  • the entire amount of the photosensitive resin composition as the content was pressure filtered with a mesh having a pore diameter of 0.8 ⁇ m, and the presence or absence of foreign matter on the mesh was visually observed, and the presence or absence of precipitates was determined as follows.
  • D Solid precipitated within 30 days.
  • the photosensitive resin composition was applied by spinning on a silicon wafer.
  • the silicon wafer coated with the photosensitive resin composition was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform film having a thickness of 10 ⁇ m on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed using an aligner (manufactured by SUSS MICROTEC AG, Karl-Suss MA150 [trade name]).
  • the exposure was performed with a high-pressure mercury lamp, and the exposure energy required to cure the 10 ⁇ m uniform film at a wavelength of 365 nm was measured. The lower the exposure energy, the higher the sensitivity and the better result.
  • B2 Radical polymerizable compound (all are trade names) B2-1: NK ester M-40G (manufactured by Shin-Nakamura Chemical Co., Ltd.) B2-2: SR-209 (Sartomer) B2-3: NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) B2-4: A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • C Photoradical polymerization initiator (both are trade names)
  • C-1 IRGACURE OXE 01 (manufactured by BASF)
  • C-2 IRGACURE OXE 02 (manufactured by BASF)
  • C-3 IRGACURE OX 04 (manufactured by BASF)
  • C-4 IRGACURE-784 (manufactured by BASF)
  • C-5 NCI-831 (manufactured by ADEKA Corporation)
  • Et represents an ethyl group.
  • Example 1 As is clear from the results in Table 1 above, it was found that when a radically polymerizable compound having a sulfur atom was used, it was excellent in storage stability and high sensitivity (Examples 1 to 16). In particular, as shown in Example 20, even when a radically polymerizable compound having a trace amount of sulfur atom is blended, the superiority of the present invention can be seen in that excellent storage stability and high sensitivity are achieved. On the other hand, when no radical polymerizable compound having a sulfur atom was added, the sensitivity was low (Comparative Examples 1 to 3).
  • Example 100> Using the photosensitive resin composition of Example 1, the photosensitive resin composition was applied on a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 ⁇ m on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (NSR 2005 i9C [trade name] manufactured by Nikon Corporation), and the exposed photosensitive resin composition layer. The (resin layer) was developed with cyclopentanone for 60 seconds to form a 10 ⁇ m diameter hole.
  • NSR 2005 i9C trade name
  • the temperature was increased at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours.
  • a thin copper layer (metal layer) having a thickness of 2 ⁇ m was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion.
  • the same kind of photosensitive resin composition is used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the patterned film is heated for 3 hours from the filtration of the photosensitive resin composition in the same manner as described above.
  • the procedure up to was performed again, and a laminate composed of a resin layer / metal layer / resin layer was produced.
  • This interlayer insulation film for rewiring layers was excellent in insulation. Moreover, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problem.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Laminated Bodies (AREA)
  • Polyamides (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

L'invention concerne : une composition de résine photosensible qui présente une excellente stabilité au stockage, tout en présentant une sensibilité élevée ; et un film durci, un stratifié, un procédé de production d'un film durci, et un dispositif à semi-conducteur, dont chacun utilise cette composition de résine photosensible. L'invention concerne également un nouveau composé qui est utilisé dans le but de former une composition de résine photosensible. Une composition de résine photosensible qui contient : un précurseur de polymère qui est choisi parmi des précurseurs de polyimide et des précurseurs de polybenzoxazole ; un composé polymérisable par voie radicalaire ayant un atome de soufre ; un initiateur de photopolymérisation radicalaire ; et un solvant.
PCT/JP2018/021347 2017-06-06 2018-06-04 Composition de résine photosensible, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et composé Ceased WO2018225676A1 (fr)

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JP2019523520A JP6808831B2 (ja) 2017-06-06 2018-06-04 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイスおよび化合物
CN201880037130.9A CN110741318B (zh) 2017-06-06 2018-06-04 感光性树脂组合物、固化膜、层叠体、固化膜的制造方法及半导体装置

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WO2020226131A1 (fr) * 2019-05-08 2020-11-12 富士フイルム株式会社 Composition de résine durcissable, film durci ainsi que procédé de fabrication de celui-ci, stratifié, et dispositif à semi-conducteurs
WO2020226132A1 (fr) * 2019-05-08 2020-11-12 富士フイルム株式会社 Composition de résine durcissable, film durci ainsi que procédé de fabrication de celui-ci, stratifié, et dispositif à semi-conducteurs
JPWO2021020463A1 (fr) * 2019-07-29 2021-02-04
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WO2022145136A1 (fr) * 2020-12-28 2022-07-07 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, dispositif semi-conducteur, et composé
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KR102767265B1 (ko) * 2022-01-12 2025-02-11 삼성에스디아이 주식회사 네거티브 감광성 수지 조성물, 이를 이용하여 제조된 절연막 및 반도체 디바이스

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090126370A (ko) * 2008-06-04 2009-12-09 주식회사 동진쎄미켐 반응성 단량체, 이의 제조방법 및 이로부터 얻어진포지티브형 감광성 폴리이미드 전구체
JP2012141447A (ja) * 2010-12-28 2012-07-26 Nippon Zeon Co Ltd 感光性ポリイミド前駆体及び感光性樹脂組成物
JP2015151405A (ja) * 2014-02-10 2015-08-24 日立化成デュポンマイクロシステムズ株式会社 ポリイミド前駆体を含む樹脂組成物、硬化膜の製造方法及び電子部品
JP2017049382A (ja) * 2015-08-31 2017-03-09 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネル
WO2017043474A1 (fr) * 2015-09-11 2017-03-16 富士フイルム株式会社 Procédé de production d'un matériau précurseur de polymère contenant un hétérocycle et application associée
WO2018043250A1 (fr) * 2016-08-29 2018-03-08 東レ株式会社 Composition de résine photosensible, film durci, dispositif d'affichage el organique, composant électronique semi-conducteur, et dispositif à semi-conducteur

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0675411A1 (fr) * 1994-03-31 1995-10-04 Hitachi Chemical Company, Ltd. Composition à base de résine photosensible et film photosensible avec cette composition
JP5874904B2 (ja) * 2010-12-15 2016-03-02 Jsr株式会社 液晶表示素子の製造方法
JP6136486B2 (ja) 2013-04-08 2017-05-31 日立化成デュポンマイクロシステムズ株式会社 樹脂組成物及びそれを用いたパターン形成方法
JP6451065B2 (ja) * 2014-03-27 2019-01-16 住友ベークライト株式会社 感光性樹脂組成物、硬化膜、保護膜、絶縁膜および電子装置
JP6167089B2 (ja) * 2014-03-27 2017-07-19 富士フイルム株式会社 感光性樹脂組成物、硬化膜、硬化膜の製造方法および半導体デバイス
JP6426563B2 (ja) * 2015-08-31 2018-11-21 富士フイルム株式会社 感光性組成物、硬化膜の製造方法、液晶表示装置の製造方法、有機エレクトロルミネッセンス表示装置の製造方法、およびタッチパネルの製造方法
US10802401B2 (en) * 2015-09-30 2020-10-13 Toray Industries, Inc. Negative-type photosensitive resin composition, cured film, element and display apparatus that include cured film, production method for the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090126370A (ko) * 2008-06-04 2009-12-09 주식회사 동진쎄미켐 반응성 단량체, 이의 제조방법 및 이로부터 얻어진포지티브형 감광성 폴리이미드 전구체
JP2012141447A (ja) * 2010-12-28 2012-07-26 Nippon Zeon Co Ltd 感光性ポリイミド前駆体及び感光性樹脂組成物
JP2015151405A (ja) * 2014-02-10 2015-08-24 日立化成デュポンマイクロシステムズ株式会社 ポリイミド前駆体を含む樹脂組成物、硬化膜の製造方法及び電子部品
JP2017049382A (ja) * 2015-08-31 2017-03-09 富士フイルム株式会社 感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置、有機エレクトロルミネッセンス表示装置およびタッチパネル
WO2017043474A1 (fr) * 2015-09-11 2017-03-16 富士フイルム株式会社 Procédé de production d'un matériau précurseur de polymère contenant un hétérocycle et application associée
WO2018043250A1 (fr) * 2016-08-29 2018-03-08 東レ株式会社 Composition de résine photosensible, film durci, dispositif d'affichage el organique, composant électronique semi-conducteur, et dispositif à semi-conducteur

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JPWO2020226131A1 (fr) * 2019-05-08 2020-11-12
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JPWO2020226132A1 (fr) * 2019-05-08 2020-11-12
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KR102697029B1 (ko) * 2019-07-29 2024-08-20 아사히 가세이 가부시키가이샤 네거티브형 감광성 수지 조성물, 폴리이미드의 제조 방법, 경화 릴리프 패턴의 제조 방법, 및 반도체 장치
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KR102279447B1 (ko) 2021-07-20
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