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WO2018225676A1 - Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor device and compound - Google Patents

Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor device and compound 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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WO
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
Application number
PCT/JP2018/021347
Other languages
French (fr)
Japanese (ja)
Inventor
健志 川端
健太 吉田
悠 岩井
渋谷　明規
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to JP2019523520A priority Critical patent/JP6808831B2/en
Priority to CN201880037130.9A priority patent/CN110741318B/en
Priority to KR1020197035583A priority patent/KR102279447B1/en
Publication of WO2018225676A1 publication Critical patent/WO2018225676A1/en
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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Abstract

Provided are: a photosensitive resin composition which has excellent storage stability, while exhibiting high sensitivity; and a cured film, a laminate, a method for producing a cured film, and a semiconductor device, each of which uses this photosensitive resin composition. Also provided is a novel compound which is used for the purpose of forming a photosensitive resin composition. A photosensitive resin composition which contains: a polymer precursor that is selected from among polyimide precursors and polybenzoxazole precursors; a radically polymerizable compound having a sulfur atom; a radical photopolymerization initiator; and a solvent.

Description

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Photosensitive resin composition, cured film, laminate, method for producing cured film, semiconductor device and compound

　本発明は、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に関する。 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.

　従来、半導体素子の保護膜および層間絶縁膜には優れた耐熱性と電気特性、機械特性等を併せ持つポリイミド樹脂が用いられている。しかし、近年半導体素子の高集積化、大型化が進む中、封止樹脂パッケージの薄型化小型化の要求がありＬＯＣ（リード・オン・チップ）や半田リフロー法を用いた表面実装などの方式が取られてきている。 Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics, and the like has been used for a protective film and an interlayer insulating film of a semiconductor element. However, in recent years, as semiconductor devices have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and methods such as surface mounting using LOC (lead-on-chip) or solder reflow methods are available. Has been taken.

　このような半導体素子の作製には、ポリイミド樹脂自身に感光性を付与した感光性樹脂組成物が用いられてきている。感光性樹脂組成物を用いることにより、パターン形成工程が簡略化できるためである。例えば、特許文献１には、（ａ）所定の構造を有するポリイミド前駆体と、（ｂ）活性光線照射によってラジカルを発生する化合物と、（ｃ）下記式（４ａ）または（４ｂ）で表される化合物と、（ｄ）溶剤とを含む樹脂組成物が開示されている。

Figure JPOXMLDOC01-appb-C000006
（式（４ａ）中、ｎａは３以下の整数である。式（４ｂ）中、Ｒ１０１およびＲ１０２は、各々独立に水素原子または１価の基である。ｍｂは９以下の整数である。）
　具体的に式（４ａ）または（４ｂ）で表される化合物として、トリプロピレングリコールジアクリレートまたはトリプロピレングリコール等が開示されている。 For the production of such a semiconductor element, 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. For example, in 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.
Figure JPOXMLDOC01-appb-C000006
 (In formula (4a), na is an integer of 3 or less. In formula (4b), R 101 and R 102 are each independently a hydrogen atom or a monovalent group. Mb is an integer of 9 or less. .)
Specifically, tripropylene glycol diacrylate, tripropylene glycol or the like is disclosed as a compound represented by the formula (4a) or (4b).

特開２０１４－２０１６９５号公報JP 2014-201695 A

　しかしながら、上記特許文献１に記載の組成物は、必ずしも、光に対する感度が高いとは言えないことが分かった。また、感光性樹脂組成物を一定時間保存した後、硬化膜とする場合、感光性樹脂組成物の保存安定性も求められる。
　本発明は、上記課題を解決することを目的とするものであって、保存安定性に優れ、感度の高い感光性樹脂組成物、ならびに、これを用いた、硬化膜、積層体、硬化膜の製造方法および半導体デバイスを提供することを目的とする。また、上記感光性樹脂組成物を製造するための化合物を提供することを目的とする。 However, it has been found that 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.

　上記課題のもと、本発明者が鋭意検討を行った結果、感光性樹脂組成物に、硫黄原子を有するラジカル重合性化合物を配合することにより、上記課題を解決しうることを見出した。具体的には、下記手段＜１＞により、好ましくは＜２＞～＜２２＞により、上記課題は解決された。
＜１＞ポリイミド前駆体およびポリベンゾオキサゾール前駆体から選択されるポリマー前駆体と、硫黄原子を有するラジカル重合性化合物と、光ラジカル重合開始剤と、溶剤とを含む感光性樹脂組成物。
＜２＞上記ポリマー前駆体が、下記式（１）で表される繰り返し単位または式（２）で表される繰り返し単位を含む、＜１＞に記載の感光性樹脂組成物；

Figure JPOXMLDOC01-appb-C000007
　式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、
　Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；
Figure JPOXMLDOC01-appb-C000008
 　式（２）中、Ｒ１２１は、２価の有機基を表し、Ｒ１２２は、４価の有機基を表し、Ｒ１２３およびＲ１２４は、それぞれ独立に、水素原子または１価の有機基を表す。
＜３＞上記ポリマー前駆体が、式（１）で表される繰り返し単位を含む、＜２＞に記載の感光性樹脂組成物。
＜４＞上記硫黄原子を有するラジカル重合性化合物が、下記式（３－１）で表される、＜１＞～＜３＞のいずれか１つに記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000009
 　式（３－１）中、Ｌ１１は、硫黄原子を含有する二価の連結基を表し、Ｘ１１およびＸ１２は、それぞれ独立に単結合、または、二価の連結基を表し、Ｒ１１およびＲ１２は、それぞれ独立に水素原子または一価の有機基を表す；ただし、Ｒ１１およびＲ１２の少なくとも一方が、少なくとも１つのラジカル重合性基を含む一価の有機基を表す；Ｒ１１およびＲ１２は互いに結合して環を形成していてもよい。
＜５＞上記式（３－１）が、下記式（３－２）で表される、＜４＞に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000010
 　式（３－２）中、Ｌ１は、－Ｓ－、－Ｓ－Ｓ－、－Ｓ（＝Ｏ）－、または、－Ｓ（＝Ｏ）２－を表し、Ｘ１およびＸ２は、それぞれ独立に単結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－ＯＣ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－または－ＮＲ３ＣＯ－を表し、Ｒ１およびＲ２は、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アリール基またはラジカル重合性基を表し、Ｌａ１～Ｌａ４は、それぞれ独立に、単結合、アルキレン基およびフェニレン基の１つまたは２つ以上の組み合わせからなる基、ならびに、アルキレン基およびフェニレン基の１つまたは２つ以上と－Ｏ－との組み合わせからなる基のいずれかを表す；Ｒ３は、水素原子またはアルキル基を表す；ただし、Ｒ１およびＲ２の少なくとも一方が、ラジカル重合性基である。
＜６＞上記Ｒ１およびＲ２は、その両方が、それぞれ独立にラジカル重合性基である、＜５＞に記載の感光性樹脂組成物。
＜７＞上記Ｘ１およびＸ２は、－Ｏ－である、＜５＞または＜６＞に記載の感光性樹脂組成物。
＜８＞上記Ｌ１は、－Ｓ（＝Ｏ）－である、＜５＞～＜７＞のいずれか１つに記載の感光性樹脂組成物。
＜９＞上記Ｒ１およびＲ２は、それぞれ独立にアクリロイル基またはメタクリロイル基を有する一価の有機基である、＜５＞～＜８＞のいずれか１つに記載の感光性樹脂組成物。
＜１０＞上記式（３－１）は、下記式（４）で表される、＜４＞に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000011
 式（４）中、Ｒは、水素原子またはメチル基である。
＜１１＞上記硫黄原子を有するラジカル重合性化合物を、上記感光性樹脂組成物に含まれる固形分の０．００１質量％以上の割合で含む、＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物。
＜１２＞さらに、硫黄原子を有するラジカル重合性化合物以外のラジカル重合性化合物を含む、＜１＞～＜１１＞のいずれか１つに記載の感光性樹脂組成物。
＜１３＞さらに、塩基発生剤を含む、＜１＞～＜１２＞のいずれか１つに記載の感光性樹脂組成物。
＜１４＞現像に用いられる、＜１＞～＜１３＞のいずれか１つに記載の感光性樹脂組成物。
＜１５＞有機溶剤を含む現像液を用いて現像する用途に用いられる、＜１＞～＜１４＞のいずれか１つに記載の感光性樹脂組成物。
＜１６＞再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜１５＞のいずれか１つに記載の感光性樹脂組成物。
＜１７＞＜１＞～＜１６＞のいずれか１つに記載の感光性樹脂組成物から形成される硬化膜。
＜１８＞＜１７＞に記載の硬化膜を２層以上有する、積層体。
＜１９＞上記硬化膜の間に、金属層を有する、＜１８＞に記載の積層体。
＜２０＞＜１＞～＜１６＞のいずれか１つに記載の感光性樹脂組成物を用いることを含む、硬化膜の製造方法。
＜２１＞上記感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、上記感光性樹脂組成物層を露光する露光工程と、上記露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程とを有する、＜２０＞に記載の硬化膜の製造方法。
＜２２＞＜１７＞に記載の硬化膜、あるいは、＜１８＞または＜１９＞に記載の積層体を有する半導体デバイス。 As a result of intensive studies by the present inventors based on the above problems, it has been found that the above problems can be solved by blending a radical polymerizable compound having a sulfur atom into the photosensitive resin composition. Specifically, the above problem has been solved by the following means <1>, preferably <2> to <22>.
<1> 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.
<2> The photosensitive resin composition according to <1>, wherein the polymer precursor includes a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2);
Figure JPOXMLDOC01-appb-C000007
 In 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 represent a hydrogen atom or a monovalent organic group;
Figure JPOXMLDOC01-appb-C000008
 In Formula (2), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group. To express.
<3> The photosensitive resin composition according to <2>, wherein the polymer precursor includes a repeating unit represented by the formula (1).
<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the radical polymerizable compound having a sulfur atom is represented by the following formula (3-1):
Figure JPOXMLDOC01-appb-C000009
 In 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, and 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.
<5> The photosensitive resin composition according to <4>, wherein the formula (3-1) is represented by the following formula (3-2);
Figure JPOXMLDOC01-appb-C000010
 In formula (3-2), L 1 represents —S—, —SS—, —S (═O) —, or —S (═O) 2 —, and 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, and 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 and —O—; R 3 represents a hydrogen atom or an alkyl group; provided that when less of R 1 and R 2 On the other hand but a radical polymerizable group.
<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) —.
<9> The photosensitive resin composition according to any one of <5> to <8>, wherein R 1 and R 2 are each independently a monovalent organic group having an acryloyl group or a methacryloyl group.
<10> The photosensitive resin composition according to <4>, wherein the formula (3-1) is represented by the following formula (4):
Figure JPOXMLDOC01-appb-C000011
 In formula (4), R is a hydrogen atom or a methyl group.
<11> In any one of <1> to <10>, the radical polymerizable compound having a sulfur atom is contained in a proportion of 0.001% by mass or more of the solid content in the photosensitive resin composition. The photosensitive resin composition as described.
<12> The photosensitive resin composition according to any one of <1> to <11>, further comprising a radical polymerizable compound other than the radical polymerizable compound having a sulfur atom.
<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>.

　本発明により、保存安定性に優れ、感度の高い感光性樹脂組成物、ならびに、上記感光性樹脂組成物を用いた優れた硬化膜、積層体、硬化膜の製造方法および半導体デバイスを提供可能になった。また、上記感光性樹脂組成物に用いる新規化合物を提供可能になった。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive resin composition having excellent storage stability and high sensitivity, and an excellent cured film, laminate, cured film manufacturing method and semiconductor device using the photosensitive resin composition. became. Moreover, it has become possible to provide a novel compound used in the photosensitive resin composition.

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

　以下に記載する本発明における構成要素の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
　本明細書における基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「（メタ）アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において、固形分とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、固形分濃度は、特に述べない限り２５℃における濃度をいう。
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィ（ＧＰＣ測定）に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００、およびＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用いることによって求めることができる。溶離液は特に述べない限り、ＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。また、検出は特に述べない限り、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。 The description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In the present specification, 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.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) acryl” represents both “acryl” and “methacryl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, solid content is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.

　本発明の感光性樹脂組成物（以下、単に、「本発明の組成物」ということがある）は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体から選択されるポリマー前駆体と、硫黄原子を有するラジカル重合性化合物と、光ラジカル重合開始剤と、溶剤とを含むことを特徴とする。このような構成とすることにより、保存安定性に優れ、感度の高い感光性樹脂組成物が得られる。この理由は、硫黄原子を有するラジカル重合性化合物は、室温の熱では重合反応を生じにくく、かつ、組成物のラジカル重合性を高めることに基づくと推定される。 The photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the 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.

＜ポリマー前駆体＞
　本発明の感光性樹脂組成物は、ポリイミド前駆体およびポリベンゾオキサゾール前駆体から選択されるポリマー前駆体を含む。ポリマー前駆体としては、ポリイミド前駆体またはポリベンゾオキサゾール前駆体を含むことが好ましく、ポリイミド前駆体を含むことがより好ましく、後述する式（１）で表される繰り返し単位を含むポリイミド前駆体であることがさらに好ましい。 <Polymer precursor>
The photosensitive resin composition of the present invention includes 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.

＜＜ポリイミド前駆体＞＞
　ポリイミド前駆体としては下記式（１）で表される繰り返し単位を含むことが好ましい。

Figure JPOXMLDOC01-appb-C000012
　式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す。 << Polyimide precursor >>
The polyimide precursor preferably contains a repeating unit represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000012
 In 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.

　式（１）におけるＡ１およびＡ２は、酸素原子またはＮＨであり、酸素原子が好ましい。
　式（１）におけるＲ１１１は、２価の有機基を表す。２価の有機基としては、直鎖または分岐の脂肪族基、環状の脂肪族基および芳香族基を含む基が例示され、炭素数２～２０の直鎖の脂肪族基、炭素数３～２０の分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数６～２０の芳香族基、または、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族基からなる基がより好ましい。 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. Examples of 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

　Ｒ１１１は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖または分岐の脂肪族、環状の脂肪族または芳香族ジアミンなどが挙げられる。ジアミンは、１種のみ用いてもよいし、２種以上用いてもよい。
　具体的には、ジアミンは、炭素数２～２０の直鎖脂肪族基、炭素数３～２０の分岐または環状の脂肪族基、炭素数６～２０の芳香族基、または、これらの組み合わせからなる基を含むものであることが好ましく、炭素数６～２０の芳香族基からなる基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。 R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. 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.

Figure JPOXMLDOC01-appb-C000013
　式中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｏ－、－Ｓ－、－Ｓ（＝Ｏ）２－、－Ｃ（ＣＦ３）２－、および、－Ｃ（ＣＨ３）２－からなる群から選択される２価の基であることがさらに好ましい。
Figure JPOXMLDOC01-appb-C000013
 In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (═O) 2 —, —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O— , —C (═O) —, —S—, —S (═O) 2 — is more preferred, and —CH 2 —, —O—, —S—, —S (= More preferably, it is a divalent group selected from the group consisting of O) 2 —, —C (CF 3 ) 2 —, and —C (CH 3 ) 2 —.

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

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

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

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

　また、少なくとも２つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましい例として挙げられる。好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれかまたは両方を一分子中にあわせて２つ以上含むジアミン、より好ましくは芳香環を含まないジアミンである。具体例としては、ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６、Ｄ－２００、Ｄ－４００、Ｄ－２０００、Ｄ－４０００（以上商品名、ＨＵＮＴＳＭＡＮ社製）、１－（２－（２－（２－アミノプロポキシ）エトキシ）プロポキシ）プロパン－２－アミン、１－（１－（１－（２－アミノプロポキシ）プロパン－２－イル）オキシ）プロパン－２－アミンなどが挙げられるが、これらに限定されない。
　ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６の構造を以下に示す。 A diamine having at least two alkylene glycol units in the main chain is also a preferred example. Preferred is a diamine containing 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.
Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.

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

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

　Ｒ１１１は、得られる硬化膜の柔軟性の観点から、－Ａｒ０－Ｌ－Ａｒ０－で表されることが好ましい。但し、Ａｒ０は、それぞれ独立に、芳香族炭化水素基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）、であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－または－ＮＨＣＯ－、ならびに、上記の２つ以上の組み合わせからなる基である。Ａｒ０は、フェニレン基が好ましく、Ｌは、フッ素原子で置換されていてもよい炭素数１～３の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－または－Ｓ（＝Ｏ）２－がさらに好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 R 111 is preferably represented by -Ar 0 -L-Ar 0 -from the viewpoint of the flexibility of the resulting cured film. However, Ar 0 is each independently an aromatic hydrocarbon group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and L is substituted with a fluorine atom. An aliphatic hydrocarbon group having 1 to 10 carbon atoms, —O—, —C (═O) —, —S—, —S (═O) 2 — or —NHCO—, and 2 A group consisting of two or more combinations. Ar 0 is preferably a phenylene group, and 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.

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

Figure JPOXMLDOC01-appb-C000017
式（５１）中、Ｒ５０～Ｒ５７は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ５０～Ｒ５７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　Ｒ５０～Ｒ５７の１価の有機基として、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。
　式（６１）
Figure JPOXMLDOC01-appb-C000018
 式（６１）中、Ｒ５８およびＲ５９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　式（５１）または（６１）の構造を与えるジアミン化合物としては、ジメチル－４,４’－ジアミノビフェニル、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらの１種を用いるか、２種以上を組み合わせて用いてもよい。 R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, the divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-line transmittance and availability.
Formula (51)
Figure JPOXMLDOC01-appb-C000017
 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)
Figure JPOXMLDOC01-appb-C000018
 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.

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

Figure JPOXMLDOC01-appb-C000019
　式（５）中、Ｒ１１２は、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－および－Ｓ（＝Ｏ）２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｃ（ＣＦ３）２－、－Ｃ（ＣＨ３）２－、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－および－Ｓ（＝Ｏ）２－からなる群から選択される２価の基がさらに好ましい。 R 115 in formula (1) represents a tetravalent organic group. As the 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.
Formula (5)
Figure JPOXMLDOC01-appb-C000019
 In the formula (5), 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 —.

式（６）

Figure JPOXMLDOC01-appb-C000020
Formula (6)
Figure JPOXMLDOC01-appb-C000020

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

Figure JPOXMLDOC01-appb-C000021
　式（Ｏ）中、Ｒ１１５は、４価の有機基を表す。Ｒ１１５は式（１）のＲ１１５と同義である。 Specific examples of the tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).
Formula (O)
Figure JPOXMLDOC01-appb-C000021
 In formula (O), R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (1).

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

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

Figure JPOXMLDOC01-appb-C000022
Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
Figure JPOXMLDOC01-appb-C000022

　式（１）におけるＲ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ１１３およびＲ１１４の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことがより好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を有する基が挙げられる。
　エチレン性不飽和結合を有する基としては、ビニル基、アリル基、（メタ）アクリロイル基、下記式（ＩＩＩ）で表される基などが挙げられる。なお、（メタ）アクリロイル基とは、アクリロイル基とメタクリロイル基の総称である。 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.

Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023

　式（ＩＩＩ）において、Ｒ２００は、水素原子またはメチル基を表し、メチル基がより好ましい。
　式（ＩＩＩ）において、Ｒ２０１は、炭素数２～１２のアルキレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－または炭素数４～３０のポリオキシアルキレン基（アルキレン基としては炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい；繰り返し数は１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）を表す。
　好適なＲ２０１の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、１，２－ブタンジイル基、１，３－ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－が挙げられ、エチレン基、プロピレン基、トリメチレン基、－ＣＨ２ＣＨ（ＯＨ）ＣＨ２－がより好ましい。
　特に好ましくは、Ｒ２００がメチル基で、Ｒ２０１がエチレン基である。
　Ｒ１１３またはＲ１１４が表す１価の有機基としては、現像液の溶解度を向上させる置換基が好ましく用いられる。 In the formula (III), R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH (OH) CH 2 — or a 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.
Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butanediyl group, 1,3-butanediyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , —CH 2 CH (OH) CH 2 —, and ethylene group, propylene group, trimethylene group, and —CH 2 CH (OH) CH 2 — are more preferable.
Particularly preferably, R 200 is a methyl group and R 201 is an ethylene group.
As the monovalent organic group represented by R113 or R114, a substituent that improves the solubility of the developer is preferably used.

　Ｒ１１３またはＲ１１４が１価の有機基の場合、アリール基を構成する炭素に結合している１、２または３つの、好ましくは１つの酸性基を有する、芳香族基およびアラルキル基などが挙げられる。具体的には、酸性基を有する炭素数６～２０の芳香族基、酸性基を有する炭素数７～２５のアラルキル基が挙げられる。より具体的には、酸性基を有するフェニル基および酸性基を有するベンジル基が挙げられる。酸性基は、ＯＨ基が好ましい。
　Ｒ１１３またはＲ１１４が、水素原子、２－ヒドロキシベンジル、３－ヒドロキシベンジルおよび４－ヒドロキシベンジルであることが、水性現像液に対する溶解性の点からは、より好ましい。 In the case where 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.

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

　式（１）において、Ｒ１１３が水素原子である場合、または、Ｒ１１４が水素原子である場合、ポリイミド前駆体はエチレン性不飽和結合を有する３級アミン化合物と対塩を形成していてもよい。このようなエチレン性不飽和結合を有する３級アミン化合物の例としては、Ｎ，Ｎ－ジメチルアミノプロピルメタクリレートが挙げられる。 In the formula (1), 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. Good. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

　また、ポリイミド前駆体は、構造単位中にフッ素原子を有することも好ましい。ポリイミド前駆体中のフッ素原子含有量は１０質量％以上が好ましく、２０質量％以下が好ましい。上限は特にないが５０質量％以下が実際的である。 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.

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

　式（１）で表される繰り返し単位は、式（１－Ａ）で表される繰り返し単位であることが好ましい。すなわち、本発明で用いるポリイミド前駆体の少なくとも１種が、式（１－Ａ）で表される繰り返し単位を有する前駆体であることが好ましい。このような構造とすることにより、露光ラチチュードの幅をより広げることが可能になる。
式（１－Ａ）

Figure JPOXMLDOC01-appb-C000024
　式（１－Ａ）中、Ａ１１およびＡ１２は、酸素原子またはＮＨを表し、Ｒ１１１およびＲ１１２は、それぞれ独立に、２価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ１１３およびＲ１１４の少なくとも一方は、ラジカル重合性基を含む基であり、ラジカル重合性基であることが好ましい。 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.
Formula (1-A)
Figure JPOXMLDOC01-appb-C000024
 In formula (1-A), A 11 and A 12 represent an oxygen atom or NH, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently Represents a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 is a group containing a radical polymerizable group, and preferably a radical polymerizable group.

　Ａ１１、Ａ１２、Ｒ１１１、Ｒ１１３およびＲ１１４は、それぞれ、独立に、式（１）におけるＡ１、Ａ２、Ｒ１１１、Ｒ１１３およびＲ１１４と同義であり、好ましい範囲も同様である。
　Ｒ１１２は、式（５）におけるＲ１１２と同義であり、好ましい範囲も同様である。 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.

　ポリイミド前駆体において、式（１）で表される繰り返し構造単位は１種であってもよいが、２種以上であってもよい。また、式（１）で表される繰り返し単位の構造異性体を含んでいてもよい。また、ポリイミド前駆体は、上記の式（１）の繰り返し単位のほかに、他の種類の繰り返し構造単位も含んでもよい。 In the polyimide precursor, 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).

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

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

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

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

＜＜ポリベンゾオキサゾール前駆体＞＞
　本発明で用いられるポリベンゾオキサゾール前駆体は、下記式（２）で表される繰り返し単位を含むことが好ましい。

Figure JPOXMLDOC01-appb-C000025
　式（２）中、Ｒ１２１は、２価の有機基を表し、Ｒ１２２は、４価の有機基を表し、Ｒ１２３およびＲ１２４は、それぞれ独立に、水素原子または１価の有機基を表す。 << Polybenzoxazole precursor >>
The polybenzoxazole precursor used in the present invention preferably contains a repeating unit represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000025
 In Formula (2), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group. To express.

　式（２）において、Ｒ１２１は、２価の有機基を表す。２価の有機基としては、脂肪族基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）および芳香族基（炭素数６～２２が好ましく、６～１４がより好ましく、６～１０が特に好ましい）の少なくとも一方を含む基が好ましい。脂肪族基としては、直鎖の脂肪族基が好ましい。Ｒ１２１は、４，４’－オキシジベンゾイルクロリドに由来することが好ましい。
　式（２）において、Ｒ１２２は、４価の有機基を表す。４価の有機基としては、上記式（１）におけるＲ１１５と同義であり、好ましい範囲も同様である。Ｒ１２２は、２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンに由来することが好ましい。
　Ｒ１２３およびＲ１２４は、それぞれ独立に、水素原子または１価の有機基を表し、上記式（１）におけるＲ１１３およびＲ１１４と同義であり、好ましい範囲も同様である。 In the formula (2), R 121 represents a divalent organic group. Examples of the divalent organic group include aliphatic groups (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and aromatic groups (preferably having 6 to 22 carbon atoms, preferably 6 to 14 carbon atoms). Is more preferable, and 6 to 10 is particularly preferable. As the aliphatic group, a linear aliphatic group is preferable. R 121 is preferably derived from 4,4′-oxydibenzoyl chloride.
In the formula (2), R 122 represents a tetravalent organic group. The tetravalent organic group has the same meaning as R 115 in the formula (1), and preferred ranges are also the same. R 122 is preferably derived from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferred range is also the same.

　ポリベンゾオキサゾール前駆体は上記の式（２）の繰り返し単位のほかに、他の種類の繰り返し構造単位も含んでよい。
　閉環に伴う硬化膜の反りの発生を抑制できる点で、下記式（ＳＬ）で表されるジアミン残基を他の種類の繰り返し構造単位として含むことが好ましい。 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.

Figure JPOXMLDOC01-appb-C000026
　式（ＳＬ）中、Ｚは、ａ構造とｂ構造を有し、Ｒ１ｓは水素原子または炭素数１～１０の炭化水素基（好ましくは炭素数１～６、より好ましくは炭素数１～３）であり、Ｒ２ｓは炭素数１～１０の炭化水素基（好ましくは炭素数１～６、より好ましくは炭素数１～３）であり、Ｒ３ｓ、Ｒ４ｓ、Ｒ５ｓ、Ｒ６ｓのうち少なくとも１つは芳香族基（好ましくは炭素数６～２２、より好ましくは炭素数６～１８、特に好ましくは炭素数６～１０）で、残りは水素原子または炭素数１～３０（好ましくは炭素数１～１８、より好ましくは炭素数１～１２、特に好ましくは炭素数１～６）の有機基で、それぞれ同一でも異なっていてもよい。ａ構造およびｂ構造の重合は、ブロック重合でもランダム重合でもよい。Ｚ部分において、好ましくは、ａ構造は５～９５モル％、ｂ構造は９５～５モル％であり、ａ＋ｂは１００モル％である。
Figure JPOXMLDOC01-appb-C000026
 In the formula (SL), 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). An organic group having 1 to 18, more preferably 1 to 12, and particularly preferably 1 to 6 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. In the Z portion, the a structure is preferably 5 to 95 mol%, the b structure is 95 to 5 mol%, and a + b is 100 mol%.

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

　他の種類の繰り返し構造単位として式（ＳＬ）で表されるジアミン残基を含む場合、アルカリ可溶性を向上させる点で、さらに、テトラカルボン酸二無水物から酸二無水物基の除去後に残存するテトラカルボン酸残基を繰り返し構造単位として含むことが好ましい。このようなテトラカルボン酸残基の例としては、式（１）中のＲ１１５の例が挙げられる。 When the 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).

　ポリベンゾオキサゾール前駆体の重量平均分子量（Ｍｗ）は、好ましくは２０００～５０００００であり、より好ましくは５０００～１０００００であり、さらに好ましくは１００００～５００００である。また、数平均分子量（Ｍｎ）は、好ましくは８００～２５００００であり、より好ましくは、２０００～５００００であり、さらに好ましくは、４０００～２５０００である。
　ポリベンゾオキサゾール前駆体の分散度は、１．５～３．５が好ましく、２～３がより好ましい。 The weight average molecular weight (Mw) of the 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.

　本発明の感光性樹脂組成物における、ポリマー前駆体の含有量は、組成物の全固形分に対し２０～１００質量％であることが好ましく、３０～９９質量％であることがより好ましく、４０～９８質量％であることがさらに好ましく、５０～９５質量％であることが一層好ましく、６０～９５質量％であることがより一層好ましく、７０～９５質量％であることがさらに一層好ましい。
　ポリマー前駆体は１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 In the photosensitive resin composition of the present invention, the content of the polymer precursor is preferably 20 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.

＜硫黄原子を有するラジカル重合性化合物＞
　本発明の感光性樹脂組成物は、硫黄原子を有するラジカル重合性化合物を含有する。硫黄原子を有するラジカル重合性化合物の一実施形態は、ラジカル重合性基を２つ以上（好ましくは２～４つ、より好ましくは２～３つ、さらに好ましくは２つ）有する硫黄原子を有するラジカル重合性化合物である。
　また、上記硫黄原子を有するラジカル重合性化合物は、下記式（３－１）で表される化合物が好ましい。

Figure JPOXMLDOC01-appb-C000027
　式（３－１）中、Ｌ１１は、硫黄原子を含有する二価の連結基を表し、Ｘ１１およびＸ１２は、それぞれ独立に単結合、または、二価の連結基を表し、Ｒ１１およびＲ１２は、それぞれ独立に水素原子または一価の有機基を表す；ただし、Ｒ１１およびＲ１２の少なくとも一方が、少なくとも１つのラジカル重合性基を含む一価の有機基を表す；Ｒ１１およびＲ１２は互いに結合して環を形成していてもよい。 <Radically polymerizable compound having a sulfur atom>
The photosensitive resin composition of the present invention contains a radically polymerizable compound having a sulfur atom. One embodiment of the 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).
Figure JPOXMLDOC01-appb-C000027
 In 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, and 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.

　式（３－１）中、Ｌ１１は、硫黄原子を含有する二価の連結基を表す。好ましくは硫黄原子を１つまたは２つ有する連結基であり、より好ましくは硫黄原子を１つまたは２つ有しかつ酸素原子を有する原子数２～６の連結基である。さらに好ましくは、後述する式（３－２）のＬ１と同義のものであり、好ましい範囲も同様である。 In formula (3-1), 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.

　式（３－１）中、Ｘ１１およびＸ１２は、それぞれ独立に単結合、または、二価の連結基を表す。二価の連結基としては、直鎖または分岐のアルキレン基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）、芳香族基（炭素数６～２２が好ましく、６～１４がより好ましく、６～１０が特に好ましい）、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－ＮＲ３－、－ＮＲ３ＣＯ－、およびそれらの組み合わせに係る連結基が挙げられる。Ｒ３は後述する式（３－２）におけるＲ３と同義である。また、連結基としては炭化水素基であってもよい。炭化水素基は、オリゴ炭化水素基であってもよく、そのときの繰り返し数は１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい。炭化水素基の炭素数は１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい。連結基の原子数はオリゴ炭化水素基以外のとき、原子数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい。（オリゴ）炭化水素基のときは、原子数２～６４が好ましく、２～３２がより好ましく、２～１８が特に好ましい。Ｘ１１およびＸ１２が表す二価の連結基は、酸素原子、硫黄原子、もしくは窒素原子を含有する二価の連結基（原子数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）であることが好ましく、酸素原子を含む二価の連結基であることがより好ましい。 In formula (3-1), X 11 and X 12 each independently represent a single bond or a divalent linking group. Examples of 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. Further, 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. In the case of an (oligo) hydrocarbon 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.

　式（３－１）中、Ｒ１１およびＲ１２は、それぞれ独立に水素原子または一価の有機基を表す。一価の有機基としては、ラジカル重合性基を含む１価の有機基や、後述する置換基Ｔなどが挙げられる。ラジカル重合性基としては、炭素炭素不飽和二重結合を有する基が挙げられる。なかでも、ラジカル重合性基としては、ビニル基、アリル基、アクリロイル基、またはメタクリロイル基を有する基が好ましく、アクリロイル基、またはメタクリロイル基を有する基がより好ましい。より具体的には、アクリロイル基、メタクリロイル基、アクリロイルオキシ基、メタクリロイルオキシ基、アクリロイルアミノ基、メタクリロイルアミノ基、ビニル基、ビニルフェニル基（ｏ，ｍ，ｐ）、ビニルフェニルオキシ基（ｏ，ｍ，ｐ）、ビニルフェニルメチル基（ｏ，ｍ，ｐ）が好ましく、アクリロイル基、メタクリロイル基、アクリロイルオキシ基、メタクリロイルオキシ基、アクリロイルアミノ基、メタクリロイルアミノ基がより好ましく、アクリロイルオキシ基、メタクリロイルオキシ基がさらに好ましい。
　ラジカル重合性基を含む１価の有機基は、ラジカル重合性基を１個のみ有する基であってもよく、ラジカル重合性基を２個以上有する基であってもよい。ラジカル重合性基を含む１価の有機基がラジカル重合性基を２個以上有する場合、複数個のラジカル重合性基は、互いに、同一であってもよく、異なっていてもよい。また、ラジカル重合性基を含む１価の有機基は、本発明の効果を損ねない範囲で、後述する置換基をさらに有していてもよい。置換基としては、後述する置換基Ｔが例示される。１つの１価の有機基に含まれるラジカル重合性基の数は、３個以下が好ましく、２個以下がより好ましい。本発明では、ラジカル重合性基を含む１価の有機基が、置換基を有さない態様が好ましく例示される。 In formula (3-1), R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group. Examples of the monovalent organic group include a monovalent organic group containing a radical polymerizable group and a substituent T described later. Examples of the radical polymerizable group include a group having a carbon-carbon unsaturated double bond. Among them, 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. More specifically, 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. When the monovalent organic group containing a radical polymerizable group has two or more radical polymerizable groups, the plurality of radical polymerizable groups may be the same as or different from each other. Moreover, 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.

　式（３－１）において、Ｒ１１およびＲ１２の少なくとも一方が、少なくとも１つのラジカル重合性基を含む１価の有機基を表す。なかでも、Ｒ１１およびＲ１２はその両方がそれぞれ独立してラジカル重合性基を含む１価の有機基であることが好ましい。
　また、式（３－１）において、一分子中のラジカル重合性基の数は、２個以上であることが好ましく、また、４個以下であることが好ましく、３個以下であることがより好ましく、２個であることがさらに好ましい。 In the formula (3-1), at least one of 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.
In the formula (3-1), 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.

　式（３－１）において、Ｒ１１およびＲ１２は、互いに結合して、環を形成していてもよい。Ｒ１１およびＲ１２が環を形成するとき、Ｒ１１およびＲ１２が直接連結してもよく、後述の連結基Ｌを介して連結していてもよい。また、形成される環が縮環していてもよい。連結基Ｌとしては、直鎖または分岐のアルキレン基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－ＮＲ３－、－ＮＲ３ＣＯ－、およびそれらの組み合わせに係る連結基が挙げられる。Ｒ３は、後述する、式（３－２）におけるＲ３と同義であり好ましい範囲も同様である。 In formula (3-1), R 11 and R 12 may be bonded to each other to form a ring. When R 11 and R 12 form a ring, R 11 and R 12 may be directly connected or may be connected via a connecting group L described later. Moreover, 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.

　硫黄原子を有するラジカル重合性化合物は下記式（３－２）で表されることがより好ましい。

Figure JPOXMLDOC01-appb-C000028
　式（３－２）中、Ｌ１は、－Ｓ－、－Ｓ－Ｓ－、－Ｓ（＝Ｏ）－、または、－Ｓ（＝Ｏ）２－を表し、Ｘ１およびＸ２は、それぞれ独立に単結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－ＯＣ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－または－ＮＲ３ＣＯ－を表し、Ｒ１およびＲ２は、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アリール基またはラジカル重合性基を表し、Ｌａ１～Ｌａ４は、それぞれ独立に、単結合、アルキレン基およびフェニレン基の１つまたは２つ以上の組み合わせからなる基、ならびに、アルキレン基およびフェニレン基の１つまたは２つ以上と－Ｏ－との組み合わせからなる基のいずれかを表す；Ｒ３は、水素原子またはアルキル基を表す；ただし、Ｒ１およびＲ２の少なくとも一方が、ラジカル重合性基である。 The radically polymerizable compound having a sulfur atom is more preferably represented by the following formula (3-2).
Figure JPOXMLDOC01-appb-C000028
 In formula (3-2), L 1 represents —S—, —SS—, —S (═O) —, or —S (═O) 2 —, and 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, and 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 and —O—; R 3 represents a hydrogen atom or an alkyl group; provided that when less of R 1 and R 2 On the other hand but a radical polymerizable group.

　式（３－２）中、Ｌ１は、－Ｓ－、－Ｓ－Ｓ－、－Ｓ（＝Ｏ）－、または、－Ｓ（＝Ｏ）２－を表し、－Ｓ（＝Ｏ）－であることが好ましい。
　Ｘ１およびＸ２は、それぞれ独立に単結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－ＯＣ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－または－ＮＲ３ＣＯ－を表し、単結合または－Ｏ－であることが好ましく、－Ｏ－がより好ましい。Ｒ３は、水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、アルキニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）を表し、水素原子または上記炭素数のアルキル基が好ましい。
　Ｒ１およびＲ２は、それぞれ独立にラジカル重合性基、水素原子、アルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）、シクロアルキル基（炭素数３～２４が好ましく、３～１２がより好ましく、３～６が特に好ましい）またはアリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）を表す。
　Ｒ１およびＲ２が、アルキル基、シクロアルキル基、または、アリール基のとき、本発明の効果を損ねない範囲で任意の置換基Ｔを有していてもよい。任意の置換基Ｔとしては、分岐または直鎖のアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）、シクロアルキル基（炭素数３～２４が好ましく、３～１２がより好ましく、３～６が特に好ましい）、ヒドロキシル基、ヒドロキシルアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい；ヒドロキシル基の数は１～６が好ましく、１～３がより好ましい）、アミノ基（炭素数０～２４が好ましく、０～１２がより好ましく、０～６が特に好ましい）、アミノアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい；アミノ基の数は１～６が好ましく、１～３がより好ましい）、チオール基、チオールアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい；チオール基の数は１～６が好ましく、１～３がより好ましい）、カルボキシル基、カルボキシアルキル基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい；カルボキシル基の数は１～６が好ましく、１～３がより好ましい）、アシル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アシルオキシ基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アリーロイル基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が特に好ましい）、アリーロイルオキシ基（炭素数７～２３が好ましく、７～１９がより好ましく、７～１１が特に好ましい）、オキソ基（＝Ｏ）、イミノ基（＝ＮＲ３）、アルキリデン基（＝Ｃ（Ｒ３）２）などが挙げられる。
　ただし、Ｒ１およびＲ２の少なくとも一方が、ラジカル重合性基を表す。 In Formula (3-2), L 1 represents —S—, —SS—, —S (═O) —, or —S (═O) 2 —, and —S (═O) — It is preferable that
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 CO—, preferably a single bond or —O—, more preferably —O—. 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.
When 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). Preferably, 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). Preferably 1 to 3), acyloxy groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms), aryloyl groups (preferably 7 to 23 carbon atoms, 7 to 19 carbon atoms). More preferably, 7 to 11 are particularly preferable), aryloyloxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 and particularly preferably 7 to 11), oxo group (═O) Imino (= NR 3), an alkylidene group (= C (R 3) 2 ) , and the like.
However, at least one of R 1 and R 2 represents a radical polymerizable group.

　Ｒ１およびＲ２が表すラジカル重合性基は、上述した式（３－１）で例示したものと同義の基が挙げられる。Ｒ１およびＲ２はその両方がそれぞれ独立してラジカル重合性基であることが好ましく、同じラジカル重合性基であることがより好ましい。 Examples of the radical polymerizable group represented by R 1 and R 2 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.

　式（３－２）において、Ｌａ１～Ｌａ４は、それぞれ独立に、単結合、アルキレン基およびフェニレン基の１つまたは２つ以上の組み合わせからなる基、ならびに、アルキレン基およびフェニレン基の１つまたは２つ以上と－Ｏ－との組み合わせからなる基のいずれかを表す。Ｌａ１～Ｌａ４は、それぞれ独立に、単結合、アルキレン基（炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい）、フェニレン基、（オリゴ）オキシアルキレン基（アルキレン基は炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい。繰り返し数は１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい。）、（オリゴ）アルキレンオキシ基（アルキレン基は炭素数１～２４が好ましく、１～１２がより好ましく、１～６が特に好ましい。繰り返し数は１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい。）、またはそれらの組合せによる連結基を有していてもよい。（オリゴ）オキシアルキレン基とは、オキシアルキレン基またはオリゴオキシアルキレン基を意味する。他の「（オリゴ）」という記載を含む基についても同様に考える。
　上記アルキレン基、フェニレン基、（オリゴ）オキシアルキレン基、（オリゴ）アルキレンオキシ基は本発明の効果を損ねない範囲でさらに上記任意の置換基Ｔを有していてもよい。
　Ｌａ１～Ｌａ４は、より好ましくは、それぞれ独立に、単結合またはアルキレン基であり、さらに好ましくは、Ｌａ２およびＬａ３は、単結合であり、Ｌａ１およびＬａ４は、アルキレン基である。 In formula (3-2), 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. .

　Ｒ１およびＲ２は互いに結合して環を形成していてもよい。Ｒ１およびＲ２が環を形成するとき、Ｒ１およびＲ２が直接連結しても、上記連結基Ｌを介して連結していてもよい。また、形成される環が縮環していてもよい。
　本発明で用いる、硫黄原子を有するラジカル重合性化合物は、低分子（例えば、分子量２０００未満、さらには１０００未満）であっても、高分子であってもよいが、好ましくは低分子である。 R 1 and R 2 may be bonded to each other to form a ring. When R 1 and R 2 form a ring, R 1 and R 2 may be directly connected or connected via the connecting group L. Moreover, 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.

　硫黄原子を有するラジカル重合性化合物として下記の例示化合物を挙げることができるが、本発明がこれらに限定して解釈されるものではない。この例示化合物のなかでも、下記化合物３０１、３０２、３０３、３０４、３１２、３２２が好ましく、３０１および３０２（式（４）で表される化合物）がより好ましく、３０２が特に好ましい。 Examples of the radical polymerizable compound having a sulfur atom include the following exemplary compounds, but the present invention is not construed as being limited thereto. Among these exemplified compounds, 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.

Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029

Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030

　上記例示化合物中、ｍは１～３０であり、ｎは１～３０である。
　本発明の感光性樹脂組成物における、硫黄原子を有するラジカル重合性化合物の含有量は、組成物の全固形分に対し下限値として０．００１質量％以上であることが好ましく、０．００５質量％以上であることがより好ましく、０．０１質量％以上であることがさらに好ましく、０．０５質量％以上であることが一層好ましく、０．１質量％以上であることがより一層好ましく、０．３質量％以上であることがさらに一層好ましい。上限値としては、２０質量％以下であることが好ましく、１５質量％以下であることがより好ましく、１０質量％以下であることがさらに好ましく、さらには、７質量％以下、５質量％以下、２質量％以下、１質量％以下であってもよい。
　ポリマー前駆体１００質量部に対する硫黄原子を有するラジカル重合性化合物の配合量は、後述するその他の重合性化合物との合計で、重合性化合物として７０質量部以下であることが好ましく、６０質量部以下であることがより好ましく、５５質量部以下であることがさらに好ましく、５０質量部以下であることが一層好ましく、４５質量部以下であることが特に好ましい。重合性化合物として０．１質量部以上であることが好ましく、１質量部以上、３質量部以上、５質量部以上、１０質量部以上であってもよい。
　後述するその他の重合性化合物を含む全重合性化合物中の硫黄原子を有するラジカル重合性化合物の割合は、下限値としては０．０１質量％以上が好ましく、０．０２質量％以上がより好ましく、０．１質量％以上がさらに好ましく、０．３質量％以上が一層好ましく、０．５質量％以上がより一層好ましい。上限値としては１００質量％以下が好ましく、５０質量％以下、３０質量％以下、２０質量％以下、１０質量％以下、７質量％以下、５質量％以下、２質量％以下、１質量％以下であってもよい。
　硫黄原子を有するラジカル重合性化合物を上記のような割合で組成物中に含有させることで、一層高い安定性と一層高い露光感度を達成することができる。
　硫黄原子を有するラジカル重合性化合物は１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 In the above exemplary compounds, 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. As an upper limit, it is preferable that it is 20 mass% or less, It is more preferable that it is 15 mass% or less, It is further more preferable that it is 10 mass% or less, Furthermore, 7 mass% or less, 5 mass% or less, It may be 2% by mass or less and 1% by mass or less.
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. As an upper limit, 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.
By containing 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.

＜光ラジカル重合開始剤＞
　本発明の感光性樹脂組成物は、光ラジカル重合開始剤を含有する。
　本発明で用いることができる光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
　光ラジカル重合開始剤は、約３００～８００ｎｍ（好ましくは３３０～５００ｎｍ）の範囲内で少なくとも約５０のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶剤を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 <Radical radical polymerization initiator>
The photosensitive resin composition of the present invention contains a radical photopolymerization initiator.
There is no restriction | limiting in particular as radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators. For example, a 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.

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

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

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

　光ラジカル重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、および、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ　１８４（ＩＲＧＡＣＵＲＥは登録商標）、ＤＡＲＯＣＵＲ　１１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ　１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ　９０７、ＩＲＧＡＣＵＲＥ　３６９、および、ＩＲＧＡＣＵＲＥ　３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の波長光源に吸収極大波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができる。
　アシルホスフィン系開始剤としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドなどが挙げられる。また、市販品であるＩＲＧＡＣＵＲＥ－８１９やＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　メタロセン化合物としては、ＩＲＧＡＣＵＲＥ－７８４（ＢＡＳＦ社製）などが例示される。 As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).

　光ラジカル重合開始剤として、より好ましくはオキシム化合物が挙げられる。オキシム化合物を用いることにより、露光ラチチュードをより効果的に向上させることが可能になる。オキシム化合物は、露光ラチチュード（露光マージン）が広く、かつ、光塩基発生剤としても働くため、特に好ましい。
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物を用いることができる。
　好ましいオキシム化合物としては、例えば、下記の構造の化合物や、３－ベンゾオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。本発明の感光性樹脂組成物においては、特にこのオキシム系の光重合開始剤を用いることが好ましい。オキシム系の光重合開始剤は、分子内に　＞Ｃ＝Ｎ－Ｏ－Ｃ（＝Ｏ）－　の連結基を有する。

Figure JPOXMLDOC01-appb-C000031
　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１およびアデカアークルズＮＣＩ－９３０（（株）ＡＤＥＫＡ製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス（株）製）を用いることができる。
　さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の段落０３４５に記載されている化合物２４、段落０３４７～０３４８に記載されている化合物３６～４０、特開２０１３－１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ－３）などが挙げられる。
　最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。 More preferable examples of the photo radical polymerization initiator include oxime compounds. By using the oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photobase generator.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, 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. In the photosensitive resin composition of the present invention, 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.
Figure JPOXMLDOC01-appb-C000031
 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. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daitokemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in 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.

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

Figure JPOXMLDOC01-appb-C000032
　式（Ｉ）中、ＲＩ００は、炭素数１～２０のアルキル基、１個以上の酸素原子によって中断された炭素数２～２０のアルキル基、炭素数１～１２のアルコキシ基、フェニル基、炭素数１～２０のアルキル基、炭素数１～１２のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基および炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基、またはビフェニリルであり、ＲＩ０１は、式（ＩＩ）で表される基であるか、ＲＩ００と同じ基であり、ＲＩ０２～ＲＩ０４は各々独立に炭素数１～１２のアルキル、炭素数１～１２のアルコキシまたはハロゲンである。
Figure JPOXMLDOC01-appb-C000033
 式中、ＲＩ０５～ＲＩ０７は、上記式（Ｉ）のＲＩ０２～ＲＩ０４と同じである。 Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.
More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is even more preferable.
Further, photo radical polymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc. It is also possible to use quinones fused with the aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal. A compound represented by the following formula (I) can also be used.
Figure JPOXMLDOC01-appb-C000032
 In formula (I), R I00 represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an 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.
Figure JPOXMLDOC01-appb-C000033
 In the formula, R I05 to R I07 are the same as R I02 to R I04 in the above formula (I).

　また、光ラジカル重合開始剤は、国際公開ＷＯ２０１５／１２５４６９号の段落００４８～００５５に記載の化合物を用いることもできる。 Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can be used.

　光ラジカル重合開始剤の含有量は、本発明の感光性樹脂組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは０．５～１５質量％であり、一層好ましくは１．０～１０質量％である。光ラジカル重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。光ラジカル重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 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.

＜熱ラジカル重合開始剤＞
　本発明の感光性樹脂組成物は、本発明の趣旨を逸脱しない範囲で熱ラジカル重合開始剤を含んでいてもよい。
　熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤を添加することによって、ポリマー前駆体の環化と共に、ポリマー前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。
　熱ラジカル重合開始剤として、具体的には、特開２００８－６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられる。 <Thermal radical polymerization initiator>
The photosensitive resin composition of the present invention may contain a thermal radical polymerization initiator without departing from the gist of the present invention.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the polymer precursor can be promoted together with the cyclization of the polymer precursor, so that higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.

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

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

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

　溶剤の含有量は、塗布性の観点から、本発明の感光性樹脂組成物の全固形分濃度が５～８０質量％になる量にすることが好ましく、５～７５質量％となる量にすることがより好ましく、１０～７０質量％となる量にすることがさらに好ましく、４０～７０質量％となるようにすることが一層好ましい。溶剤含有量は、所望の厚さと塗布方法によって調節すればよい。
　溶剤は１種のみ含有していてもよいし、２種以上含有していてもよい。溶剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the solvent is preferably an amount such that the total solid 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.

＜その他の重合性化合物＞
＜＜硫黄原子を含まないラジカル重合性化合物＞＞
　本発明の感光性樹脂組成物は、上記硫黄原子を含むラジカル重合性化合物に加え、硫黄原子を含まないラジカル重合性化合物（以下、「硫黄原子を含まない重合性モノマー」ともいう）も含むことが好ましい。このような構成とすることにより、耐熱性に優れた硬化膜を形成することができる。 <Other polymerizable compounds>
<< Radically polymerizable compound containing no sulfur atom >>
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.

　硫黄原子を含まない重合性モノマーは、ラジカル重合性基を有する化合物を用いることができる。ラジカル重合性基としては、スチリル基、ビニル基、（メタ）アクリロイル基およびアリル基などのエチレン性不飽和結合を有する基が挙げられる。ラジカル重合性基は、（メタ）アクリロイル基が好ましい。 As the polymerizable monomer not containing a sulfur atom, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.

　硫黄原子を含まない重合性モノマーが有するラジカル重合性基の数は、１個でもよく、２個以上でもよいが、硫黄原子を含まない重合性モノマーはラジカル重合性基を２個以上有することが好ましく、３個以上有することがより好ましい。上限は、１５個以下が好ましく、１０個以下がより好ましく、８個以下がさらに好ましい。 The number of radical polymerizable groups contained in the 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.

　硫黄原子を含まない重合性モノマーの分子量は、２０００以下が好ましく、１５００以下がより好ましく、９００以下がさらに好ましい。重合性モノマーの分子量の下限は、１００以上が好ましい。 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.

　本発明の感光性樹脂組成物は、現像性の観点から、重合性基を２個以上含む２官能以上の硫黄原子を含まない重合性モノマーを少なくとも１種含むことが好ましく、３官能以上の硫黄原子を含まない重合性モノマーを少なくとも１種含むことがより好ましい。また、２官能の硫黄原子を含まない重合性モノマーと３官能以上の硫黄原子を含まない重合性モノマーとの混合物であってもよい。なお、硫黄原子を含まない重合性モノマーの官能基数は、１分子中におけるラジカル重合性基の数を意味する。 From the viewpoint of developability, the photosensitive resin composition of the present invention preferably contains at least one 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. In addition, 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.

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

　また、硫黄原子を含まない重合性モノマーは、常圧下で１００℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後、（メタ）アクリレート化した化合物、特公昭４８－４１７０８号公報、特公昭５０－６０３４号公報、特開昭５１－３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレートおよびこれらの混合物を挙げることができる。また、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物も好適である。また、多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和結合を有する化合物を反応させて得られる多官能（メタ）アクリレートなども挙げることができる。
　また、上述以外の好ましい硫黄原子を含まない重合性モノマーとして、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を２個以上有する化合物や、カルド樹脂も使用することが可能である。
　さらに、その他の例としては、特公昭４６－４３９４６号公報、特公平１－４０３３７号公報、特公平１－４０３３６号公報に記載の特定の不飽和化合物や、特開平２－２５４９３号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭６１－２２０４８号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。さらに日本接着協会誌　ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光重合性モノマーおよびオリゴマーとして紹介されているものも使用することができる。 The 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. Many such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, JP-B-48-4170 Urethane (meth) acrylates as described in JP-A Nos. 50-6034 and 51-37193, JP-A 48-64183, JP-B 49-43191, Mention may be made of 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. In addition, polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated bond can also be exemplified.
In addition, as 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. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.

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

　また、特開平１０－６２９８６号公報において式（１）および式（２）としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、硫黄原子を含まない重合性モノマーとして用いることができる。 In addition, compounds described in JP-A-10-62986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a polymerizable monomer containing no sulfur atom.

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

　硫黄原子を含まない重合性モノマーとしては、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製、Ａ－ＴＭＭＴ：新中村化学工業（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、Ａ－ＤＰＨ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。 Examples of the 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 residues are preferred There. These oligomer types can also be used.

　硫黄原子を含まない重合性モノマーの市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、エチレンオキシ鎖を４個有する２官能メタクリレートであるサートマー社製のＳＲ－２０９、日本化薬（株）製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（日本製紙社製）、ＮＫエステルＭ－４０Ｇ、ＮＫエステル４Ｇ、ＮＫエステルＭ－９３００、ＮＫエステルＡ－９３００、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株）製）、ブレンマーＰＭＥ４００（日油（株）製）などが挙げられる。 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.

　他の重合性モノマーとしては、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。さらに、硫黄原子を含まない重合性モノマーとして、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造を有する化合物を用いることもできる。 Other 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.

　硫黄原子を含まない重合性モノマーは、カルボキシル基、リン酸基等の酸基を有する重合性モノマーであってもよい。酸基を有する重合性モノマーは、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性モノマーがより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシル基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性モノマーにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトールおよび／またはジペンタエリスリトールである化合物である。市販品としては、例えば、東亞合成（株）製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。
　酸基を有する重合性モノマーは、１種を単独で用いてもよいが、２種以上を混合して用いてもよい。また、必要に応じて酸基を有しない重合性モノマーと酸基を有する重合性モノマーを併用してもよい。
　酸基を有する重合性モノマーの好ましい酸価は、０．１～４０ｍｇＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性モノマーの酸価が上記範囲であれば、製造や取扱性に優れ、さらには、現像性に優れる。また、重合性が良好である。 The 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. Particularly preferably, in the polymerizable monomer in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol 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.
As the polymerizable monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polymerizable monomer which does not have an acid group, and the polymerizable monomer which has an acid group as needed.
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. When 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.

　本発明の感光性樹脂組成物は、硬化膜の弾性率制御に伴う反り抑制の観点から、硫黄原子を含まない重合性モノマーとして、単官能重合性モノマーを好ましく用いることができる。単官能重合性モノマーとしては、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸誘導体、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等のＮ－ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能重合性モノマーとしては、露光前の揮発を抑制するため、常圧下で１００℃以上の沸点を持つ化合物も好ましい。 In the photosensitive resin composition of the present invention, a monofunctional 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. Allylation of acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Goods and the like are preferably used. As 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.

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

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

Figure JPOXMLDOC01-appb-C000034
（式中、ｔは、１～２０の整数を示し、Ｒ４は炭素数１～２００のｔ価の有機基を示し、Ｒ５は、－ＯＲ６または、－ＯＣＯ－Ｒ７で示される基を示し、Ｒ６は、水素原子または炭素数１～１０の有機基を示し、Ｒ７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000034
 (Wherein t represents an integer of 1 to 20, R 4 represents a t-valent organic group having 1 to 200 carbon atoms, and 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, and R 7 represents an organic group having 1 to 10 carbon atoms.)

Figure JPOXMLDOC01-appb-C000035
（式中、Ｒ４０４は炭素数１～２００の２価の有機基を示し、Ｒ４０５は、－ＯＲ４０６または、－ＯＣＯ－Ｒ４０７で示される基を示し、Ｒ４０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ４０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000035
 (Wherein R 404 represents a divalent organic group having 1 to 200 carbon atoms, R 405 represents a group represented by —OR 406 or —OCO—R 407 , and R 406 represents a hydrogen atom or a carbon atom. An organic group having 1 to 10 carbon atoms, and R 407 represents an organic group having 1 to 10 carbon atoms.)

Figure JPOXMLDOC01-appb-C000036
（式中ｕは３～８の整数を示し、Ｒ５０４は炭素数１～２００のｕ価の有機基を示し、Ｒ５０５は、－ＯＲ５０６または、－ＯＣＯ－Ｒ５０７で示される基を示し、Ｒ５０６は、水素原子または炭素数１～１０の有機基を示し、Ｒ５０７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000036
 (Wherein u represents an integer of 3 to 8, R 504 represents a u-valent organic group having 1 to 200 carbon atoms, and R 505 represents a group represented by —OR 506 or —OCO—R 507. R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 507 represents an organic group having 1 to 10 carbon atoms.)

　上述のヒドロキシメチル基等を有する化合物を用いることで、凹凸のある基板上に感光性樹脂組成物を適用した際に、クラックの発生をより効果的に抑制できる。また、パターン加工性に優れ、５質量％減少温度が３５０℃以上、より好ましくは３８０℃以上となる高い耐熱性を有する硬化膜を形成することができる。式（ＡＭ４）で示される化合物の具体例としては、４６ＤＭＯＣ、４６ＤＭＯＥＰ（以上、商品名、旭有機材（株）製）、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＥＰ、ＤＭＬ－ＰＯＰ、ｄｉｍｅｔｈｙｌｏｌＢｉｓＯＣ－Ｐ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＭＴｒｉｓＰＣ（以上、商品名、本州化学工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２９０（商品名、（株）三和ケミカル製）、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－４－ｔ－ｂｕｔｈｙｌｐｈｅｎｏｌ、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌ、２，６－ｄｉａｃｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌなどが挙げられる。 By using the above-mentioned compound having a hydroxymethyl group or the like, 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. .

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

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

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

　エポキシ化合物の例としては、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；プロピレングリコールジグリシジルエーテル等のアルキレングリコール型エポキシ樹脂；ポリメチル（グリシジロキシプロピル）シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン（登録商標）８５０－Ｓ、エピクロン（登録商標）ＨＰ－４０３２、エピクロン（登録商標）ＨＰ－７２００、エピクロン（登録商標）ＨＰ－８２０、エピクロン（登録商標）ＨＰ－４７００、エピクロン（登録商標）ＥＸＡ－４７１０、エピクロン（登録商標）ＨＰ－４７７０、エピクロン（登録商標）ＥＸＡ－８５９ＣＲＰ、エピクロン（登録商標）ＥＸＡ－１５１４、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８５０－１５０、エピクロンＥＸＡ－４８５０－１０００、エピクロン（登録商標）ＥＸＡ－４８１６、エピクロン（登録商標）ＥＸＡ－４８２２（以上商品名、ＤＩＣ（株）製）、リカレジン（登録商標）ＢＥＯ－６０Ｅ（商品名、新日本理化（株））、ＥＰ－４００３Ｓ、ＥＰ－４０００Ｓ（以上商品名、（株）ＡＤＥＫＡ製）などが挙げられる。この中でも、ポリエチレンオキサイド基を含有するエポキシ樹脂が、反りの抑制および耐熱性に優れる点で好ましい。例えば、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８２２、リカレジン（登録商標）ＢＥＯ－６０Ｅは、ポリエチレンオキサイド基を含有するので好ましい。 Examples of 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. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Corporation), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nippon Rika Co., Ltd.), EP- 003S, EP-4000S (trade names, Co., Ltd. ADEKA), and the like. Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.

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

（ベンゾオキサジン化合物（ベンゾオキサゾリル基を有する化合物））
　ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、さらに熱収縮を小さくして反りの発生が抑えられることから好ましい。 (Benzoxazine compound (compound having 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.

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

　硫黄原子を有するラジカル重合性化合物以外の重合性化合物の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０～６０質量％であることが好ましい。下限は５質量％以上がより好ましい。上限は、５０質量％であることがより好ましく、３０質量％以下であることがさらに好ましい。
　その他の重合性化合物は１種を単独で用いてもよいが、２種以上を混合して用いてもよい。２種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 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.

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

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

　その他のマイグレーション抑制剤としては、特開２０１３－１５７０１号公報の段落００９４に記載の防錆剤、特開２００９－２８３７１１号公報の段落００７３～００７６に記載の化合物、特開２０１１－５９６５６号公報の段落００５２に記載の化合物、特開２０１２－１９４５２０号公報の段落０１１４、０１１６および０１１８に記載の化合物などを使用することができる。 Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-15701A, 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.

　マイグレーション抑制剤の具体例としては、下記化合物を挙げることができる。

Figure JPOXMLDOC01-appb-C000037
Specific examples of the migration inhibitor include the following compounds.
Figure JPOXMLDOC01-appb-C000037

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

＜重合禁止剤＞
　本発明の感光性樹脂組成物は、重合禁止剤を含むことが好ましい。
　重合禁止剤としては、例えば、ヒドロキノン、１，４－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｐ－ｔｅｒｔ－ブチルカテコール、１，４－ベンゾキノン、ジフェニル－ｐ－ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、Ｎ－ニトロソジフェニルアミン、Ｎ－フェニルナフチルアミン、エチレンジアミン四酢酸、１，２－シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、５－ニトロソ－８－ヒドロキシキノリン、１－ニトロソ－２－ナフトール、２－ニトロソ－１－ナフトール、２－ニトロソ－５－（Ｎ－エチル－Ｎ－スルホプロピルアミノ）フェノール、Ｎ－ニトロソ－Ｎ－（１－ナフチル）ヒドロキシアミンアンモニウム塩、ビス（４－ヒドロキシ－３，５－ｔｅｒｔ－ブチル）フェニルメタンなどが好適に用いられる。また、特開２０１５－１２７８１７号公報の段落００６０に記載の重合禁止剤、および、国際公開ＷＯ２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもできる。
　また、下記化合物を用いることができる（Ｍｅはメチル基である）。

Figure JPOXMLDOC01-appb-C000038
　本発明の感光性樹脂組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の感光性樹脂組成物の全固形分に対して、０．０１～５質量％であることが好ましく、０．０２～３質量％であることがより好ましく、０．０５～２．５質量％であることが特に好ましい。
　重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 <Polymerization inhibitor>
The photosensitive resin composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, 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-8-hydroxyquinoline , 1-Nito So-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4-Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. In addition, a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used.
Moreover, the following compound can be used (Me is a methyl group).
Figure JPOXMLDOC01-appb-C000038
 When the photosensitive resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 5% by mass with respect to the total solid content of the photosensitive resin composition of the present invention. Is 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.

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

　シランカップリング剤の例としては、特開２０１４－１９１００２号公報の段落００６２～００７３に記載の化合物、国際公開ＷＯ２０１１／０８０９９２Ａ１号の段落００６３～００７１に記載の化合物、特開２０１４－１９１２５２号公報の段落００６０～００６１に記載の化合物、特開２０１４－４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開ＷＯ２０１４／０９７５９４号の段落００５５に記載の化合物が挙げられる。また、特開２０１１－１２８３５８号公報の段落００５０～００５８に記載のように異なる２種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Ｅｔはエチル基を表す。

Figure JPOXMLDOC01-appb-C000039
Examples of the silane coupling agent 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.
Figure JPOXMLDOC01-appb-C000039

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

　金属接着性改良剤の含有量はポリマー前駆体１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは０．５～１５質量部の範囲であり、特に好ましくは０．５～５質量部の範囲である。上記下限値以上とすることで硬化工程後の硬化膜と金属層との接着性が良好となり、上記上限値以下とすることで硬化工程後の硬化膜の耐熱性、機械特性が良好となる。金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 The content of the metal adhesion 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.

＜塩基発生剤＞
　本発明の感光性樹脂組成物は、塩基発生剤を含んでいてもよい。塩基発生剤は、熱塩基発生剤でも光塩基発生剤でもよい。 <Base generator>
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.

＜＜熱塩基発生剤＞＞
　熱塩基発生剤としては、その種類等は特に定めるものではないが、４０℃以上に加熱すると塩基を発生する酸性化合物、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩から選ばれる少なくとも一種を含む熱塩基発生剤を含むことが好ましい。ここで、ｐＫａ１とは、多価の酸の第一のプロトンの解離定数（Ｋａ）の対数表示（－Ｌｏｇ１０Ｋａ）を示す。
　このような化合物を配合することにより、ポリマー前駆体の環化反応を低温で行うことができ、また、より安定性に優れた組成物とすることができる。また、熱塩基発生剤は、加熱しなければ塩基を発生しないので、ポリマー前駆体と共存させても、保存中におけるポリマー前駆体の環化を抑制でき、保存安定性に優れている。 << 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. Here, pKa1 represents a logarithmic representation (−Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
By blending such a compound, the cyclization reaction of the polymer precursor can be performed at a low temperature, and a composition having more excellent stability can be obtained. In addition, since the thermal base generator does not generate a base unless it is heated, cyclization of the polymer precursor during storage can be suppressed even if it coexists with the polymer precursor, and the storage stability is excellent.

　本発明における熱塩基発生剤は、４０℃以上に加熱すると塩基を発生する酸性化合物（Ａ１）、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩（Ａ２）から選ばれる少なくとも一種を含むことが好ましい。
　上記酸性化合物（Ａ１）および上記アンモニウム塩（Ａ２）は、加熱すると塩基を発生するので、これらの化合物から発生した塩基により、ポリマー前駆体の環化反応を促進でき、ポリマー前駆体の環化を低温で行うことができる。また、これらの化合物は、塩基により環化して硬化するポリマー前駆体と共存させても、加熱しなければポリマー前駆体の環化が殆ど進行しないので、安定性に優れたポリマー前駆体を調製することができる。
　なお、本明細書において、酸性化合物とは、化合物を容器に１ｇ採取し、イオン交換水とテトラヒドロフランとの混合液（質量比は水／テトラヒドロフラン＝１／４）を５０ｍＬ加えて、室温で１時間撹拌する。その溶液をｐＨメーターを用いて、２０℃にて測定した値が７未満である化合物を意味する。 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. In addition, even if these compounds coexist with a polymer precursor that is cured by cyclization with a base, cyclization of the polymer precursor hardly proceeds unless heated, so that a polymer precursor having excellent stability is prepared. be able to.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. Stir. The value of the solution measured at 20 ° C. using a pH meter is less than 7.

　本発明において、酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度は、４０℃以上が好ましく、１２０～２００℃がより好ましい。塩基発生温度の上限は、１９０℃以下が好ましく、１８０℃以下がより好ましく、１６５℃以下がさらに好ましい。塩基発生温度の下限は、１３０℃以上が好ましく、１３５℃以上がより好ましい。
　酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度が１２０℃以上であれば、保存中に塩基が発生しにくいので、安定性に優れたポリマー前駆体を調製することができる。酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度が２００℃以下であれば、ポリマー前駆体の環化温度を低下できる。塩基発生温度は、例えば、示差走査熱量測定を用い、化合物を耐圧カプセル中５℃／分で２５０℃まで加熱し、最も温度が低い発熱ピークのピーク温度を読み取り、ピーク温度を塩基発生温度として測定することができる。 In the present invention, 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. If 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.

　本発明において、熱塩基発生剤により発生する塩基は、２級アミンまたは３級アミンが好ましく、３級アミンがより好ましい。３級アミンは、塩基性が高いので、ポリマー前駆体の環化温度をより低下できる。また、熱塩基発生剤により発生する塩基の沸点は、８０℃以上であることが好ましく、１００℃以上であることがより好ましく、１４０℃以上であることがさらに好ましい。また、発生する塩基の分子量は、８０～２０００が好ましい。下限は１００以上がより好ましい。上限は５００以下がより好ましい。なお、分子量の値は、構造式から求めた理論値である。 In the present invention, 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.

　本発明において、上記酸性化合物（Ａ１）は、アンモニウム塩および後述する式（１０１）または（１０２）で表される化合物から選ばれる１種以上を含むことが好ましい。 In the present invention, 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.

　本発明において、上記アンモニウム塩（Ａ２）は、酸性化合物であることが好ましい。なお、上記アンモニウム塩（Ａ２）は、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を含む化合物であってもよいし、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を除く化合物であってもよい。 In the present invention, 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.

　熱塩基発生剤として用いられるアンモニウム塩は、下記式（１０１）または式（１０２）で表されるアンモニウムカチオンと、アニオンとの塩が好ましい。アニオンは、アンモニウムカチオンのいずれかの一部と共有結合を介して結合していてもよく、アンモニウムカチオンの分子外に有していてもよいが、アンモニウムカチオンの分子外に有していることが好ましい。なお、アニオンが、アンモニウムカチオンの分子外に有するとは、アンモニウムカチオンとアニオンが共有結合を介して結合していない場合をいう。以下、カチオン部の分子外のアニオンを対アニオンともいう。

Figure JPOXMLDOC01-appb-C000040
　式中ＲＮ１～ＲＮ６は、それぞれ独立に、水素原子または炭化水素基（炭素数１～３６が好ましく、１～２４がより好ましく、１～１２が特に好ましい）を表し、アルキル基（炭素数１～３６が好ましく、１～２４がより好ましく、１～２３が特に好ましい）、アルケニル基（炭素数２～３６が好ましく、２～２４がより好ましく、２～２３が特に好ましい）、アルキニル基（炭素数１～３６が好ましく、１～２４がより好ましく、１～２３が特に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）が好ましい。
　ＲＮ７は炭化水素基（炭素数１～２４が好ましく、１～１２がより好ましい）を表し、アルキリデン基（炭素数１～２４が好ましく、１～１２がより好ましい）が好ましい。
　ＲＮ１とＲＮ２、ＲＮ３とＲＮ４、ＲＮ５とＲＮ６、ＲＮ５とＲＮ７はそれぞれ結合して環を形成してもよい。環を形成する際にはその途中に上記連結基Ｌ、あるいは、後記ヘテロ連結基Ｌｈを介在していてもよい。ＲＮ１～ＲＮ７は、本発明の効果を損ねない範囲で、前述の置換基Ｔを有していてもよい。 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. In addition, that an anion has outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.
Figure JPOXMLDOC01-appb-C000040
 In the formula, 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. When the ring is formed, 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.

　アンモニウムカチオンは、下記式（Ｙ１－１）～（Ｙ１－６）のいずれかで表されることが好ましい。

Figure JPOXMLDOC01-appb-C000041
The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-6).
Figure JPOXMLDOC01-appb-C000041

　式（Ｙ１－１）～（Ｙ１－６）において、ＲＮ１０１は、Ｎｎ価（Ｎｎは、１～１２の整数）の有機基を表し、アルカンを基礎とするＮｎ価の基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アルケンを基礎とするＮｎ価の基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、芳香族炭化水素を基礎とするＮｎ価の基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）、またはそれらの組み合わせが挙げられる。ＲＮ１０１は中でも芳香族炭化水素基であることが好ましい。ＲＮ１０１は本発明の効果を損ねない範囲で、前述の置換基Ｔを有していてもよい。ＲＮ１０１がアルカンを基礎とする基またはアルケンを基礎とする基の場合、下記ヘテロ連結基Ｌｈを介在していてもよい。
　ＲＮ１およびＲＮ７は、式（１０１）または式（１０２）におけるＲＮ１およびＲＮ７と同義である。
　ＲＮ８はアルキル基（炭素数１～３６が好ましく、２～２４がより好ましく、４～１８が特に好ましい）、アルケニル基（炭素数２～３６が好ましく、２～２４がより好ましく、４～１８が特に好ましい）、アルキニル基（炭素数２～３６が好ましく、２～２４がより好ましく、４～１８が特に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）である。このとき、アルキル基、アルケニル基、アルキニル基、アリール基には、鎖の途中に、あるいは母核との連結に、ヘテロ原子を有する連結基Ｌｈが介在していてもよい。ヘテロ原子を有する連結基Ｌｈとしては、－Ｏ－、－Ｓ－、－Ｃ（＝Ｏ）－、－ＮＲ３－、またはこれらの組み合わせに係る連結基が挙げられる。ヘテロ原子を有する連結基Ｌｈの数は、１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい。Ｒ３は水素原子またはアルキル基（好ましくはメチル基）である。ＲＮ８は本発明の効果を損ねない範囲で、さらに前述の置換基Ｔを有していてもよい。
　ＲＮ９はＲＮ８と同義の基であることが好ましい。なかでも、アリール基含有基が好ましく、アリーロイル基含有基がより好ましく、アリーロイルアルキル基（アルキル基は炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）が特に好ましい。このとき、アリール基ないしアリーロイル基の芳香環には本発明の効果を損ねない範囲でさらに置換基Ｔが導入されていてもよい。
　式（Ｙ１－４）において、ＡｒＮ１０１およびＡｒＮ１０２は、それぞれ独立に、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）を表す。
　Ｎｎは、１以上１２以下の整数を表す。Ｎｍは、０～５の整数を表す。Ｎｏは１～１２の整数が好ましく、１～６の整数がより好ましく、１～３の整数が特に好ましい。
　ＲＮ１どうし、ＲＮ１とＲＮ８、ＲＮ１とＲＮ７、ＲＮ１とＲＮ９、ＲＮ１とＡｒＮ１０１、ＲＮ１とＡｒＮ１０２、ＡｒＮ１０１とＡｒＮ１０２は、それぞれ結合して環を形成してもよい。環を形成する際にはその途中に上記連結基Ｌ、あるいは、後記ヘテロ連結基Ｌｈを介在していてもよい。 In Formula (Y1-1) ~ (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. An alkene-based Nn-valent group (2 to 12 carbon atoms is preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable) ), Nn-valent groups based on aromatic hydrocarbons (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), or combinations thereof. Among these, 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. In the case where 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). Is particularly preferred), 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). At this time, 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 . Among them, 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. At this time, a substituent T may be further introduced into the aromatic ring of the aryl group or aryloyl group as long as the effects of the present invention are not impaired.
In formula (Y1-4), 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. When the ring is formed, the linking group L or a hetero linking group Lh described later may be interposed in the middle of the ring.

　本実施形態において、アンモニウム塩は、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有することが好ましい。アニオンのｐＫａ１の上限は、３．５以下がより好ましく、３．２以下が一層好ましい。下限は、０．５以上が好ましく、１．０以上がより好ましい。アニオンのｐＫａ１が上記範囲であれば、ポリマー前駆体をより低温で環化でき、さらには、組成物の安定性を向上できる。ｐＫａ１が４以下であれば、熱塩基発生剤の安定性が良好で、加熱なしに塩基が発生することを抑制でき、組成物の安定性が良好である。ｐＫａ１が０以上であれば、発生した塩基が中和されにくく、ポリマー前駆体などの環化効率が良好である。
　アニオンの種類は、カルボン酸アニオン、フェノールアニオン、リン酸アニオンおよび硫酸アニオンから選ばれる１種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
　カルボン酸アニオンは、２個以上のカルボキシル基を持つ２価以上のカルボン酸のアニオンが好ましく、２価のカルボン酸のアニオンがより好ましい。この態様によれば、組成物の安定性、硬化性および現像性をより向上できる熱塩基発生剤とすることができる。特に、２価のカルボン酸のアニオンを用いることで、組成物の安定性、硬化性および現像性をさらに向上できる。
　本実施形態において、カルボン酸アニオンは、ｐＫａ１が４以下のカルボン酸のアニオンであることが好ましい。ｐＫａ１は、３．５以下がより好ましく、３．２以下が一層好ましい。この態様によれば、組成物の安定性をより向上できる。
　ここでｐＫａ１とは、多価の酸の第一のプロトンの解離定数（Ｋａ）の対数表示（－Ｌｏｇ１０Ｋａ）を示し、、Ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　Ｏｒｇａｎｉｃ　Ｓｔｒｕｃｔｕｒｅｓ　ｂｙ　Ｐｈｙｓｉｃａｌ　Ｍｅｔｈｏｄｓ（著者：Ｂｒｏｗｎ，　Ｈ．　Ｃ．，　ＭｃＤａｎｉｅｌ，　Ｄ．　Ｈ．，　Ｈａｆｌｉｇｅｒ，　Ｏ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　編纂：Ｂｒａｕｄｅ，　Ｅ．　Ａ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ，　Ｎｅｗ　Ｙｏｒｋ，　１９５５）や、Ｄａｔａ　ｆｏｒ　Ｂｉｏｃｈｅｍｉｃａｌ　Ｒｅｓｅａｒｃｈ（著者：Ｄａｗｓｏｎ，　Ｒ．Ｍ．Ｃ．ｅｔ　ａｌ；　Ｏｘｆｏｒｄ，　Ｃｌａｒｅｎｄｏｎ　Ｐｒｅｓｓ，　１９５９）に記載の値を参照することができる。これらの文献に記載の無い化合物については、ＡＣＤ／ｐＫａ（ＡＣＤ／Ｌａｂｓ製）のソフトを用いて構造式より算出した値を用いることとする。 In this embodiment, 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. If pKa1 is 0 or more, the generated base is hardly neutralized, and the cyclization efficiency of the polymer precursor and the like 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. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability and developability of the composition. In particular, the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
In the present embodiment, 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. According to this aspect, the stability of the composition can be further improved.
Here, 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.

　カルボン酸アニオンは、下記式（Ｘ１）で表されることが好ましい。

Figure JPOXMLDOC01-appb-C000042
　式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。 The carboxylate anion is preferably represented by the following formula (X1).
Figure JPOXMLDOC01-appb-C000042
 In the formula (X1), EWG represents an electron withdrawing group.

　本実施形態において電子求引性基とは、ハメットの置換基定数σｍが正の値を示すものを意味する。ここでσｍは、都野雄甫総説、有機合成化学協会誌第２３巻第８号（１９６５）ｐ．６３１－６４２に詳しく説明されている。なお、本実施形態における電子求引性基は、上記文献に記載された置換基に限定されるものではない。
　σｍが正の値を示す置換基の例としては例えば、ＣＦ３基（σｍ＝０．４３）、ＣＦ３ＣＯ基（σｍ＝０．６３）、ＨＣ≡Ｃ基（σｍ＝０．２１）、ＣＨ２＝ＣＨ基（σｍ＝０．０６）、Ａｃ基（σｍ＝０．３８）、ＭｅＯＣＯ基（σｍ＝０．３７）、ＭｅＣＯＣＨ＝ＣＨ基（σｍ＝０．２１）、ＰｈＣＯ基（σｍ＝０．３４）、Ｈ２ＮＣＯＣＨ２基（σｍ＝０．０６）などが挙げられる。なお、Ｍｅはメチル基を表し、Ａｃはアセチル基を表し、Ｐｈはフェニル基を表す（以下、同じ）。 In the present embodiment, the electron withdrawing group means a group in which Hammett's substituent constant σm exhibits a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include, for example, CF 3 group (σm = 0.43), CF 3 CO group (σm = 0.63), HC≡C group (σm = 0.21), CH 2 ═CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0.34), H 2 NCOCH 2 group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).

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

Figure JPOXMLDOC01-appb-C000043
　式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒｘ１～Ｒｘ３は、それぞれ独立に、水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、アリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）、ヒドロキシル基、またはカルボキシル基を表す。ただし、式（ＥＷＧ－１）のＲＸ１、式（ＥＷＧ－４）のＲＸ１がカルボキシル基であることはない。Ａｒは芳香族基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）を表す。Ｒｘ１～Ｒｘ３がアルキル基、アルケニル基、アリール基のとき、環を形成してもよく、環を形成する際にはその途中に上記連結基Ｌ、あるいは、後記ヘテロ連結基Ｌｈを介在していてもよい。Ｒｘ１～Ｒｘ３が、アルキル基、アルケニル基、アリール基のとき、ならびに、Ａｒは、本発明の効果を損ねない範囲で、置換基Ｔを有していてもよい。なかでも、Ａｒは特にカルボキシル基（好ましくは１～３個）を有することが好ましい。
　Ｎｐは１～６が好ましく、１～３がより好ましく、１または２が特に好ましい。 EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
Figure JPOXMLDOC01-appb-C000043
 In formulas (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom or an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 and more preferably 1 to 3). Particularly preferred), 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 is particularly preferred), and represents a hydroxyl group or a carboxyl group. However, 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). When R x1 to R x3 are an alkyl group, an alkenyl group, or an aryl group, a ring may be formed, and when the ring is formed, the linking group L or the hetero linking group Lh described later is interposed in the middle of the ring. It may be. When 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. Among these, 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.

　本実施形態において、カルボン酸アニオンは、下記式（ＸＡ）で表されるものも好ましい。
式（ＸＡ）

Figure JPOXMLDOC01-appb-C000044
　式（ＸＡ）において、Ｌ１０は、単結合、または、アルキレン基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アルケニレン基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）、芳香族基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）、－ＮＲＸ－およびこれらの組み合わせから選ばれる２価の連結基を表し、ＲＸは、水素原子、アルキル基（炭素数１～１２が好ましく、１～６がより好ましく、１～３が特に好ましい）、アルケニル基（炭素数２～１２が好ましく、２～６がより好ましく、２～３が特に好ましい）またはアリール基（炭素数６～２２が好ましく、６～１８がより好ましく、６～１０が特に好ましい）を表す。 In the present embodiment, the carboxylate anion is also preferably represented by the following formula (XA).
Formula (XA)
Figure JPOXMLDOC01-appb-C000044
 In the 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). Preferably 2 to 6, more preferably 2 to 3), an aromatic group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 and particularly preferably 6 to 10), -NR X -and these R X represents a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 3 carbon atoms), an alkenyl group (carbon The number 2 to 12 is preferable, 2 to 6 is more preferable, and 2 to 3 is particularly preferable) or an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 10 carbon atoms).

　カルボン酸アニオンの具体例としては、マレイン酸アニオン、フタル酸アニオン、Ｎ－フェニルイミノ二酢酸アニオンおよびシュウ酸アニオンが挙げられる。
　熱塩基発生剤の詳細は、特開２０１６－０２７３５７号公報の段落００２１～００７７の記載を参酌でき、これらの内容は本明細書に組み込まれる。
　熱塩基発生剤としては、以下の化合物が例示される。

Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
 Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion.
Details of 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.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046

Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048

　熱塩基発生剤を用いる場合、組成物における熱塩基発生剤の含有量は、組成物の全固形分に対し、０．１～５０質量％であることが好ましい。下限は、０．２５質量％以上がより好ましく、０．５質量％以上がさらに好ましい。上限は、２０質量％以下がより好ましく、１０質量％以下がさらに好ましい。
　熱塩基発生剤は、１種または２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。
　また、本発明の一実施形態として、熱塩基発生剤を実質的に含まない構成とすることもできる。実質的に含まないとは、組成物の全固形分の０．１質量％未満であることをいい、さらには、０．０１質量％以下、特には、０．００１質量％以下とすることもできる。 When a thermal base generator is used, 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.
In addition, as an embodiment of the present invention, 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.

＜＜光塩基発生剤＞＞
　本発明で用いる感光性樹脂組成物は、光塩基発生剤を含んでいてもよい。光塩基発生剤とは、露光により塩基を発生するものであり、常温常圧の通常の条件下では活性を示さないが、外部刺激として電磁波の照射と加熱が行なわれると、塩基（塩基性物質）を発生するものであれば特に限定されるものではない。露光により発生した塩基はポリマー前駆体を加熱により硬化させる際の触媒として働くため、現像処理を行う場合に好適に用いることができる。 << Photobase generator >>
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. However, when an electromagnetic wave is irradiated and heated as an external stimulus, 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.

　本発明においては、光塩基発生剤として公知のものを用いることができる。例えば、Ｍ．Ｓｈｉｒａｉ，　ａｎｄ　Ｍ．Ｔｓｕｎｏｏｋａ，　Ｐｒｏｇ．Ｐｏｌｙｍ．Ｓｃｉ．，２１，１（１９９６）；角岡正弘，高分子加工，４６，２（１９９７）；Ｃ．Ｋｕｔａｌ，Ｃｏｏｒｄ．Ｃｈｅｍ．Ｒｅｖ．，２１１，３５３（２００１）；Ｙ．Ｋａｎｅｋｏ，Ａ．Ｓａｒｋｅｒ，　ａｎｄ　Ｄ．Ｎｅｃｋｅｒｓ，Ｃｈｅｍ．Ｍａｔｅｒ．，１１，１７０（１９９９）；Ｈ．Ｔａｃｈｉ，Ｍ．Ｓｈｉｒａｉ，　ａｎｄ　Ｍ．Ｔｓｕｎｏｏｋａ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，１３，１５３（２０００）；Ｍ．Ｗｉｎｋｌｅ，　ａｎｄ　Ｋ．Ｇｒａｚｉａｎｏ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，３，４１９（１９９０）；Ｍ．Ｔｓｕｎｏｏｋａ，Ｈ．Ｔａｃｈｉ，　ａｎｄ　Ｓ．Ｙｏｓｈｉｔａｋａ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，９，１３（１９９６）；Ｋ．Ｓｕｙａｍａ，Ｈ．Ａｒａｋｉ，Ｍ．Ｓｈｉｒａｉ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，１９，８１（２００６）に記載されているように、遷移金属化合物錯体や、アンモニウム塩などの構造を有するものや、アミジン部分がカルボン酸と塩を形成することで潜在化されたもののように、塩基成分が塩を形成することにより中和されたイオン性の化合物や、カルバメート誘導体、オキシムエステル誘導体、アシル化合物などのウレタン結合やオキシム結合などにより塩基成分が潜在化された非イオン性の化合物を挙げることができる。 In the present invention, known photobase generators can be used. For example, 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. Technol. 3,419 (1990); Tsunooka, H .; Tachi, and S. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), such as those having a structure such as a transition metal compound complex, an ammonium salt, or the like that is latentized by forming a salt with a carboxylic acid in the amidine moiety. 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.

　光塩基発生剤から発生される塩基性物質としては特に限定されないが、アミノ基を有する化合物、特にモノアミンや、ジアミンなどのポリアミン、また、アミジンなどが挙げられる。
　発生する塩基性物質は、より塩基性度の高いアミノ基を有する化合物が好ましい。このような化合物は、ポリマー前駆体のイミド化における脱水縮合反応等に対する触媒作用が強く、より少量の添加で、より低い温度での脱水縮合反応等における触媒効果の発現が可能となるからである。つまりは、発生した塩基性物質の触媒効果が大きいため、感光性樹脂組成物としての見た目の感度は向上する。
　上記触媒効果の観点から、塩基性物質は、アミジン、脂肪族アミンであることが好ましい。
　本発明で用いる光塩基発生剤としては、芳香環を含み、発生する塩基性物質が、アミノ基を有する化合物であることが好ましい。 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.

　本発明に係る光塩基発生剤としては、例えば、特開２００９－８０４５２号公報および国際公開第２００９／１２３１２２号パンフレットで開示されたような桂皮酸アミド構造を有する光塩基発生剤、特開２００６－１８９５９１号公報および特開２００８－２４７７４７号公報で開示されたようなカルバメート構造を有する光塩基発生剤、特開２００７－２４９０１３号公報および特開２００８－００３５８１号公報で開示されたようなオキシム構造、カルバモイルオキシム構造を有する光塩基発生剤等が挙げられるが、これらに限定されず、その他にも公知の光塩基発生剤の構造を用いることができる。 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.

　その他、光塩基発生剤としては、特開２０１２－９３７４６号公報の段落０１８５～０１８８、０１９９～０２００および０２０２に記載の化合物、特開２０１３－１９４２０５号公報の段落００２２～００６９に記載の化合物、特開２０１３－２０４０１９号公報の段落００２６～００７４に記載の化合物、ならびに国際公開ＷＯ２０１０／０６４６３１号公報の段落００５２に記載の化合物が例として挙げられる。 Other 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.

　光塩基発生剤の市販品としては、ＷＰＢＧ－２６６、ＷＰＢＧ－３００、ＷＰＧＢ－３４５、ＷＰＧＢ－１４０、ＷＰＢＧ－１６５、ＷＰＢＧ－０２７、ＰＢＧ－０１８、ＷＰＧＢ－０１５、ＷＰＢＧ－０４１、ＷＰＧＢ－１７２、ＷＰＧＢ－１７４、ＷＰＢＧ－１６６、ＷＰＧＢ－１５８、ＷＰＧＢ－０２５、ＷＰＧＢ－１６８、ＷＰＧＢ－１６７およびＷＰＢＧ－０８２（和光純薬工業（株）製）を用いることもできる。
　また、光塩基発生剤としては、下記化合物が例示される。Ｅｔはエチル基を表し、Ｍｅはメチル基を表す。

Figure JPOXMLDOC01-appb-C000049
Commercially available 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.
Figure JPOXMLDOC01-appb-C000049

　光塩基発生剤を用いる場合、組成物における光塩基発生剤の含有量は、組成物の全固形分に対し、０．１～５０質量％であることが好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上がさらに好ましい。上限は、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。
　光塩基発生剤は、１種または２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。
　また、本発明の一実施形態として、光塩基発生剤を実質的に含まない構成とすることもできる。実質的に含まないとは、組成物の全固形分の０．１質量％未満であることをいい、さらには、０．０１質量％以下、特には、０．００１質量％以下とすることもできる。 When a photobase generator is used, 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.
In addition, as an embodiment of the present invention, 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.

＜その他の添加剤＞
　本発明の感光性樹脂組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、熱酸発生剤、増感色素、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は組成物の固形分の３質量％以下とすることが好ましい。 <Other additives>
The photosensitive resin composition of the present invention 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. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.

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

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

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

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

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

　本発明の感光性樹脂組成物が連鎖移動剤を有する場合、連鎖移動剤の含有量は、本発明の感光性樹脂組成物の全固形分１００質量部に対し、０．０１～２０質量部が好ましく、１～１０質量部がより好ましく、１～５質量部がさらに好ましい。連鎖移動剤は１種のみでもよいし、２種以上であってもよい。連鎖移動剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition of the present invention. Preferably, 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.

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

Figure JPOXMLDOC01-appb-C000050
<< Surfactant >>
Various types of surfactants may be added to the photosensitive resin composition of the present invention from the viewpoint of further improving coatability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.
Figure JPOXMLDOC01-appb-C000050

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

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

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

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

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

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

＜組成物の調製＞
　本発明の感光性樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
　また、組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、１μｍ以下が好ましく、０．５μｍ以下がより好ましく、０．１μｍ以下がさらに好ましい。フィルターの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルターろ過工程では、複数種のフィルターを直列または並列に接続して用いてもよい。複数種のフィルターを使用する場合は、孔径および／または材質が異なるフィルターを組み合わせて使用してもよい。また、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であってもよい。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は０．０５ＭＰａ以上０．３ＭＰａ以下が好ましい。
　フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 <Preparation of composition>
The photosensitive resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and filter. When the pressure is applied for filtration, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

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

　本発明の硬化膜を２層以上積層して積層体としてもよい。本発明の硬化膜を２層以上有する積層体は、硬化膜の間に金属層を有する態様が好ましい。このような金属層は、再配線層などの金属配線として好ましく用いられる。 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.

　本発明の硬化膜の適用可能な分野としては、半導体デバイスの絶縁膜、再配線層用層間絶縁膜などが挙げられる。特に、解像性が良好であるため、３次元実装デバイスにおける再配線層用層間絶縁膜などに好ましく用いることができる。 The fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, 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.

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

　本発明の硬化膜の製造方法は、本発明の感光性樹脂組成物を用いることを含む。好ましくは、本発明の感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、上記感光性樹脂組成物層を露光する露光工程と、上記露光された感光性樹脂組成物層（樹脂層）に対して、現像処理を行う現像処理工程とを有する、硬化膜の製造方法が挙げられる。本発明の感光性樹脂組成物は、現像を行う場合に好ましく用いられる。 The method for producing a cured film of the present invention includes using the photosensitive resin composition of the present invention. Preferably, 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.

　本発明の積層体の製造方法は、本発明の硬化膜の製造方法を含む。本発明の積層体の製造方法は、本発明の硬化膜の製造方法に従って、硬化膜を形成後、さらに、再度、感光性樹脂組成物層形成工程、露光工程、および、現像処理工程を、上記順に再度行うことが好ましい。特に、感光性樹脂組成物層形成工程、露光工程、および、現像処理工程を、さらに、上記順に２～５回（すなわち、合計で３～６回）行うことが好ましい。このように硬化膜を積層することにより、積層体とすることができる。本発明では特に、硬化膜を設けて現像した後、現像除去された部分に金属層を設けることが好ましい。
　以下これらの詳細を説明する。 The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. According to the method for producing a laminate of the present invention, after forming a cured film according to the method for producing a cured film of the present 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. In particular, 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). Thus, a laminated body can be obtained by laminating a cured film. In the present invention, in particular, it is preferable to provide a metal layer in a portion that has been developed and removed after providing and developing a cured film.
These details will be described below.

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

＜＜乾燥工程＞＞
　本発明の積層体の製造方法は、感光性樹脂組成物層を形成後、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は５０～１５０℃で、７０℃～１３０℃がより好ましく、９０℃～１１０℃がさらに好ましい。乾燥時間としては、３０秒～２０分が例示され、１分～１０分が好ましく、３分～７分がより好ましい。 << Drying process >>
The manufacturing method of 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.

＜＜露光工程＞＞
　本発明の積層体の製造方法は、上記感光性樹脂組成物層を露光する露光工程を含んでもよい。露光量は、感光性樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長３６５ｎｍでの露光エネルギー換算で１００～１００００ｍＪ／ｃｍ２照射することが好ましく、２００～８０００ｍＪ／ｃｍ２照射することがより好ましい。
　露光波長は、１９０～１０００ｎｍの範囲で適宜定めることができ、２４０～５５０ｎｍが好ましい。
　露光波長は、光源との関係でいうと、（１）半導体レーザー（波長　８３０ｎｍ、５３２ｎｍ、４８８ｎｍ、４０５ｎｍ　ｅｔｃ．）、（２）メタルハライドランプ、（３）高圧水銀灯、ｇ線（波長　４３６ｎｍ）、ｈ線（波長　４０５ｎｍ）、ｉ線（波長　３６５ｎｍ）、ブロード（ｇ，ｈ，ｉ線の３波長）、（４）エキシマレーザー、ＫｒＦエキシマレーザー（波長　２４８ｎｍ）、ＡｒＦエキシマレーザー（波長　１９３ｎｍ）、Ｆ２エキシマレーザー（波長　１５７ｎｍ）、（５）極端紫外線；ＥＵＶ（波長　１３．６ｎｍ）、（６）電子線等が挙げられる。本発明に感光性樹脂組成物については、特に高圧水銀灯による露光が好ましく、なかでも、ｉ線による露光が好ましい。これにより、特に高い露光感度が得られる。 << Exposure process >>
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. For the photosensitive resin composition of the present invention, 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.

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

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

＜＜加熱工程＞＞
　本発明の積層体の製造方法は、現像後に加熱する工程を含むことが好ましい。加熱工程では、ポリマー前駆体の環化反応が進行する。また、本発明の組成物はポリマー前駆体以外のラジカル重合性化合物を含むが、未反応のポリマー前駆体以外のラジカル重合性化合物の硬化なども進行する。加熱温度（最高加熱温度）としては、５０～４５０℃が好ましく、１４０～４００℃がより好ましく、１６０～３５０℃がさらに好ましい。
　加熱は、加熱開始時の温度から最高加熱温度まで１～１２℃／分の昇温速度で行うことが好ましく、２～１０℃／分がより好ましく、３～１０℃／分がさらに好ましい。昇温速度を２℃／分以上とすることにより、生産性を確保しつつ、アミンの過剰な揮発を防止することができ、昇温速度を１２℃／分以下とすることにより、硬化膜の残存応力を緩和することができる。
　加熱開始時の温度は、２０℃～１５０℃が好ましく、２０℃～１３０℃がより好ましく、２５℃～１２０℃がさらに好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の温度のことをいう。例えば、感光性樹脂組成物を基板の上に適用した後、乾燥させる場合、この乾燥後の温度であり、例えば、感光性樹脂組成物に含まれる溶剤の沸点よりも、３０～２００℃低い温度から徐々に昇温させることが好ましい。
　加熱時間（最高加熱温度での加熱時間）は、１０～３６０分であることが好ましく、２０～３００分であることがさらに好ましく、３０～２４０分であることが特に好ましい。
　特に多層の積層体を形成する場合、硬化膜の層間の密着性の観点から、加熱温度は１８０℃～３２０℃で加熱することが好ましく、１８０℃～２６０℃で加熱することがより好ましい。その理由は定かではないが、この温度とすることで、層間のポリマー前駆体のエチニル基同士が架橋反応を進行しているためと考えられる。 << Heating process >>
It is preferable that 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 (maximum 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. By setting the heating rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the heating rate to 12 ° C./min or less, the cured film Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto a substrate and then dried, 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.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason is not certain, it is considered that the ethynyl groups of the polymer precursors between layers proceed with a crosslinking reaction at this temperature.

　加熱は段階的に行ってもよい。例として、２５℃から１８０℃まで３℃／分で昇温し、１８０℃にて６０分保持し、１８０℃から２００℃まで２℃／分で昇温し、２００℃にて１２０分保持する、といった前処理工程を行ってもよい。前処理工程としての加熱温度は１００～２００℃が好ましく、１１０～１９０℃であることがより好ましく、１２０～１８５℃であることがさらに好ましい。この前処理工程においては、米国ＵＳ９１５９５４７号公報に記載のように紫外線を照射しながら処理することも好ましい。このような前処理工程により膜の特性を向上させることが可能である。前処理工程は１０秒間～２時間程度の短い時間で行うとよく、１５秒～３０分間がより好ましい。前処理は２段階以上のステップとしてもよく、例えば１００～１５０℃の範囲で前処理工程１を行い、その後に１５０～２００℃の範囲で前処理工程２を行ってもよい。
　さらに、加熱後冷却してもよく、この場合の冷却速度としては、１～５℃／分であることが好ましい。 Heating may be performed in stages. For example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min, held at 180 ° C. for 60 minutes, heated from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. You may perform the pre-processing process of these. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

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

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

＜＜積層工程＞＞
　本発明の製造方法は、さらに、積層工程を含むことが好ましい。
　積層工程とは、再度、上記感光性樹脂組成物層形成工程、上記露光工程、および、上記現像処理工程を、上記順に行うことを含む一連の工程である。積層工程には、さらに、上記乾燥工程や加熱工程等を含んでいてもよいことは言うまでもない。
　積層工程後、さらに積層工程を行う場合には、上記露光工程後、または、上記金属層形成工程後に、さらに、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。
　上記積層工程は、２～５回行うことが好ましく、３～５回行うことがより好ましい。
　例えば、樹脂層／金属層／樹脂層／金属層／樹脂層／金属層のような、樹脂層が３層以上７層以下の構成が好ましく、３層以上５層以下がさらに好ましい。
　すなわち、本発明では特に、金属層を設けた後、さらに、上記金属層を覆うように、上記感光性樹脂組成物層形成工程、上記露光工程、および、上記現像処理工程を、上記順に行うことが好ましい。感光性樹脂組成物層（樹脂層）を積層する積層工程と、金属層形成工程を交互に行うことにより、感光性樹脂組成物層（樹脂層）と金属層を交互に積層することができる。 << Lamination process >>
The production method of the present invention preferably further includes a lamination step.
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.
When a lamination process is further performed after the lamination process, 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.
For example, the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers.
That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition 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.

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

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

（合成例１）
［４，４’－オキシジフタル酸二無水物、２－ヒドロキシエチルメタクリレートおよび下記に示すジアミン（ａ）からのポリイミド前駆体Ａ－１の合成］
　２１．２ｇの４，４’－オキシジフタル酸二無水物と、１８．０ｇの２－ヒドロキシエチルメタクリレートと、２３．９ｇのピリジンと、２５０ｍＬのジグリム（ジエチレングリコールジメチルエーテル）とを混合し、６０℃の温度で４時間撹拌して、４，４’－オキシジフタル酸二無水物と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０℃に保ちながら１７．０ｇのＳＯＣｌ２を６０分かけて加えた。５０ｍＬのＮ－メチルピロリドンで希釈した後、１００ｍＬのＮ－メチルピロリドンに３８．０ｇの下記に示すヒドロキシル基含有ジアミン（ａ）を溶解させた溶液を－１０℃で６０分かけて反応混合物に滴下して、混合物を２時間撹拌した後、２０ｍＬのエチルアルコールを加えた。次いで、６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を１５分間撹拌した。ポリイミド前駆体の固体を濾過してテトラヒドロフラン３８０ｇに溶解させた。得られた溶液を６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ濾過して、減圧下４５℃で３日間乾燥した。このポリイミド前駆体は、重量平均分子量２７４００、数平均分子量１０１００であった。 (Synthesis Example 1)
[Synthesis of polyimide precursor A-1 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and diamine (a) shown below]
21.2 g of 4,4′-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine, and 250 mL of diglyme (diethylene glycol dimethyl ether) were mixed at a temperature of 60 ° C. For 4 hours to produce a diester of 4,4′-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, a solution of 38.0 g of the hydroxyl group-containing diamine (a) shown below in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −10 ° C. over 60 minutes. After stirring the mixture for 2 hours, 20 mL of ethyl alcohol was added. Subsequently, it was poured into 6 liters of water to precipitate the polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. 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.

ジアミン（ａ）

Figure JPOXMLDOC01-appb-C000051
Diamine (a)
Figure JPOXMLDOC01-appb-C000051

（合成例２）
［ピロメリット酸二無水物、２－ヒドロキシエチルメタクリレートおよび４,４'－ジアミノ－２,２'-ビス(トリフルオロメチル)ビフェニルからのポリイミド前駆体Ａ－２の合成］
　１４．９ｇのピロメリット酸二無水物と、１８．０ｇの２－ヒドロキシエチルメタクリレートと、２３．９ｇのピリジンと、２５０ｍＬのジグリムとを混合し、６０℃の温度で４時間撹拌して、ピロメリット酸二無水物と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０℃に保ちながら１７．０ｇのＳＯＣｌ２を６０分かけて加えた。５０ｍＬのＮ－メチルピロリドンで希釈した後、１００ｍＬのＮ－メチルピロリドンに２０．１ｇの４,４'－ジアミノ－２,２'-ビス(トリフルオロメチル)ビフェニルを溶解させた溶液を－１０℃で６０分かけて反応混合物に滴下して、混合物を２時間撹拌した後、２０ｍＬのエチルアルコールを加えた。次いで、６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を１５分間撹拌した。ポリイミド前駆体の固体を濾過してテトラヒドロフラン３８０ｇに溶解させた。得られた溶液を６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ濾過して、減圧下４５℃で３日間乾燥した。このポリイミド前駆体は、重量平均分子量２３１００、数平均分子量９７００であった。 (Synthesis Example 2)
[Synthesis of polyimide precursor A-2 from pyromellitic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl]
14.9 g of pyromellitic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. A diester of merit acid dianhydride and 2-hydroxyethyl methacrylate was prepared. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 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. Subsequently, it was poured into 6 liters of water to precipitate the polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. 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.

（合成例３）
［４，４’－オキシジフタル酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノ－２,２'-ビス(トリフルオロメチル)ビフェニルからのポリイミド前駆体Ａ－３の合成］
　２１．２ｇの４，４’－オキシジフタル酸二無水物と、１８．０ｇの２－ヒドロキシエチルメタクリレートと、２３．９ｇのピリジンと、２５０ｍＬのジグリムとを混合し、６０℃の温度で４時間撹拌して、４，４’－オキシジフタル酸二無水物と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０℃に保ちながら１７．０ｇのＳＯＣｌ２を６０分かけて加えた。５０ｍＬのＮ－メチルピロリドンで希釈した後、１００ｍＬのＮ－メチルピロリドンに２０．１ｇの４,４'－ジアミノ－２,２'-ビス(トリフルオロメチル)ビフェニルを溶解させた溶液を－１０℃で６０分かけて反応混合物に滴下して、混合物を２時間撹拌した後、２０ｍＬのエチルアルコールを加えた。次いで、６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を１５分間撹拌した。ポリイミド前駆体の固体を濾過してテトラヒドロフラン３８０ｇに溶解させた。得られた溶液を６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ濾過して、減圧下４５℃で３日間乾燥した。このポリイミド前駆体は、重量平均分子量２３５００、数平均分子量９４００であった。 (Synthesis Example 3)
[Synthesis of polyimide precursor A-3 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl]
21.2 g of 4,4′-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at −10 ° C. After diluting with 50 mL of N-methylpyrrolidone, 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. Subsequently, it was poured into 6 liters of water to precipitate the polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. 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 23,500 and a number average molecular weight of 9,400.

（合成例４）
［４，４’－オキシジフタル酸二無水物、２－ヒドロキシエチルメタクリレートおよび４，４’－ジアミノジフェニルエーテルからのポリイミド前駆体Ａ－４の合成］
　２１．２ｇの４，４’－オキシジフタル酸二無水物と、１８．０ｇの２－ヒドロキシエチルメタクリレートと、２３．９ｇのピリジンと、２５０ｍＬのジグリムとを混合し、６０℃の温度で４時間撹拌して、４，４’－オキシジフタル酸二無水物と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０℃に保ちながら１７．０ｇのＳＯＣｌ２を６０分かけて加えた。５０ｍＬのＮ－メチルピロリドンで希釈した後、１００ｍＬのＮ－メチルピロリドンに２５．１ｇの４，４’－ジアミノジフェニルエーテルを溶解させた溶液を－１０℃で６０分かけて反応混合物に滴下して、混合物を２時間撹拌した後、２０ｍＬのエチルアルコールを加えた。次いで、６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を１５分間撹拌した。ポリイミド前駆体の固体を濾過してテトラヒドロフラン３８０ｇに溶解させた。得られた溶液を６リットルの水に投入して水の中でポリイミド前駆体を沈殿させ濾過して、減圧下４５℃で３日間乾燥した。このポリイミド前駆体は、重量平均分子量２３２００、数平均分子量９６００であった。 (Synthesis Example 4)
[Synthesis of polyimide precursor A-4 from 4,4′-oxydiphthalic dianhydride, 2-hydroxyethyl methacrylate and 4,4′-diaminodiphenyl ether]
21.2 g of 4,4′-oxydiphthalic dianhydride, 18.0 g of 2-hydroxyethyl methacrylate, 23.9 g of pyridine and 250 mL of diglyme are mixed and stirred at a temperature of 60 ° C. for 4 hours. Thus, a diester of 4,4′-oxydiphthalic dianhydride and 2-hydroxyethyl methacrylate was produced. The reaction mixture was then cooled to −10 ° C. and 17.0 g of SOCl 2 was added over 60 minutes while maintaining the temperature at −10 ° C. After dilution with 50 mL of N-methylpyrrolidone, a solution of 25.1 g of 4,4′-diaminodiphenyl ether dissolved in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −10 ° C. over 60 minutes. After the mixture was stirred for 2 hours, 20 mL of ethyl alcohol was added. Subsequently, it was poured into 6 liters of water to precipitate the polyimide precursor in water, and the water-polyimide precursor mixture was stirred for 15 minutes. 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.

（合成例５）
［２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンおよび４，４’－オキシジベンゾイルクロリドからのポリベンゾオキサゾール前駆体組成物Ａ－５の合成］
　２８．０ｇの２，２'－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパンを２００ｍＬのＮ－メチルピロリドンに撹拌溶解した。続いて、温度を０～５℃に保ちながら、２５．０ｇの４，４’－オキシジベンゾイルクロリドを３０分間で滴下した後、６０分間撹拌を続けた。得られた反応液に６Ｌの水を投入してポリベンゾオキサゾール前駆体を沈殿させ、固体をろ過して減圧下で、４５℃で２日間乾燥した。このポリベンゾオキサゾール前駆体は、重量平均分子量２５８００、数平均分子量９３００であった。 (Synthesis Example 5)
[Synthesis of Polybenzoxazole Precursor Composition A-5 from 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 4,4′-oxydibenzoyl chloride]
28.0 g of 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved by stirring in 200 mL of N-methylpyrrolidone. Subsequently, 25.0 g of 4,4′-oxydibenzoyl chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5 ° C., and stirring was continued for 60 minutes. 6 L of water was added to the obtained reaction solution to precipitate a polybenzoxazole precursor, and the solid was filtered and dried at 45 ° C. for 2 days under reduced pressure. This polybenzoxazole precursor had a weight average molecular weight of 25800 and a number average molecular weight of 9300.

（合成例６）
［硫黄原子を有するラジカル重合性化合物Ｂ１－１の合成］
　１０９．４ｇの２－ヒドロキシエチルメタクリレートと、７０．０ｇのピリジンと、５００ｍＬのテトラヒドロフランとを混合した。混合液を０℃に冷却し、温度を５℃以下に保ちながら５０．０ｇのＳＯＣｌ２を６０分かけて滴下して、その後１時間撹拌した。蒸留水２００ｍＬを加えて反応を停止して酢酸エチル５００ｍＬを加えた。得られた有機層を蒸留水で５回洗浄した後、エバポレーターで低沸点溶媒を除去して、２２０．１ｇのラジカル重合性化合物Ｂ１－１を得た。得られた化合物は、上述の硫黄原子を有するラジカル重合性化合物の例示化合物３０２である。
1H NMR (400 MHz, CDCl3)δ(ppm)： 6.15(ｔ, 2H), 5.62(ｔ, 2H), 4.37(m, 4H), 4.30(m, 2H), 4.21(m, 2H), 1.95(dd, 6H)。 (Synthesis Example 6)
[Synthesis of radical polymerizable compound B1-1 having sulfur atom]
109.4 g of 2-hydroxyethyl methacrylate, 70.0 g of pyridine, and 500 mL of tetrahydrofuran were mixed. The mixture was cooled to 0 ° C., 50.0 g of SOCl 2 was added dropwise over 60 minutes while keeping the temperature at 5 ° C. or lower, and then stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. 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.
1 H NMR (400 MHz, CDCl 3 ) δ (ppm): 6.15 (t, 2H), 5.62 (t, 2H), 4.37 (m, 4H), 4.30 (m, 2H), 4.21 (m, 2H), 1.95 (dd, 6H).

（合成例７）
［硫黄原子を有するラジカル重合性化合物Ｂ１－２の合成］
　１０１．８ｇの４－ビニルベンジルアルコールと、７０．０ｇのピリジンと、５００ｍＬのテトラヒドロフランとを混合した。混合液を０℃に冷却し、温度を５℃以下に保ちながら５０．０ｇのＳＯＣｌ２を６０分かけて滴下して、その後１時間撹拌した。蒸留水２００ｍＬを加えて反応を停止して酢酸エチル５００ｍＬを加えた。得られた有機層を蒸留水で５回洗浄した後、エバポレーターで低沸点溶媒を除去して、２００．２ｇのラジカル重合性化合物Ｂ１－２を得た。得られた化合物は、上述の硫黄原子を有するラジカル重合性化合物の例示化合物３１２である。 (Synthesis Example 7)
[Synthesis of radically polymerizable compound B1-2 having a sulfur atom]
101.8 g of 4-vinylbenzyl alcohol, 70.0 g of pyridine, and 500 mL of tetrahydrofuran were mixed. The mixture was cooled to 0 ° C., 50.0 g of SOCl 2 was added dropwise over 60 minutes while keeping the temperature at 5 ° C. or lower, and then stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. 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.

（合成例８）
［硫黄原子を有するラジカル重合性化合物Ｂ１－３の合成］
　１９．０ｇのビス（４－ヒドロキシフェニル）スルホンと、７．０ｇのピリジンと、１００ｍＬのテトラヒドロフランとを混合した。混合液を０℃に冷却し、温度を５℃以下に保ちながら１９．０ｇのメタクリル酸クロリドを６０分かけて滴下して、その後１時間撹拌した。蒸留水２００ｍＬを加えて反応を停止して酢酸エチル５００ｍＬを加えた。得られた有機層を蒸留水で５回洗浄した後、エバポレーターで低沸点溶媒を除去して、２２０．１ｇのラジカル重合性化合物Ｂ１－３を得た。得られた化合物は、上述の硫黄原子を有するラジカル重合性化合物の例示化合物３２２である。 (Synthesis Example 8)
[Synthesis of radically polymerizable compound B1-3 having a sulfur atom]
19.0 g of bis (4-hydroxyphenyl) sulfone, 7.0 g of pyridine, and 100 mL of tetrahydrofuran were mixed. The mixture was cooled to 0 ° C., 19.0 g of methacrylic acid chloride was added dropwise over 60 minutes while keeping the temperature at 5 ° C. or lower, and then stirred for 1 hour. 200 mL of distilled water was added to stop the reaction, and 500 mL of ethyl acetate was added. 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.

＜分子量の測定方法＞
　上記のポリマー前駆体の分子量（重量平均分子量、数平均分子量）については、ゲル浸透クロマトグラフィ（ＧＰＣ法）に従い、ポリスチレン換算値として定義した。具体的には、ＨＬＣ－８２２０（商品名：東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００、およびＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（商品名：東ソー（株）製）を用いることによって求めた。溶離液はＴＨＦ（テトラヒドロフラン）を用いて測定した。また、検出はＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用した。なお、本明細書に規定される分子量は特に断らない限りいずれも上記の測定方法に従って測定した値である。 <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 | regulated in this specification are the values measured according to said measuring method.

＜実施例１～１６、比較例１～３＞
＜＜感光性樹脂組成物の調製＞＞
　下記表１に記載の各成分を混合し、均一な溶液に調製した。得られた溶液を、細孔の幅が０．８μｍのフィルターを通して圧力０．３ＭＰａにて、加圧ろ過し、感光性樹脂組成物を得た。 <Examples 1 to 16, Comparative Examples 1 to 3>
<< Preparation of photosensitive resin composition >>
Each component described in Table 1 below was mixed to prepare a uniform solution. The obtained solution was filtered under pressure at a pressure of 0.3 MPa through a filter having a pore width of 0.8 μm to obtain a photosensitive resin composition.

＜＜保存安定性＞＞
　上記感光性樹脂組成物１０ｇを容器（容器の材質：遮光ガラス、容量：１００ｍＬ）に密閉し、２５℃、相対湿度６５％の環境下に静置した。感光性樹脂組成物から固体が析出するまでの時間で安定性を評価した。析出するまでの時間が長ければ長いほど、感光性樹脂組成物の安定性が高く、好ましい結果となる。固体の析出は、１種類の感光性樹脂組成物について、容器に保存したサンプルを３本作製し、３０日、６０日、１２０日を経過した時点で、それぞれ、１本のサンプルの容器を開封し、内容物である感光性樹脂組成物全量を孔径０．８μｍのメッシュで加圧ろ過し、メッシュ上の異物の有無を目視で観察し、析出物の有無を以下の通り判定した。
Ａ：１２０日を超えても固体の析出が見られなかった。
Ｂ：６０日を超えて、１２０日以内に固体が析出した。
Ｃ：３０日を超えて、６０日以内に固体が析出した。
Ｄ：３０日以内に固体が析出した。 << 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. Then, the entire amount of the photosensitive resin composition as the content was pressure filtered with a mesh having a pore diameter of 0.8 μm, 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.
A: Precipitation of solid was not seen even if it exceeded 120 days.
B: Solids were deposited within 120 days beyond 60 days.
C: The solid precipitated within 60 days beyond 30 days.
D: Solid precipitated within 30 days.

＜＜露光エネルギーの測定＞＞
　感光性樹脂組成物を、シリコンウェハ上にスピニングして塗布した。感光性樹脂組成物を塗布したシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に厚さ１０μｍの均一な膜を形成した。シリコンウェハ上の感光性樹脂組成物層を、アライナー（ＳＵＳＳ　ＭＩＣＲＯＴＥＣ　ＡＧ社製、Ｋａｒｌ－Ｓｕｓｓ ＭＡ１５０［商品名］）を用いて露光した。露光は高圧水銀ランプで行い、波長３６５ｎｍでの上記１０μｍの均一な膜を硬化するのに必要な露光エネルギーを測定した。露光エネルギーは低ければ低いほど高感度なことを表し、好ましい結果となる。 << Measurement of exposure energy >>
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 μm 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 μm uniform film at a wavelength of 365 nm was measured. The lower the exposure energy, the higher the sensitivity and the better result.

Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052

（Ａ）ポリマー前駆体
Ａ－１～Ａ－５：合成例１～５で製造したポリマー前駆体 (A) Polymer precursors A-1 to A-5: Polymer precursors produced in Synthesis Examples 1 to 5

（Ｂ１）硫黄原子を有するラジカル重合性化合物
Ｂ１－１～Ｂ１－３：合成例６～８で製造した硫黄原子を有するラジカル重合性化合物 (B1) Radical polymerizable compounds having sulfur atoms B1-1 to B1-3: Radical polymerizable compounds having sulfur atoms produced in Synthesis Examples 6 to 8

（Ｂ２）ラジカル重合性化合物（いずれも商品名）
Ｂ２－１：ＮＫエステル　Ｍ－４０Ｇ（新中村化学工業（株）製）
Ｂ２－２：ＳＲ－２０９（サートマー社製）
Ｂ２－３：ＮＫエステル　Ａ－９３００（新中村化学工業（株）製）
Ｂ２－４：Ａ－ＴＭＭＴ（新中村化学工業（株）製） (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）光ラジカル重合開始剤（いずれも商品名）
Ｃ－１：ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１（ＢＡＳＦ社製）
Ｃ－２：ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２（ＢＡＳＦ社製）
Ｃ－３：ＩＲＧＡＣＵＲＥ　ＯＸＥ　０４（ＢＡＳＦ社製）
Ｃ－４：ＩＲＧＡＣＵＲＥ－７８４（ＢＡＳＦ社製）
Ｃ－５：ＮＣＩ－８３１（（株）ＡＤＥＫＡ製） (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)

（Ｄ）塩基発生剤
Ｄ－１：下記化合物
Ｄ－２：下記化合物
Ｄ－３：下記化合物 (D) Base generator D-1: Compound D-2 below: Compound D-3 below: Compound below

Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053

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

（Ｆ）添加剤（マイグレーション抑制剤）
Ｆ－１：１，２，４－トリアゾール
Ｆ－２：１Ｈ－テトラゾール (F) Additive (migration inhibitor)
F-1: 1,2,4-triazole F-2: 1H-tetrazole

（Ｇ）シランカップリング剤
Ｇ－１：下記化合物
Ｇ－２：下記化合物
Ｇ－３：下記化合物 (G) Silane coupling agent G-1: the following compound G-2: the following compound G-3: the following compound

Figure JPOXMLDOC01-appb-C000054
Ｅｔはエチル基を表す。
Figure JPOXMLDOC01-appb-C000054
 Et represents an ethyl group.

（Ｈ）溶剤
Ｈ－１：γ－ブチロラクトン
Ｈ－２：ジメチルスルホキシド
Ｈ－３：Ｎ－メチル－２－ピロリドン
Ｈ－４：乳酸エチル
　なお、表１における溶剤について、例えば、種類の欄が「Ｈ－１／Ｈ－２」、質量部の欄が「４８＋１２」となっている場合、Ｈ－１を４８質量部、Ｈ－２を１２質量部含んでいることを意味する。 (H) Solvent H-1: γ-butyrolactone H-2: Dimethyl sulfoxide H-3: N-methyl-2-pyrrolidone H-4: Ethyl lactate For the solvents in Table 1, for example, the column “H” -1 / H-2 "and" parts by mass "of" 48 + 12 "mean that 48 parts by mass of H-1 and 12 parts by mass of H-2 are included.

　上記表１の結果から明らかなとおり、硫黄原子を有するラジカル重合性化合物を用いた場合、保存安定性に優れ、かつ、高感度であることが分かった（実施例１～１６）。特に、実施例２０に示す様に、微量の硫黄原子を有するラジカル重合性化合物を配合した場合でも、優れた保存安定性および高感度を達成している点で、本発明の優位性が分かる。
　これに対し、硫黄原子を有するラジカル重合性化合物を配合しない場合、感度が低くなってしまった（比較例１～３）。 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).

＜実施例１００＞
　実施例１の感光性樹脂組成物を用いてシリコンウェハ上にスピンコート法により感光性樹脂組成物を塗布した。感光性樹脂組成物層が塗布されたシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に１５μｍの厚さの均一な感光性樹脂組成物層を形成した。シリコンウェハ上の感光性樹脂組成物層を、ステッパー（（株）Ｎｉｋｏｎ製　ＮＳＲ　２００５　ｉ９Ｃ［商品名］）を用いて、５００ｍＪ/ｃｍ２の露光エネルギーで露光し、露光した感光性樹脂組成物層（樹脂層）を、シクロペンタノンで６０秒間現像して、直径１０μｍのホールを形成した。次いで、窒素雰囲気下で、１０℃／分の昇温速度で昇温し、２５０℃に達した後、３時間加熱した。室温まで冷却後、上記ホール部分を覆うように、感光性樹脂組成物層の表面の一部に、蒸着法により厚さ２μｍの銅薄層（金属層）を形成した。さらに、金属層および感光性樹脂組成物層の表面に、再度、同じ種類の感光性樹脂組成物を用いて、上記と同様に感光性樹脂組成物の濾過から、パターン化した膜の３時間加熱までの手順を再度実施して、樹脂層／金属層／樹脂層からなる積層体を作製した。
　この再配線層用層間絶縁膜は、絶縁性に優れていた。
　また、この再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <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 μm 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 μm diameter hole. Next, 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. After cooling to room temperature, a thin copper layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. Furthermore, 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.

Claims (22)

　ポリイミド前駆体およびポリベンゾオキサゾール前駆体から選択されるポリマー前駆体と、
　硫黄原子を有するラジカル重合性化合物と、
　光ラジカル重合開始剤と、
　溶剤と
　を含む感光性樹脂組成物。 A polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor;
A radically polymerizable compound having a sulfur atom;
A radical photopolymerization initiator;
A photosensitive resin composition comprising a solvent. 　前記ポリマー前駆体が、下記式（１）で表される繰り返し単位または式（２）で表される繰り返し単位を含む、請求項１に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000001
 　式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、
　Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；
Figure JPOXMLDOC01-appb-C000002
 　式（２）中、Ｒ１２１は、２価の有機基を表し、Ｒ１２２は、４価の有機基を表し、Ｒ１２３およびＲ１２４は、それぞれ独立に、水素原子または１価の有機基を表す。 The photosensitive resin composition according to claim 1, wherein the polymer precursor includes a repeating unit represented by the following formula (1) or a repeating unit represented by the formula (2);
Figure JPOXMLDOC01-appb-C000001
 In 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 represent a hydrogen atom or a monovalent organic group;
Figure JPOXMLDOC01-appb-C000002
 In Formula (2), R 121 represents a divalent organic group, R 122 represents a tetravalent organic group, and R 123 and R 124 each independently represents a hydrogen atom or a monovalent organic group. To express. 　前記ポリマー前駆体が、式（１）で表される繰り返し単位を含む、請求項２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 2, wherein the polymer precursor includes a repeating unit represented by the formula (1). 　前記硫黄原子を有するラジカル重合性化合物が、下記式（３－１）で表される、請求項１～３のいずれか１項に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000003
 　式（３－１）中、Ｌ１１は、硫黄原子を含有する二価の連結基を表し、Ｘ１１およびＸ１２は、それぞれ独立に単結合、または、二価の連結基を表し、Ｒ１１およびＲ１２は、それぞれ独立に水素原子または一価の有機基を表す；ただし、Ｒ１１およびＲ１２の少なくとも一方が、少なくとも１つのラジカル重合性基を含む一価の有機基を表す；Ｒ１１およびＲ１２は互いに結合して環を形成していてもよい。 The photosensitive resin composition according to any one of claims 1 to 3, wherein the radically polymerizable compound having a sulfur atom is represented by the following formula (3-1):
Figure JPOXMLDOC01-appb-C000003
 In 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, and 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. 　前記式（３－１）が、下記式（３－２）で表される、請求項４に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000004
 　式（３－２）中、Ｌ１は、－Ｓ－、－Ｓ－Ｓ－、－Ｓ（＝Ｏ）－、または、－Ｓ（＝Ｏ）２－を表し、Ｘ１およびＸ２は、それぞれ独立に単結合、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）Ｏ－、－ＯＣ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－または－ＮＲ３ＣＯ－を表し、Ｒ１およびＲ２は、それぞれ独立に水素原子、アルキル基、シクロアルキル基、アリール基またはラジカル重合性基を表し、Ｌａ１～Ｌａ４は、それぞれ独立に、単結合、アルキレン基およびフェニレン基の１つまたは２つ以上の組み合わせからなる基、ならびに、アルキレン基およびフェニレン基の１つまたは２つ以上と－Ｏ－との組み合わせからなる基のいずれかを表す；Ｒ３は、水素原子またはアルキル基を表す；ただし、Ｒ１およびＲ２の少なくとも一方が、ラジカル重合性基である。 The photosensitive resin composition according to claim 4, wherein the formula (3-1) is represented by the following formula (3-2);
Figure JPOXMLDOC01-appb-C000004
 In formula (3-2), L 1 represents —S—, —SS—, —S (═O) —, or —S (═O) 2 —, and 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, and 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 and —O—; R 3 represents a hydrogen atom or an alkyl group; provided that when less of R 1 and R 2 On the other hand but a radical polymerizable group. 　前記Ｒ１およびＲ２は、その両方が、それぞれ独立にラジカル重合性基である、請求項５に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 5, wherein both of R 1 and R 2 are each independently a radical polymerizable group. 　前記Ｘ１およびＸ２は、－Ｏ－である、請求項５または６に記載の感光性樹脂組成物。 7. The photosensitive resin composition according to claim 5, wherein X 1 and X 2 are —O—. 　前記Ｌ１は、－Ｓ（＝Ｏ）－である、請求項５～７のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 5 to 7, wherein L 1 is -S (= O)-. 　前記Ｒ１およびＲ２は、それぞれ独立にアクリロイル基またはメタクリロイル基を有する一価の有機基である、請求項５～８のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 5 to 8, wherein R 1 and R 2 are each independently a monovalent organic group having an acryloyl group or a methacryloyl group. 　前記式（３－１）は、下記式（４）で表される、請求項４に記載の感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000005
 式（４）中、Ｒは、水素原子またはメチル基である。 The photosensitive resin composition according to claim 4, wherein the formula (3-1) is represented by the following formula (4);
Figure JPOXMLDOC01-appb-C000005
 In formula (4), R is a hydrogen atom or a methyl group. 　前記硫黄原子を有するラジカル重合性化合物を、前記感光性樹脂組成物に含まれる固形分の０．００１質量％以上の割合で含む、請求項１～１０のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin according to any one of claims 1 to 10, comprising the radically polymerizable compound having a sulfur atom in a proportion of 0.001% by mass or more of a solid content in the photosensitive resin composition. Composition. 　さらに、硫黄原子を有するラジカル重合性化合物以外のラジカル重合性化合物を含む、請求項１～１１のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 11, further comprising a radical polymerizable compound other than the radical polymerizable compound having a sulfur atom. 　さらに、塩基発生剤を含む、請求項１～１２のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 12, further comprising a base generator. 　現像に用いられる、請求項１～１３のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 13, which is used for development. 　有機溶剤を含む現像液を用いて現像する用途に用いられる、請求項１～１４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 14, which is used for development using a developer containing an organic solvent. 　再配線層用層間絶縁膜の形成に用いられる、請求項１～１５のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 15, which is used for forming an interlayer insulating film for a rewiring layer. 　請求項１～１６のいずれか１項に記載の感光性樹脂組成物から形成される硬化膜。 A cured film formed from the photosensitive resin composition according to any one of claims 1 to 16. 　請求項１７に記載の硬化膜を２層以上有する、積層体。 A laminate having two or more cured films according to claim 17. 　前記硬化膜の間に、金属層を有する、請求項１８に記載の積層体。 The laminate according to claim 18, comprising a metal layer between the cured films. 　請求項１～１６のいずれか１項に記載の感光性樹脂組成物を用いることを含む、硬化膜の製造方法。 A method for producing a cured film, comprising using the photosensitive resin composition according to any one of claims 1 to 16. 　前記感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、
　前記感光性樹脂組成物層を露光する露光工程と、
　前記露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程とを有する、請求項２０に記載の硬化膜の製造方法。 Applying the photosensitive resin composition to a substrate to form a layer, a photosensitive resin composition layer forming step;
An exposure step of exposing the photosensitive resin composition layer;
The manufacturing method of the cured film of Claim 20 which has the image development process process which performs image development processing with respect to the said exposed photosensitive resin composition layer. 　請求項１７に記載の硬化膜、あるいは、請求項１８または１９に記載の積層体を有する半導体デバイス。 A semiconductor device comprising the cured film according to claim 17 or the laminate according to claim 18 or 19.
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