JP2009192632A - Resin composition for insulating material, photosensitive film, and photosensitive laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for insulating materials which is applicable to DI (digital imaging) exposure and enables to form a permanent pattern (solder resist pattern) excellent in cold impact properties, and to provide a photosensitive film and a photosensitive laminate. <P>SOLUTION: The resin composition for insulating materials includes a core-shell type elastomer in a resin composition for insulating materials including a binder, a photopolymerization initiator, a polymerizable compound having at least one unsaturated double bond, and a thermal crosslinking agent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition for an insulating material, a photosensitive film, and a photosensitive laminate suitable as a solder resist material for forming an image by DI (digital imaging) exposure.

  Conventionally, when forming a permanent pattern such as a solder resist, a photosensitive film is used in which a photosensitive composition (resin composition for an insulating material) is applied on a support and dried to form a photosensitive layer. . As a method for forming such a permanent pattern, for example, a laminate is formed by laminating a photosensitive film on a substrate on which a permanent pattern is formed, and the photosensitive layer in the laminate is exposed, After exposure, the photosensitive layer is developed to form a pattern, and then subjected to a curing process or the like to form a permanent pattern.

  The formation of the permanent pattern is also applied to a package substrate interposed between a semiconductor chip and a printed board. Since the package substrate is soldered to the printed circuit board, the package substrate is required to have excellent thermal shock characteristics (thermocycle test (TCT) characteristics). Further, as the wiring pattern on a package substrate becomes more precise (finer), the package substrate is exposed to DI (digital imaging) exposure having high alignment accuracy rather than analog exposure having lower alignment accuracy. It is preferably used (for example, Patent Document 1).

  Due to the above circumstances, it is desired to provide a photosensitive composition (resin composition for an insulating material) that can be applied to DI (digital imaging) exposure and has excellent thermal shock characteristics. The core-shell particles are described in Patent Documents 2 to 11.

JP 2006-243564 A JP-A-5-65391 JP 7-84369 A Japanese Patent Laid-Open No. 11-288087 JP 2000-169672 A JP 2003-128873 A JP 2001-188340 A JP 2002-244280 A JP 2004-315572 A Japanese Patent Laying-Open No. 2005-239921 Japanese Patent Laid-Open No. 2007-1266

An object of the present invention is to solve the conventional problems and achieve the following objects.
That is, the present invention can be applied to DI (digital imaging) exposure, and can form a permanent pattern (solder resist pattern) excellent in thermal shock characteristics, a resin composition for an insulating material, a photosensitive film, and a photosensitive film An object of the present invention is to provide a conductive laminate.

Means for solving the above problems are as follows. That is,
<1> A resin composition for an insulating material containing a binder, a photopolymerization initiator, a polymerizable compound having at least one unsaturated double bond, and a thermal crosslinking agent, comprising a core-shell elastomer. It is a resin composition for materials.
<2> The core-shell type elastomer is the resin composition for an insulating material according to <1>, wherein the shell portion is an acrylic resin.
<3> The core-shell type elastomer is the resin composition for an insulating material according to any one of <1> to <2>, wherein the core portion is a silicone elastomer.
<4> The resin composition for an insulating material according to any one of <1> to <3>, wherein the photopolymerization initiator includes an oxime derivative.
<5> The resin composition for an insulating material according to <4>, wherein the oxime derivative is represented by the following general formula (1).
However, in the general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹ may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heterocyclic ring. A represents any of 4, 5, 6, and 7-membered rings and may contain a hetero atom.
<6> The resin composition for an insulating material according to <5>, wherein the oxime derivative is represented by the following general formula (2).
However, in the general formula (2), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹ may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heterocyclic ring. X represents one of O and S. A represents either a 5- or 6-membered ring.
<7> The resin composition for an insulating material according to <6>, wherein the oxime derivative is represented by the following general formulas (3) and (4).
However, in the general formulas (3) and (4), R ³ represents an alkyl group, and the alkyl group may further have a substituent. l represents an integer of 0 to 6. R ⁴ represents an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, or an acyloxy group. When l is 2 or more, the R ^{4 s} may be the same or different. May be. X represents either O or S. A represents either a 5- or 6-membered ring.
<8> A photosensitive film comprising a photosensitive layer comprising a resin composition for an insulating material according to any one of <1> to <7> on a support.
<9> A photosensitive laminate comprising a photosensitive layer made of the resin composition for an insulating material according to any one of <1> to <7> on a substrate.

  INDUSTRIAL APPLICABILITY According to the present invention, a resin for an insulating material that can solve conventional problems, can be applied to DI (digital imaging) exposure, and can form a permanent pattern (solder resist pattern) having excellent thermal shock characteristics. A composition, a photosensitive film, and a photosensitive laminate can be provided.

[Resin composition for insulating material]
The resin composition for an insulating material contains a binder, a photopolymerization initiator, a polymerizable compound having at least one unsaturated double bond, a thermal crosslinking agent, and a core-shell type elastomer.

  The resin composition for insulating materials of this invention contains another component as needed. Examples of other components include a fluorescent brightener, a sensitizer, a thermal polymerization inhibitor, a color pigment, a filler, and an adhesion promoter.

(binder)
The binder includes an aromatic group that may include a heterocycle in the side chain and a polymer compound having an ethylenically unsaturated bond in the side chain, and the polymer compound has a carboxyl group in the side chain. preferable.
The binder is preferably a compound that is insoluble in water and swells or dissolves in an alkaline aqueous solution.

-Aromatic group which may contain a heterocycle-
Examples of the aromatic group that may contain the heterocycle (hereinafter, also simply referred to as “aromatic group”) include, for example, a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, Examples include those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples of the aromatic group include phenyl group, naphthyl group, anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, benzopyrrole ring group, benzofuran ring group, benzothiophene ring group, pyrazole ring group, isoxazole. Ring group, isothiazole ring group, indazole ring group, benzisoxazole ring group, benzisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring Group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, phthalazine ring group, quinazoline ring group, quinoxaline ring group, acylidine ring group, phenanthridine ring group, carbazole ring Group, purine ring group, pyran ring group, Lysine ring group, a piperazine ring group, an indole ring group, an indolizine ring group, a chromene ring group, a cinnoline ring group, an acridine ring group, a phenothiazine ring group, a tetrazole ring group, such as a triazine ring group. In these, a hydrocarbon aromatic group is preferable and a phenyl group and a naphthyl group are more preferable.

  The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an amino group which may have a substituent, an alkoxycarbonyl group, a hydroxyl group, an ether group, a thiol group, A thioether group, a silyl group, a nitro group, a cyano group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and the like, each of which may have a substituent, may be mentioned.

Examples of the alkyl group include linear alkyl groups having 1 to 20 carbon atoms, branched alkyl groups, and cyclic alkyl groups.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group. , Octadecyl group, eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group , Cyclopentyl group, 2-norbornyl group and the like. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are preferable.

Examples of the substituent that the alkyl group may have include a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom. Examples of such substituents include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups, aryloxy groups, mercapto groups, alkylthio groups, arylthio groups, alkyldithio groups, aryldithio groups. Group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfo Xyl group, acylthio group, acylamino group, N-a Killacylamino group, N-arylacylamino group, ureido group, N′-alkylureido group, N ′, N′-dialkylureido group, N′-arylureido group, N ′, N′-diarylureido group, N '-Alkyl-N'-arylureido group, N-alkylureido group, N-arylureido group, N'-alkyl-N-alkylureido group, N'-alkyl-N-arylureido group, N', N ' -Dialkyl-N-alkylureido group, N ', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N-arylureido group, N', N ' -Diaryl-N-alkylureido group, N ', N'-diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N '-Aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N- Alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl Group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group ( Referred to as -SO ₃ H) and its conjugated base group (a sulfonato group), alkoxy sulfonyl group, aryloxy sulfonyl group, sulfinamoyl group, N- alkylsulfinamoyl group, N, N- dialkyl sulfide Inamo yl group, N- Arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N - arylsulfamoyl group, (referred to as phosphonato group) N, N- diaryl sulfamoyl group, N- alkyl -N- arylsulfamoyl group, a phosphono group (-PO ₃ H ₂₎ and its conjugated base group, dialkylphosphono group _{(-PO 3 (alkyl) 2)} ( hereinafter, "alkyl" is to mean an alkyl group . ), Diaryl phosphono group _{(-PO 3 (aryl) 2)} ( hereinafter, "aryl" means an aryl group.), Alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphonates Group (—PO ₃ (alkyl)) and its conjugate base group (referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (referred to as arylphosphonate group) ), A phosphonooxy group (—OPO ₃ H ₂ ) and its conjugate base group (referred to as a phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (aryl)) ) _2), alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), monoalkyl phosphonates Oxy group _(-OPO 3 H (alkyl)) and its conjugated base group (referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugate base (aryl phosphite Hona preparative oxy Group), cyano group, nitro group, aryl group, alkenyl group, alkynyl group, heterocyclic group, silyl group and the like.

Specific examples of the alkyl group in these substituents include the aforementioned alkyl groups.
Specific examples of the aryl group in the substituent include phenyl, biphenyl, naphthyl, tolyl, xylyl, mesityl, cumenyl, chlorophenyl, bromophenyl, chloromethylphenyl, hydroxyphenyl, methoxy Phenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxy Carbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulphonatophenyl group, phosphonopheny Groups, such as phosphate Hona preparative phenyl group.

Specific examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnamyl group, 2-chloro-1-ethenyl group and the like.
Specific examples of the alkynyl group in the substituent include ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like.
Examples of ^{R 01} of the acyl group in the substituents ^(R 01 CO-), a hydrogen atom, an alkyl group described above, and aryl groups.
Among these substituents, halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups, acyloxy groups Group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N- Dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-aryl Sulfamoyl group, N-alkyl N-arylsulfamoyl group, phosphono group, phosphonato group, dialkylphosphono group, diarylphosphono group, monoalkylphosphono group, alkylphosphonato group, monoarylphosphono group, arylphosphonato group, phosphonooxy group, phosphonatoxy Group, aryl group, alkenyl group and the like are preferable.
Moreover, examples of the heterocyclic group in the substituent include a pyridyl group and a piperidinyl group, and examples of the silyl group in the substituent include a trimethylsilyl group.

On the other hand, examples of the alkylene group in the alkyl group include those obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms to obtain a divalent organic residue. For example, a linear alkylene group having 1 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, and a cyclic alkylene group having 5 to 10 carbon atoms are preferable.
Preferable specific examples of the substituted alkyl group obtained by combining such a substituent and an alkylene group include a chloromethyl group, a bromomethyl group, a 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, and an isopropoxymethyl group. , Butoxymethyl group, s-butoxybutyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetra Methylpiperidinylmethyl group, trimethylsilylmethyl group, methoxyethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N-cyclohexylcarbamoyloxyethyl Group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethyl group, allyloxycarbonylbutyl group, chloro Phenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl-N- (sulfophenyl) carbamoylmethyl group, Sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl group, N-methyl-N- (phosphonov Nyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, methylphosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl Group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p-methylbenzyl group, cinnamyl group, allyl group, 1- Examples include propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group and the like.

Examples of the aryl group include a benzene ring, a group in which 2 to 3 benzene rings form a condensed ring, and a group in which a benzene ring and a 5-membered unsaturated ring form a condensed ring.
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. In these, a phenyl group and a naphthyl group are preferable.
The alkyl group may have a substituent, and examples of the aryl group having such a substituent (hereinafter sometimes referred to as “substituted aryl group”) include the ring-forming carbon of the above-described aryl group. The thing which has group which consists of monovalent nonmetallic atomic groups other than a hydrogen atom as a substituent on an atom is mentioned.
As the substituent that the aryl group may have, for example, those described above as the substituent that the alkyl group, the substituted alkyl group, and the alkyl group may have are preferable.

  Preferred examples of the substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenyl. Group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, benzoyloxyphenyl Group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, Nyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methyl Phosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2- Examples thereof include a methylpropenylphenyl group, a 2-propynylphenyl group, a 2-butynylphenyl group, and a 3-butynylphenyl group.

Examples of the alkenyl group (—C (R ⁰² ) ═C (R ⁰³ ) (R ⁰⁴ )) and the alkynyl group (—C≡C (R ⁰⁵ )) include, for example, R ⁰² , R ⁰³ , R ⁰⁴ , and R ^A group in which ⁰⁵ is a group composed of a monovalent non-metallic atomic group is exemplified.
Examples of R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. Specific examples thereof include those shown as the above-mentioned examples. Among these, a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group, and a cyclic alkyl group are preferable.

Preferable specific examples of the alkenyl group and alkynyl group include a vinyl group, 1-propenyl group, 1-butenyl group, 1-pentenyl group, 1-hexenyl group, 1-octenyl group, 1-methyl-1-propenyl group, 2-methyl-1-propenyl group, 2-methyl-1-butenyl group, 2-phenyl-1-ethenyl group, 2-chloro-1-ethenyl group, ethynyl group, 1-propynyl group, 1-butynyl group, phenyl Examples include an ethynyl group.
As said heterocyclic group, the pyridyl group illustrated as a substituent of a substituted alkyl group etc. are mentioned, for example.

Examples of the oxy group (R ⁰⁶ O—) include those in which R ⁰⁶ is a group composed of a monovalent nonmetallic atomic group excluding a hydrogen atom.
Examples of such oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N, N- A diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy group, arylsulfoxy group, phosphonooxy group, phosphonatoxy group and the like are preferable.
Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Examples of the acyl group (R ⁰⁷ CO—) in the acyloxy group include those in which R ⁰⁷ is an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group mentioned as the previous example. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an arylsulfoxy group are more preferable.
Specific examples of preferred oxy groups include methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, pentyloxy, hexyloxy, dodecyloxy, benzyloxy, allyloxy, phenethyloxy, carboxy Ethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy Group, tolyloxy group, xylyloxy group, mesityloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group, a phenylsulfonyloxy group, a phosphonooxy group, a phosphonatooxy group.

As the amino group (R ⁰⁸ NH—, (R ⁰⁹ ) (R ⁰¹⁰ ) N—) which may contain an amide group, for example, R ⁰⁸ , R ⁰⁹ , and R ⁰¹⁰ are monovalent nonmetallic atoms excluding a hydrogen atom A group consisting of a group is mentioned. R ⁰⁹ and R ⁰¹⁰ may be bonded to form a ring.
Examples of the amino group include N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acylamino group, N -Alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'-diarylureido group, N′-alkyl-N′-arylureido group, N-alkylureido group, N-arylureido group, N′-alkyl-N-alkylureido group, N′-alkyl-N-arylureido group, N ′, N '-Dialkyl-N-alkylureido group, N'-alkyl-N'-arylureido group, N', N'-dialkyl-N-alkylureido group, N ', N'- Alkyl-N′-arylureido group, N′-aryl-N-alkylureido group, N′-aryl-N-arylureido group, N ′, N′-diaryl-N-alkylureido group, N ′, N ′ -Diaryl-N-arylureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino Group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group and the like. It is done. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Also, ^{R 07} acylamino group, N- alkylacylamino group, N- arylacylamino group definitive acyl group ^(R 07 CO-) are as defined above. Of these, an N-alkylamino group, an N, N-dialkylamino group, an N-arylamino group, and an acylamino group are more preferable.
Specific examples of preferred amino groups include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Examples of the sulfonyl group (R ⁰¹¹ —SO ₂ —) include those in which R ⁰¹¹ is a group composed of a monovalent nonmetallic atomic group.
As such a sulfonyl group, for example, an alkylsulfonyl group, an arylsulfonyl group, and the like are preferable. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
Specific examples of the sulfonyl group include a butylsulfonyl group, a phenylsulfonyl group, and a chlorophenylsulfonyl group.

As described above, the sulfonate group (—SO ₃ —) means a conjugate base anion group of a sulfo group (—SO ₃ H), and is usually preferably used together with a counter cation.
As such counter cations, generally known ones can be appropriately selected and used. For example, oniums (for example, ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (For example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^{2+ and the} like).

Examples of the carbonyl group (R ⁰¹³ —CO—) include those in which R ⁰¹³ is a group composed of a monovalent nonmetallic atomic group.
Examples of such carbonyl group include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group. N, N-diarylcarbamoyl group, N-alkyl-N′-arylcarbamoyl group and the like. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group.
As the carbonyl group, a formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, and N-arylcarbamoyl group are preferable. A group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group are more preferable.
Specific examples of the carbonyl group include formyl group, acetyl group, benzoyl group, carboxyl group, methoxycarbonyl group, ethoxycarbonyl group, allyloxycarbonyl group, dimethylaminophenylethenylcarbonyl group, methoxycarbonylmethoxycarbonyl group, N- A methylcarbamoyl group, an N-phenylcarbamoyl group, an N, N-diethylcarbamoyl group, a morpholinocarbonyl group and the like are preferable.

Examples of the sulfinyl group (R ⁰¹⁴ —SO—) include those in which R ⁰¹⁴ is a monovalent nonmetallic atomic group.
Examples of such sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N -Diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, etc. are mentioned. Examples of the alkyl group and aryl group in these include those described above as the alkyl group, substituted alkyl group, aryl group, and substituted aryl group. Among these, an alkylsulfinyl group and an arylsulfinyl group are preferable.
Specific examples of the substituted sulfinyl group include a hexylsulfinyl group, a benzylsulfinyl group, a tolylsulfinyl group and the like.

The phosphono group means one in which one or two hydroxyl groups on the phosphono group are substituted with another organic oxo group, for example, the above-mentioned dialkylphosphono group, diarylphosphono group, alkylarylphosphono group. , Monoalkylphosphono group, monoarylphosphono group and the like are preferable. Of these, dialkylphosphono groups and diarylphosphono groups are more preferred.
More preferred specific examples of the phosphono group include a diethylphosphono group, a dibutylphosphono group, a diphenylphosphono group, and the like.

The phosphonato group _{(-PO 3 H 2 -, -} PO 3 H-) and, as mentioned above, the phosphono group _(-PO 3 _{H 2),} coupled from the first dissociation acid, or the second dissociated acid bases An anionic group is meant. Usually, it is preferable to use it with a counter cation. As such counter cations, generally known ones can be appropriately selected. For example, various oniums (ammoniums, sulfoniums, phosphoniums, iodoniums, aziniums, etc.), metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn ^2+, etc.).

The phosphonato group may be a conjugated base anion group obtained by substituting one organic oxo group in the phosphono group. Specific examples thereof include the monoalkylphosphono group (—PO ₃ H (alkyl)) and a conjugate base of a monoarylphosphono group (—PO ₃ H (aryl)).

The aromatic group can be produced by an ordinary radical polymerization method by using one or more radically polymerizable compounds containing an aromatic group and, if necessary, one or more other radically polymerizable compounds as a copolymerization component. .
Examples of the radical polymerization method generally include a suspension polymerization method and a solution polymerization method.

As the radically polymerizable compound containing an aromatic group, for example, a compound represented by the following structural formula (A) and a compound represented by the following structural formula (B) are preferable.
However, in said structural formula (A), R < ₁ >, R < ₂ > and R < ₃ > represent a hydrogen atom or monovalent organic group. L represents an organic group and may not be present. Ar represents an aromatic group that may contain a heterocycle.
However, in said structural formula (B), R < ₁ >, R < ₂ >, R < ₃ >, and Ar represent the same meaning as the said structural formula (A).

The organic group of L is, for example, a polyvalent organic group composed of non-metallic atoms, and includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, and 0 to 50 oxygen atoms. Those consisting of atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms.
More specifically, examples of the organic group of L include those formed by combining the following structural units, polyvalent naphthalene, and polyvalent anthracene.

  The L linking group may have a substituent, and examples of the substituent include the aforementioned halogen atom, hydroxyl group, carboxyl group, sulfonate group, nitro group, cyano group, amide group, amino group, alkyl group, Examples include alkenyl groups, alkynyl groups, aryl groups, substituted oxy groups, substituted sulfonyl groups, substituted carbonyl groups, substituted sulfinyl groups, sulfo groups, phosphono groups, phosphonato groups, silyl groups, and heterocyclic groups.

In the compound represented by the structural formula (A) and the compound represented by the structural formula (B), the structural formula (A) is preferable in terms of sensitivity. Among the structural formulas (A), those having a linking group are preferable from the viewpoint of stability, and the organic group of L is an alkylene group having 1 to 4 carbon atoms that can remove non-image areas. It is preferable in terms of (developability).
The compound represented by the structural formula (A) is a compound containing a structural unit of the following structural formula (I). The compound represented by the structural formula (B) is a compound containing a structural unit of the following structural formula (II). Among these, the structural unit of the structural formula (I) is preferable from the viewpoint of storage stability.

However, in said structural formula (I) and (II), R < ₁ >, R < ₂ > and R < ₃ > and Ar represent the same meaning as said structural formula (A) and (B).
In the structural formulas (I) and (II), R ₁ and R ₂ are preferably a hydrogen atom, and R ₃ is preferably a methyl group from the viewpoint of removability (developability) of a non-image area.
In addition, L in the structural formula (I) is preferably an alkylene group having 1 to 4 carbon atoms from the viewpoint of removability (developability) of non-image areas.

  Although there is no restriction | limiting in particular as a compound represented by the said structural formula (A) or a structural formula (B), For example, the following exemplary compounds (1)-(30) are mentioned.

  Among the exemplary compounds (1) to (30), (5), (6), (11), (14), and (28) are preferable, and among these, (5) and (6) are storage stable. Is more preferable from the viewpoints of colorability and developability.

  The content of the aromatic group that may contain a heterocycle in the binder is not particularly limited, but the structure represented by the structural formula (I) when the total structural unit of the polymer compound is 100 mol%. It is preferable to contain 20 mol% or more of a unit, and it is more preferable to contain 30-45 mol%. When the content is less than 20 mol, storage stability may be lowered, and when it exceeds 45 mol%, developability may be lowered.

-Ethylenically unsaturated bond-
There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, what is represented by following Structural formula (III)-(V) is preferable.

However, in the structural formulas (III) to (V), R _{1 to} R ₃ and R _{5 to} R ₁₁ each independently represent a monovalent organic group. X and Y each independently represent an oxygen atom, a sulfur atom, or —N—R ₄ . Z represents an oxygen atom, a sulfur atom, —N—R ₄ , or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

In the structural formula (III), each R ₁ is independently preferably, for example, a hydrogen atom or an alkyl group which may have a substituent, since the hydrogen atom or methyl group has high radical reactivity. More preferred.
R ₂ and R ₃ are each independently, for example, a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl which may have a substituent. Group, aryl group which may have a substituent, alkoxy group which may have a substituent, aryloxy group which may have a substituent, alkylamino group which may have a substituent, substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, such as a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, a substituent An alkyl group that may have a substituent and an aryl group that may have a substituent are more preferable because of high radical reactivity.
As R ₄ , for example, an alkyl group which may have a substituent is preferable, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, and an alkoxy group. Examples include carbonyl group, sulfo group, nitro group, cyano group, amide group, alkylsulfonyl group, arylsulfonyl group and the like.

In the structural formula (IV), examples of R _{4 to} R ₈ include a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, and a substituent. An optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, and optionally having a substituent An alkylamino group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent are preferable, and a hydrogen atom, a carboxyl group, alkoxy A carbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are more preferable.
Examples of the substituent that can be introduced include those listed in the structural formula (III).

In the structural formula (V), as R ₉ , for example, a hydrogen atom or an alkyl group which may have a substituent is preferable, and a hydrogen atom or a methyl group is more preferable because of high radical reactivity.
R ₁₀ and R ₁₁ each independently have, for example, a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or a substituent. An alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino which may have a substituent Group, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like, preferably a hydrogen atom, a carboxyl group, an alkoxycarbonyl group An alkyl group which may have a substituent and an aryl group which may have a substituent are more preferable because of high radical reactivity.
Here, examples of the substituent that can be introduced include those listed in the structural formula (III).
Z represents an oxygen atom, a sulfur atom, —NR ₁₃ —, or a phenylene group which may have a substituent. R ₁₃ represents an alkyl group which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable because of high radical reactivity.

Among the side chain ethylenically unsaturated bonds represented by the structural formulas (III) to (V), those having the structural formula (III) are more preferable because of high polymerization reactivity and high sensitivity.
The content of the ethylenically unsaturated bond in the polymer compound is not particularly limited, but is preferably 0.5 to 3.0 meq / g, more preferably 1.0 to 3.0 meq / g, 1.5 ˜2.8 meq / g is particularly preferred. When the content is less than 0.5 meq / g, the curing reaction amount is small, so that the sensitivity may be low. When the content exceeds 3.0 meq / g, the storage stability may be deteriorated.
Here, the content (meq / g) can be measured by, for example, iodine value titration.

The method for introducing an ethylenically unsaturated bond represented by the structural formula (III) into the side chain is not particularly limited. For example, the polymer compound containing a carboxyl group in the side chain and the ethylenically unsaturated bond and It can be obtained by addition reaction of a compound having an epoxy group.
The polymer compound containing a carboxyl group in the side chain is usually composed of, for example, one or more radical polymerizable compounds containing a carboxyl group and, if necessary, one or more other radical polymerizable compounds as a copolymerization component. The radical polymerization method includes, for example, suspension polymerization method, solution polymerization method and the like.

The compound having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these, but for example, a compound represented by the following structural formula (VI) and a compound represented by (VII) are preferable. In particular, the use of the compound represented by the structural formula (VI) is preferable in terms of increasing sensitivity.
However, in the structural formula (VI), R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group.
In the Structural Formula (VII), R ₂ is a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.
Among the structural compound represented by (VI) and formula (VII) compounds represented by is preferably a compound represented by the structural formula (VI), also in the structural formula (VI), L ₁ is Those having 1 to 4 carbon atoms are more preferred.

Although there is no restriction | limiting in particular as a compound represented by the said structural formula (VI) or a structural formula (VII), For example, the following exemplary compounds (31)-(40) are mentioned.

  Examples of the radical polymerizable compound containing a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl styrene, and particularly preferred is acrylic acid. And methacrylic acid.

  Examples of the introduction reaction to the side chain include tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, and tetraethylammonium chloride, pyridine, triphenylphosphine, and the like. Can be carried out by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours.

The structural unit having an ethylenically unsaturated bond in the side chain is not particularly limited. For example, the structure represented by the following structural formula (i), the structure represented by the structural formula (ii), and these Those represented by mixing are preferred.
However, in the structural formulas (i) and (ii), Ra to Rc represent a hydrogen atom or a monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group that may have a linking group.

  The content in the polymer compound having the structure represented by the structural formula (i) or the structural formula (ii) is preferably 20 mol% or more, more preferably 20 to 50 mol%, and more preferably 25 to 45 mol%. Particularly preferred. If the content is less than 20 mol%, the curing reaction amount is small, so that the sensitivity may be low. If the content exceeds 50 mol%, the storage stability may be deteriorated.

-Carboxyl group-
The polymer compound may have a carboxyl group in order to improve various performances such as non-image area removability.
The carboxyl group can be imparted to the polymer compound by copolymerizing a radical polymerizable compound having an acid group.
Examples of the acid group having such radical polymerizability include carboxylic acid, sulfonic acid, and phosphoric acid group, and carboxylic acid is particularly preferable.
The radical polymerizable compound having a carboxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p -Carboxylstyrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxylstyrene are preferable. These may be used alone or in combination of two or more.

Content in the binder of the said carboxyl group is 1.0-4.0 meq / g, and 1.5-3.0 meq / g is preferable. If the content is less than 1.0 meq / g, the developability may be insufficient, and if it exceeds 4.0 meq / g, the image strength may be easily damaged by alkali water development.
Here, the content (meq / g) can be measured, for example, by titration using sodium hydroxide.

In order to improve various performances such as image strength, the polymer compound is preferably copolymerized with another radical polymerizable compound in addition to the above-described radical polymerizable compound.
Examples of the other radical polymerizable compounds include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.

Specific examples include acrylic acid esters such as alkyl acrylate, methacrylic acid esters such as aryl acrylate and alkyl methacrylate, styrenes such as aryl methacrylate, styrene and alkyl styrene, alkoxy styrene, and halogen styrene.
As the acrylate esters, alkyl groups having 1 to 20 carbon atoms are preferable. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethyl hexyl acrylate Octyl acrylate, tert-octyl acrylate, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, methoxybenzyl Examples thereof include acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate and the like.
Examples of the aryl acrylate include phenyl acrylate.

As the methacrylic acid esters, those having 1 to 20 carbon atoms in the alkyl group are preferable. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl. Methacrylate, octyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydro And furfuryl methacrylate.
Examples of the aryl methacrylate include phenyl methacrylate, cresyl methacrylate, and naphthyl methacrylate.

Examples of the styrenes include methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, and trifluoromethyl. Examples thereof include styrene, ethoxymethyl styrene, acetoxymethyl styrene and the like.
Examples of the alkoxystyrene include methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, and the like.
Examples of the halogen styrene include chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, and 2-bromo-4-trifluoro. Examples include rumethylstyrene and 4-fluoro-3-trifluoromethylstyrene.
These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

  The solvent used for synthesizing the polymer compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide , Toluene, ethyl acetate, methyl lactate, ethyl lactate and the like. These may be used alone or in combination of two or more.

The molecular weight of the polymer compound is preferably 10,000 or more and less than 100,000, and more preferably 10,000 to 50,000 in terms of mass average molecular weight. When the mass average molecular weight is less than 10,000, the cured film strength may be insufficient, and when it exceeds 100,000, the developability tends to decrease.
The polymer compound may contain an unreacted monomer. In this case, the content of the monomer in the polymer compound is preferably 15% by mass or less.

The said high molecular compound may be used individually by 1 type, and 2 or more types may be mixed and used for it. Moreover, you may mix and use another high molecular compound.
Examples of the other polymer compounds are not particularly limited and may be appropriately selected depending on the purpose. For example, JP-A Nos. 51-131706, 52-94388 and 64- Examples thereof include epoxy acrylate compounds having an acidic group described in JP-A-62375, JP-A-2-97513, JP-A-3-289656, JP-A-61-2243869, JP-A-2002-296776, and the like.
Here, the epoxy acrylate compound is a compound having a skeleton derived from an epoxy compound and containing an ethylenically unsaturated double bond and a carboxyl group in the molecule. Such a compound can be obtained, for example, by a method of reacting a polyfunctional epoxy compound with a carboxyl group-containing monomer and further adding a polybasic acid anhydride.
Examples of the other polymer compound include vinyl copolymers having a (meth) acryloyl group and an acidic group in the side chain other than the present invention.
In this case, the content of the other polymer compound in the polymer compound is preferably 50% by mass or less, and more preferably 30% by mass or less.

  5-80 mass% is preferable and, as for solid content in the resin composition for insulating materials of the said binder, 10-70 mass% is more preferable. When the solid content is less than 5% by mass, the film strength of the photosensitive layer tends to be weak, and the tackiness of the surface of the photosensitive layer may be deteriorated. When it exceeds 80% by mass, the exposure sensitivity is increased. May decrease.

(Photopolymerization initiator)
The photopolymerization initiator is an oxime derivative represented by the following general formula (1). Thereby, DI (digital imaging) exposure characteristic can be provided to the resin composition for insulating materials.
However, in the general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹ may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heterocyclic ring. A represents any of 4, 5, 6, and 7-membered rings and may contain a hetero atom.

Among the oxime derivatives represented by the general formula (1), a compound represented by the following general formula (2) is more preferable, and a compound represented by any one of the following general formulas (3) and (4) is particularly preferable. preferable.
However, in the general formula (2), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹ may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heterocyclic ring. X represents either O or S. A represents either a 5- or 6-membered ring.
However, in the general formulas (3) and (4), R ³ represents an alkyl group, and the alkyl group may further have a substituent. l represents an integer of 0 to 6. R ⁴ represents an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, or an acyloxy group. When l is 2 or more, the R ^{4 s} may be the same or different. May be. X represents either O or S. A represents either a 5- or 6-membered ring.

In the general formulas (1) and (2), the acyl group represented by R ¹ may be any of aliphatic, aromatic, and heterocyclic, and may further have a substituent.
Examples of the aliphatic acyl group include an acetyl group, a propanoyl group, a butanoyl group, a hexanoyl group, a decanoyl group, a phenoxyacetyl group, and a chloroacetyl group. Examples of the aromatic acyl group include a benzoyl group, a naphthoyl group, a methoxybenzoyl group, and a nitrobenzoyl group. Examples of the heterocyclic acyl group include a furanoyl group and a thiophenoyl group. As the substituent, any of an alkoxy group, an aryloxy group, and a halogen atom is preferable.
The acyl group preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 16 carbon atoms. Examples of the acyl group include acetyl group, propanoyl group, methylpropanoyl group, butanoyl group, pivaloyl group, hexanoyl group, cyclohexanecarbonyl group, octanoyl group, decanoyl group, dodecanoyl group, octadecanoyl group, benzylcarbonyl Group, phenoxyacetyl group, 2-ethylhexanoyl group, chloroacetyl group, benzoyl group, paramethoxybenzoyl group, 2,5-dibutoxybenzoyl group, 1-naphthoyl group, 2-naphthoyl group, pyridylcarbonyl group, furanoyl group, A thiophenoyl group, a methacryloyl group, an acryloyl group, and the like can be given.

In the general formulas (1) and (2), the alkyloxycarbonyl group represented by R ¹ may have a substituent, and is preferably an alkoxycarbonyl group having 2 to 30 carbon atoms in total. Those having 2 to 20 carbon atoms are more preferable, and those having 2 to 16 carbon atoms are particularly preferable. Examples of such alkoxycarbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonylbutoxycarbonyl group, isobutyloxycarbonyl group, aryloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, ethoxyethoxycarbonyl group. , Etc.

In the general formulas (1) and (2), the aryloxycarbonyl group represented by R ¹ may have a substituent, and is preferably an alkoxycarbonyl group having 7 to 30 carbon atoms in total. Those having a number of 7 to 20 are more preferable, and those having a total carbon number of 7 to 16 are particularly preferable. Examples of such aryloxycarbonyl groups include phenoxycarbonyl group, 2-naphthoxycarbonyl group, paramethoxyphenoxycarbonyl group, 2,5-diethoxyphenoxycarbonyl group, parachlorophenoxycarbonyl group, paranitrophenoxycarbonyl group. And paracyanophenoxycarbonyl group.

In the general formulas (1) and (2), the substituent represented by R ² is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, an acyloxy group, and a nitro group. Group, acylamino group, and the like. Among these, any of an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group is preferable.

Here, specific examples of the oxime derivative represented by the general formula (1) include compounds represented by the following structural formulas (1) to (54). However, in the present invention, the compounds are limited to these. It is not something.
However, in the structural formulas (1) to (54), Me represents a methyl group. Ph represents a phenyl group. Ac represents an acetyl group.

The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.
As content of the said photoinitiator, 0.001-30 mass% is preferable with respect to the total solid in the said resin composition for insulating materials, 0.01-20 mass% is more preferable, 0.0. 5-10 mass% is especially preferable. When the content is less than 0.01% by mass, sufficient curing sensitivity may not be obtained, and when it exceeds 30% by mass, developability and storage stability may be adversely affected.

(Polymerizable compound)
The polymerizable compound of the present invention has at least one unsaturated double bond (polymerizable group). The polymerizable compound is not particularly limited and may be appropriately selected depending on the intended purpose. A compound is preferable, for example, at least 1 sort (s) selected from the monomer which has a (meth) acryl group is mentioned suitably.

  Examples of the polymerizable group include an ethylenically unsaturated bond (for example, (meth) acryloyl group, (meth) acrylamide group, styryl group, vinyl group such as vinyl ester and vinyl ether, allyl group such as allyl ether and allyl ester). Etc.) and a polymerizable cyclic ether group (for example, epoxy group, oxetane group, etc.) and the like. Among these, an ethylenically unsaturated bond is preferable.

The compound having at least one polymerizable group in the molecule preferably has a polyalkylene oxide group.
Moreover, it is preferable that the said polymeric compound contains the compound which has at least any one of a urethane group and an aryl group.

-Compound having one polymerizable group in the molecule-

Examples of the compound having one polymerizable group in the molecule include a compound having one polymerizable group in the molecule represented by the following structural formula (Xi) and having a polyalkylene oxide chain. is there.
In the structural formula (Xi), R ¹ represents a hydrogen atom or a methyl group.
X represents an alkylene group having 2 to 6 carbon atoms, and preferably has a chain structure rather than a cyclic structure. The chain alkylene group may have a branch. Examples of the alkylene group include an ethylene group, a propylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group.
n is an integer of 1 to 30, and when n is 2 or more, a plurality of (—X—O—) may be the same as or different from each other, and (—X—O—) may be When they are different, for example, a combination of an ethylene group and a propylene group can be used.

Examples of R ² include an alkyl group, an aryl group, and an aralkyl group, and these groups may be further substituted with a substituent.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, a 2-ethylhexyl group, a dodecyl group, a hexadecyl group, and an octadecyl group. Is mentioned. The alkyl group may have a substituent, and may have a branch or a ring structure.
Examples of the aralkyl group include benzyl group and phenethyl group. The aralkyl group may have a substituent.
Examples of the aryl group include phenyl group, naphthyl group, tolyl group, xylyl group, ethylphenyl group, methoxyphenyl group, propylphenyl group, butylphenyl group, t-butylphenyl group, octylphenyl group, nonylphenyl group, Examples include chlorophenyl group, cyanophenyl group, dibromophenyl group, tribromophenyl group, biphenylyl group, benzylphenyl group, α-dimethyl-benzylphenyl group, and the like. The aryl group may have a substituent.

Examples of the substituent in the alkyl group, aralkyl group, and aryl group include a halogen atom, an aryl group, an alkenyl group, an alkoxy group, and a cyano group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
The aryl group preferably has a total carbon number of 6 to 20, and more preferably 6 to 14. Examples of the aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a methoxyphenyl group, and the like.
As said alkenyl group, C2-C10 is preferable and 2-6 are more preferable. Examples of the alkenyl group include ethynyl group, propenyl group, butyryl group and the like.
As said alkoxy group, 1-10 total carbon atoms which may be branched are preferable, and 1-5 are more preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a 2-methylpropyloxy group, and a butoxy group.

Specific examples of the compound having one polymerizable group in the molecule represented by the structural formula (Xi) include compounds represented by the following structural formula. However, in the following formula, R represents a hydrogen atom or a methyl group. n represents an integer of 1 to 30, m and L each represents an integer of 1 or more, and m + L represents an integer of 1 to 30. Me represents a methyl group, and Bu represents a butyl group.

  The content of the compound having one polymerizable group in the molecule in the polymerizable compound is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and still more preferably 1 to 25% by mass. . If the content is less than 0.1% by mass, the effect of improving peelability and development latitude may be insufficient. If the content exceeds 40% by mass, resolution, adhesion, tent properties, etc. are deteriorated. There is a case.

-Compound having two polymerizable groups in the molecule-
The compound having two polymerizable groups in the molecule is not particularly limited as long as it has two polymerizable groups in the molecule, and can be appropriately selected according to the purpose. For example, a urethane group and an aryl group A compound (monomer or oligomer) having at least one of the above and having two polymerizable groups is preferred.

--A compound having a urethane group and two polymerizable groups--
The compound having a urethane group and two polymerizable groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a diisocyanate compound having two isocyanate groups in the molecule and Examples include adducts with vinyl monomers having a hydroxyl group in the molecule.

  Examples of the diisocyanate compound include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, 3,3′dimethyl-4,4′-diphenyl. Examples thereof include diisocyanates such as diisocyanates; polyaddition products of the diisocyanates with bifunctional alcohols (in this case, both ends are isocyanate groups).

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Examples include acrylate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, and the like. It is done.

Moreover, the diol body one terminal (meth) acrylate compound etc. which have different alkylene oxide parts, such as a copolymer (random, block, etc.) of ethylene oxide and propylene oxide represented by the following structural formula (B-13), etc. are mentioned. .

In the structural formula (B-13), R ¹ and R ² each represent a hydrogen atom or a methyl group.
X ₁ and X ₂ represent an alkylene oxide group, and these may be used alone or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are particularly preferable.
In the structural formula (B-13), m1 and m2 represent an integer of 1 to 30, preferably 2 to 20, and more preferably 4 to 15.

In Structural Formula (B-13), Y ¹ represents a divalent organic group having 2 to 30 carbon atoms. Examples of the organic group include an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group (—CO—), an oxygen atom (—O—), a sulfur atom (—S—), and an imino group (—NH—). ), A substituted imino group in which a hydrogen atom of an imino group is substituted with a monovalent hydrocarbon group, a sulfonyl group (—SO ₂ —), or a combination thereof. Among these, an alkylene group, an arylene group, or a group obtained by combining these is preferable.
The alkylene group may have a branched structure or a cyclic structure. For example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, a hexylene group, Preferred examples include xylene group, cyclohexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, or any group represented by the following structural formula. It is done.

The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and a group represented by the following structural formula.
Examples of the group in which these are combined include a xylylene group.

  The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ), Aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.

Suitable examples of the compound represented by the structural formula (B-13) include compounds represented by the following structural formulas (B-15) to (B-21).
However, R represents a hydrogen atom or a methyl group in the structural formulas (B-15) to (B-21). m and n represent an integer of 1 to 60.

--A compound having an aryl group and two polymerizable groups--
Examples of the compound having an aryl group and having two polymerizable groups include at least one of a dihydric alcohol compound having an aryl group, a divalent amine compound having an aryl group, and an amino alcohol compound having an aryl group. Examples thereof include esters and amides of heel and unsaturated carboxylic acids.

Examples of the dihydric alcohol compound having an aryl group, the divalent amine compound having an aryl group, or the amino alcohol compound having an aryl group include polystyrene oxide, xylylene diol, di- (β-hydroxyethoxy) benzene, 1 , 5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2,2-diphenyl-1,3-propanediol, hydroxybenzyl alcohol, hydroxyethyl resorcinol, 1-phenyl-1,2-ethanediol, 2, 3,5,6-tetramethyl-p-xylene-α, α′-diol, 1,1,4,4-tetraphenyl-1,4-butanediol, 1,1,4,4-tetraphenyl-2 -Butyne-1,4-diol, 1,1'-bi-2-naphthol, dihydroxynaphthalene, , 1′-methylene-di-2-naphthol, biphenol, 2,2′-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (hydroxyphenyl) methane, catechol, 4-chlororesorcinol, hydroquinone, hydroxybenzyl alcohol, methylhydroquinone, resorcinol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, α- (1-aminoethyl) -p-hydroxybenzyl alcohol, 3-amino- 4-hydroxyphenyl sulfone and the like.
In addition to these, esterified products obtained from vinyl monomers containing hydroxyl groups in the molecule such as xylylene bis (meth) acrylamide and phthalic acid, diallyl phthalate, diallyl benzenedisulfonate, and cationic polymerizable dimers as polymerizable monomers. Vinyl ethers (for example, bisphenol A divinyl ether), epoxy compounds (for example, bisphenol A diglycidyl ether), vinyl esters (for example, divinyl phthalate, divinyl terephthalate, divinylbenzene-1,3-disulfonate), styrene compounds (For example, divinylbenzene, p-allyl styrene, p-isopropene styrene, etc.).
Among these, a compound represented by the following structural formula (B-38) is preferable.

In the structural formula (B-38), R ⁴ and R ^{5 each} represent a hydrogen atom or an alkyl group.
In the structural formula (B-38), X ₅ and X ₆ each represent an alkylene oxide group, which may be used alone or in combination of two or more. Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, or a group obtained by combining these (may be combined in any of random and block). And the like. Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a group obtained by combining these is preferable, and an ethylene oxide group and a propylene oxide group are particularly preferable.

In the structural formula (B-38), m5 and m6 are preferably an integer of 1 to 60, more preferably an integer of 2 to 30, and particularly preferably an integer of 4 to 15.
In the structural formula (B-38), T represents a divalent linking group, and examples thereof include methylene, ethylene, MeCMe, CF ₃ CCF ₃ , CO, and SO ₂ .

In the structural formula (B-38), Ar ¹ and Ar ² represent an aryl group which may have a substituent, and examples thereof include a phenylene group and a naphthylene group. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, a halogen group, an alkoxy group, or a combination thereof.

Specific examples of the compound having an aryl group and two polymerizable groups include 2,2-bis [4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl] propane; 2-bis [4-((meth) acryloxyethoxy) phenyl] propane, 2,2-bis (4-((meth) having 2 to 20 ethoxy groups substituted with one phenolic OH group ) Acryloyloxypolyethoxy) phenyl) propane (eg, 2,2-bis (4-((meth) acryloyloxydiethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetraethoxy)) Phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Yloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecaethoxy) phenyl) propane), 2,2-bis [4-((meth) acryloxypropoxy) phenyl Propane; 2,2-bis (4-((meth) acryloyloxypolypropoxy) phenyl) propane (for example, 2,2) having 2 to 20 ethoxy groups substituted with one phenolic OH group -Bis (4-((meth) acryloyloxydipropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxytetrapropoxy) phenyl) propane, 2,2-bis (4-((meta ) Acryloyloxypentapropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxydecap) Poxy) phenyl) propane, 2,2-bis (4-((meth) acryloyloxypentadecapropoxy) phenyl) propane), or the polyether moiety of these compounds in the same molecule, a polyethylene oxide skeleton and a polypropylene oxide skeleton (For example, a compound described in WO 01/98832, a polymerizable compound having a bisphenol skeleton and a urethane group, and the like).
Examples of the polymerizable compound having a bisphenol skeleton and a urethane group include an isocyanate group and a polymerizable group in a compound having a hydroxyl group at the terminal obtained as an adduct such as bisphenol and ethylene oxide or propylene oxide, or a polyaddition product. Compounds (for example, 2-isocyanatoethyl (meth) acrylate, α, α-dimethyl-vinylbenzyl isocyanate, etc.), and the like. In addition, the compound which changed the part originating in the bisphenol A frame | skeleton into bisphenol F or bisphenol S etc. may be sufficient.

  Moreover, as a commercial item, Shin-Nakamura Chemical Co., Ltd. make, BPE-200, BPE-500, BPE-1000) etc. are mentioned, for example.

  These compounds having two polymerizable groups in the molecule may be used alone or in combination of two or more.

  The content of the compound having two polymerizable groups in the molecule in the polymerizable compound is preferably 60 to 99% by mass, more preferably 70 to 99% by mass, and still more preferably 75 to 99% by mass.

-Polymerizable compound having 3 or more polymerizable groups in the molecule-
The polymerizable compound having three or more polymerizable groups in the molecule is not particularly limited as long as it has three or more polymerizable groups in the molecule and can be appropriately selected according to the purpose. Methylolpropane tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, trimethylolethane tri (meth) acrylate, 1,2,4-butanetriol tri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, DPHA (dipentaerythritol hexa (meth) acrylate), sorbitol tri (meth) acrylate, sorbitol tetra (meth) acrylate, sorbite Α, β- Examples thereof include compounds obtained by adding unsaturated carboxylic acids, diethylenetriamine tris (meth) acrylamide, and the like.

Examples of the compound having three or more polymerizable groups in the molecule include a polyalkylene oxide chain having three or more polymerizable groups in the molecule represented by the following structural formula (X-ii). Also suitable are compounds having
However, in the structural formula (X-ii), R ¹ represents either a hydrogen atom or a methyl group.
X represents an alkylene group which may have a branch having 2 to 6 carbon atoms, and the alkylene group may contain one kind or two or more kinds (for example, ethylene and propylene) in one molecule.
n represents an integer of 1 to 30. m represents an integer of 3 or more.
Y represents an m-valent (trivalent to hexavalent) organic group, and examples thereof include a group represented by the following structural formula.
However, Et represents an ethyl group.

As the compound represented by the structural formula (X-ii), for example, compounds represented by the following structural formulas (X-iii) to (X-iv) are preferably exemplified.
However, in the structural formulas (X-iii) and (X-iv), R _{1 to} R ₃ represent either a hydrogen atom or a methyl group.
X ₁ to X ₃ represents an optionally branched alkylene group having 2 to 6 carbon atoms, said alkylene group may in one in one molecule, two or more (e.g., ethylene and propylene) include May be.
n1-n3 represents the integer of 1-30.
R represents a monovalent organic group, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; and an aryl group such as a phenyl group and a naphthyl group.

As the compounds represented by the structural formulas (X-iii) and (X-iv), specifically, those represented by the following structural formulas are preferable. However, in the following structural formula, R represents a hydrogen atom or a methyl group. n1, n2, and n3 represent an integer of 1-30. m1, m2, and m3, and L1, L2, and L3 each represent an integer of 1 or more, and m1 + L1, m2 + L2, and m3 + L3 each represent an integer of 1-30.

  Moreover, as a compound which has three or more polymeric groups in the said molecule | numerator, the compound which has at least any one of a urethane group and an aryl group and has three or more polymeric groups is suitable, for example.

--A compound having a urethane group and having three or more polymerizable groups--
There is no restriction | limiting in particular as a compound which has the said urethane group and 3 or more polymeric groups, According to the objective, it can select suitably, For example, polyisocyanate which has 3 or more isocyanate groups in a molecule | numerator is mentioned. Examples include adducts of an isocyanate compound and a vinyl monomer having a hydroxyl group in the molecule.

  Examples of the polyisocyanate compound having three or more isocyanate groups in the molecule include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, xylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, norbornene diisocyanate, diphenyl diisocyanate, diphenylmethane diisocyanate, Adducts (terminals) of diisocyanates such as 3,3′dimethyl-4,4′-diphenyl diisocyanate and polyfunctional alcohols such as trimethylolpropane, pentaerythritol, and glycerin, or obtained polyfunctional alcohols such as ethylene oxide adducts Is an isocyanate group); a bullet or isocyanurate of the diisocyanate Like trimer.

  Examples of the vinyl monomer having a hydroxyl group in the molecule include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, and triethylene. Glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate , Tetrapropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) Chryrate, dibutylene glycol mono (meth) acrylate, tributylene glycol mono (meth) acrylate, tetrabutylene glycol mono (meth) acrylate, octabutylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, trimethylolpropane Examples include di (meth) acrylate and pentaerythritol tri (meth) acrylate. Moreover, the one terminal (meth) acrylate body of the diol body which has different alkylene oxide parts, such as a copolymer (random, a block, etc.) of ethylene oxide and propylene oxide, etc. are mentioned.

  Examples of the monomer having a urethane group include compounds having an isocyanurate ring such as tri ((meth) acryloyloxyethyl) isocyanurate and tri (meth) acrylate of ethylene oxide-modified isocyanuric acid.

A compound having a urethane group together with three or more polymerizable groups, and a compound having a polyalkylene oxide chain are also preferably used. More specifically, examples of such a compound include those represented by the following structural formula (B-14).

In the structural formula (B-14), R ³ represents a hydrogen atom or a methyl group, respectively. X ₃ represents an alkylene oxide group, which may be used alone or in combination of two or more. m3 is an integer of 1 to 30, n is an integer of 3 or more, Y2 is a divalent organic group, and Z is an n-valent organic group.

Examples of the alkylene oxide group include an ethylene oxide group, a propylene oxide group, a butylene oxide group, a pentylene oxide group, a hexylene oxide group, and a group in which these are combined (may be combined in any of random or block). Among these, an ethylene oxide group, a propylene oxide group, a butylene oxide group, or a combination thereof is preferable, and an ethylene oxide group and a propylene oxide group are more preferable.
In said structural formula (B-14), m3 represents the integer of 1-30, 2-20 are preferable and 4-15 are more preferable.

In the structural formula (B-14), Y ² represents a divalent organic group having 2 to 30 carbon atoms, such as an alkylene group, an arylene group, an alkenylene group, an alkynylene group, or a carbonyl group (—CO—). , An oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, a sulfonyl group (—SO _2- ) or a group combining these, and the like are preferable. Among these, an alkylene group, an arylene group, or a group combining these is preferable.
The alkylene group may have a branched structure or a cyclic structure. For example, a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, a pentylene group, a neopentylene group, a hexylene group, Preferred examples include xylene group, cyclohexylene group, heptylene group, octylene group, 2-ethylhexylene group, nonylene group, decylene group, dodecylene group, octadecylene group, or any group represented by the following structural formula. It is done.

The arylene group may be substituted with a hydrocarbon group, and examples thereof include a phenylene group, a tolylene group, a diphenylene group, a naphthylene group, and a group represented by the following structural formula.
Examples of the group in which these are combined include a xylylene group.

The alkylene group, arylene group, or a combination thereof may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom). ), Aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group (for example, Acetoxy group, butyryloxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group) and the like.
In the structural formula (B-14), Y ¹ represents a divalent organic group having 2 to 30 carbon atoms, such as an alkylene group, an arylene group, an alkenylene group, an alkynylene group, or a carbonyl group (—CO—). , An oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group in which the hydrogen atom of the imino group is substituted with a monovalent hydrocarbon group, a sulfonyl group (—SO _2- ) or a group combining these, and the like are preferable. Among these, an alkylene group, an arylene group, or a group combining these is preferable.

  In the structural formula (B-14), n represents an integer of 3 to 6, and 3, 4 or 6 is preferable from the viewpoint of raw material supply ability for synthesizing a polymerizable monomer.

In the structural formula (B-14), Z represents an n-valent (trivalent to hexavalent) linking group, and examples thereof include any group represented by the following structural formula.
However, _{X 4} represents an alkylene oxide. m4 represents an integer of 1 to 20. n represents an integer of 3 to 6. A represents an n-valent (trivalent to hexavalent) organic group.

  Examples of A include an n-valent aliphatic group, an n-valent aromatic group, and an alkylene group, an arylene group, an alkenylene group, an alkynylene group, a carbonyl group, an oxygen atom, a sulfur atom, an imino group, and an imino group. Are preferably a combination of a substituted imino group in which the hydrogen atom is substituted with a monovalent hydrocarbon group or a sulfonyl group, an n-valent aliphatic group, an n-valent aromatic group, or an alkylene group or arylene A group in which a group and an oxygen atom are combined is more preferable, and an n-valent aliphatic group, and a group in which an n-valent aliphatic group is combined with an alkylene group and an oxygen atom are particularly preferable.

  As the number of carbon atoms of A, for example, an integer of 1 to 100 is preferable, an integer of 1 to 50 is more preferable, and an integer of 3 to 30 is particularly preferable.

The n-valent aliphatic group may have a branched structure or a cyclic structure.
As a carbon atom number of the said aliphatic group, the integer of 1-30 is preferable, for example, the integer of 1-20 is more preferable, and the integer of 3-10 is especially preferable.
The number of carbon atoms of the aromatic group is preferably an integer of 6 to 100, more preferably an integer of 6 to 50, and particularly preferably an integer of 6 to 30.

  The n-valent aliphatic group or aromatic group may further have a substituent. Examples of the substituent include a hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom), aryl group, alkoxy group (for example, methoxy group, ethoxy group, 2-ethoxyethoxy group), aryloxy group (for example, phenoxy group), acyl group (for example, acetyl group, propionyl group), acyloxy group ( Examples thereof include an acetoxy group, a butyryloxy group), an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group), an aryloxycarbonyl group (for example, a phenoxycarbonyl group), and the like.

The alkylene group may have a branched structure or a cyclic structure.
As a carbon atom number of the said alkylene group, the integer of 1-18 is preferable, for example, and the integer of 1-10 is more preferable.

The arylene group may be further substituted with a hydrocarbon group.
The number of carbon atoms of the arylene group is preferably an integer of 6 to 18, and more preferably an integer of 6 to 10.

  As a carbon atom number of the monovalent hydrocarbon group of the said substituted imino group, the integer of 1-18 is preferable and the integer of 1-10 is more preferable.

Hereinafter, preferred examples of A are as shown by the following structural formula.

Examples of the compound represented by the structural formula (B-14) include compounds represented by the following structural formulas (B-22) to (B-37).
However, n, n1, n2, and m in the structural formulas (B-15) to (B-37) mean 1 to 60. l means 1-20. R represents a hydrogen atom or a methyl group.

--A compound having an aryl group and having three or more polymerizable groups--
Examples of the compound having an aryl group and having three or more polymerizable groups include trivalent or higher alcohol compounds having an aryl group, trivalent or higher amine compounds having an aryl group, and 3 having an aryl group. Examples include esters or amides of unsaturated carboxylic acids with at least one of higher-valent amino alcohol compounds.

Examples of the trivalent or higher alcohol compound having an aryl group, a trivalent or higher amine compound, and a trivalent or higher amino alcohol compound include 1,2,4-benzenetriol, methylene-2,4,6-trihydroxy. Examples include benzoate, phloroglicinol, pyrogallol and the like.
In addition, compounds obtained by adding α, β-unsaturated carboxylic acid to glycidyl compounds such as novolak type epoxy resin and bisphenol A diglycidyl ether, trimellitic acid and the like and vinyl monomers containing a hydroxyl group in the molecule Examples include esterified products, triallyl trimellitic acid, and epoxy compounds (for example, novolac-type epoxy resins).
Furthermore, cationically polymerizable epoxy compounds (for example, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, glycerin triglycidyl ether, etc.) can be used.

These compounds having three or more polymerizable groups may be used alone or in combination of two or more.
The content of the compound having three or more polymerizable groups in the molecule in the polymerizable compound is preferably 0.1 to 40% by mass, more preferably 1 to 30% by mass, and further 1 to 25% by mass. preferable.

-Other polymerizable compounds-
In the resin composition for an insulating material of the present invention, a polymerizable compound other than the above-described polymerizable compound may be used. For example, an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid and a polyvalent amine compound Examples include amides.

  Examples of the monomer of the ester of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include (meth) acrylic acid ester, ethylene glycol di (meth) acrylate, and polyethylene glycol having 2 to 18 ethylene groups. Di (meth) acrylate (for example, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, dodecaethylene glycol di (meth) acrylate , Tetradecaethylene glycol di (meth) acrylate, etc.), propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate having 2 to 18 propylene groups (for example, , Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, dodecapropylene glycol di (meth) acrylate, etc.), neopentyl glycol di (meth) acrylate, ethylene oxide modified Neopentyl glycol di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,3-butanediol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, 1 4-cyclohexanediol di (meth) acrylate, 1,5-pentanediol (meth) acrylate, pentaerythritol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, di (meth) acrylate of alkylene glycol chain having at least one ethylene glycol chain / propylene glycol chain (for example, International Publication No. 01/98832 pamphlet), polybutylene glycol di (meth) acrylate, glycerin di (meth) acrylate, xylenol di (meth) acrylate and the like. It is.

  Among the (meth) acrylic acid esters, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meta) from the viewpoint of easy availability. ) Acrylate, di (meth) acrylate of alkylene glycol chain each having at least one ethylene glycol chain / propylene glycol chain, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) ) Acrylate, diglycerin di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 1,5-pe Butanediol (meth) acrylate, neopentyl glycol di (meth) acrylate.

  Examples of the ester (itaconic acid ester) of the itaconic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4- Examples include butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetritaconate.

  Examples of the ester (crotonic acid ester) of the crotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Can be mentioned.

  Examples of the ester (isocrotonate) of the isocrotonic acid and the aliphatic polyhydric alcohol compound include ethylene glycol diisocrotonate and pentaerythritol diisocrotonate.

  Examples of the ester of maleic acid and the aliphatic polyhydric alcohol compound (maleic acid ester) include ethylene glycol dimaleate, triethylene glycol dimaleate, and pentaerythritol dimaleate.

  Examples of the amide derived from the polyvalent amine compound and the unsaturated carboxylic acid include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and octamethylene bis ( And (meth) acrylamide, diethylenetriamine bis (meth) acrylamide, and the like.

  In addition to the above, as the polymerizable compound, for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Compounds obtained by adding an α, β-unsaturated carboxylic acid to a glycidyl group-containing compound such as hexanediol diglycidyl ether, JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 Polyester acrylates and polyester (meth) acrylate oligomers, epoxy compounds (for example, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ester, etc. Ether, diethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, hexanediol diglycidyl ether) and (meth) acrylic acid reacted polyfunctional acrylates and methacrylates, Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308 (1984), photocurable monomers and oligomers, allyl esters (for example, diallyl phthalate, diallyl adipate, diallyl malonate, diallylamide (eg diallylacetamide, etc.), cations Polymerizable divinyl ethers (for example, butanediol-1,4-divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether) , Dipropylene glycol divinyl ether, hexanediol divinyl ether, etc.), epoxy compounds (eg, butanediol-1,4-diglycidyl ether, cyclohexanedimethanol glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, dipropylene) Glycol diglycidyl ether, hexanediol diglycidyl ether, etc.), oxetanes (eg, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, etc.), epoxy compounds, oxetanes (eg, WO01 / 2165) Compound, N-β-hydroxyethyl-β- (methacrylamide) ethyl acrylate, N, N-bis (β-methacryloxyethyl) acrylamide And compounds having two different ethylenically unsaturated double bonds, such as allyl methacrylate.

  Examples of the vinyl esters include divinyl succinate and divinyl adipate.

  The polymeric compound of this invention may be used individually by 1 type, and may use 2 or more types together.

(Thermal crosslinking agent)
The thermal crosslinking agent is not particularly limited as long as it is a compound that causes a crosslinking reaction by heating, and can be appropriately selected according to the purpose. A photosensitive layer formed using the resin composition for an insulating material In order to improve the film strength after curing, for example, an epoxy compound having at least two epoxy groups (oxirane ring) in one molecule (oxirane compound), one molecule in a range that does not adversely affect developability An oxetane compound having at least two oxetane rings can be used. Among these, an epoxy compound having at least two epoxy groups in one molecule is particularly preferable.

  Examples of the epoxy compound having at least two epoxy groups in one molecule include, for example, a bixylenol type or biphenol type epoxy resin (“YX4000 Japan Epoxy Resin” etc.) or a mixture thereof, a complex having an isocyanurate skeleton, etc. Cyclic epoxy resins ("TEPIC; manufactured by Nissan Chemical Industries", "Araldite PT810; manufactured by Ciba Specialty Chemicals"), bisphenol A type epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, halogenated epoxy resin (for example, low brominated epoxy resin, high halogenated epoxy resin, odor Phenol novolac type epoxy resin), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy resin, dicyclopentadiene type epoxy resin ("HP-7200, HP-7200H; manufactured by Dainippon Ink & Chemicals, Inc.), glycidylamine type epoxy resin (diaminodiphenylmethane type epoxy resin, diglycidylaniline, triglycidylaminophenol, etc.), glycidyl ester type epoxy resin (phthalic acid diglycidyl ester) Adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) hydantoin type epoxy resin, alicyclic epoxy resin (3,4 Poxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, “GT-300, GT-400, ZEHPE3150; manufactured by Daicel Chemical Industries”, etc. )), Imide type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylolethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (naphthol aralkyl type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type epoxy resin, commercially available products are “ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”) , “HP-4032, EXA-4750, EXA-4700; manufactured by Dainippon Ink & Chemicals, Inc.”), a polyphenol compound obtained by an addition reaction between a phenol compound and a diolefin compound such as divinylbenzene or dicyclopentadiene, Reaction product with epichlorohydrin, ring-opening polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid, epoxy resin having linear phosphorus-containing structure, epoxy resin having cyclic phosphorus-containing structure, α- Methylstilbene type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl type liquid crystal epoxy resin, azomethine phenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin (" CP 50S, CP-50M; manufactured by NOF Corporation, etc.), copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate, bis (glycidyloxyphenyl) fluorene type epoxy resin, bis (glycidyloxyphenyl) adamantane type epoxy resin, etc. Although it is mentioned, it is not restricted to these. These epoxy resins may be used individually by 1 type, and may use 2 or more types together.

The epoxy group in the epoxy compound having at least two epoxy groups in one molecule may have an alkyl group at the β-position, and an epoxy group in which the β-position is substituted with an alkyl group (more specifically, Are particularly preferably β-alkyl-substituted glycidyl groups and the like.
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of two or more epoxy groups contained in one molecule may be a β-alkyl-substituted glycidyl group, and at least one epoxy group May be a β-alkyl-substituted glycidyl group.

From the viewpoint of storage stability at room temperature, the epoxy compound containing an epoxy group having an alkyl group at the β-position is β- in all epoxy groups in the total amount of the epoxy compound contained in the resin composition for insulating materials. The ratio of the alkyl-substituted glycidyl group is preferably 30% or more, more preferably 40% or more, and particularly preferably 50% or more.
The β-alkyl-substituted glycidyl group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include β-methylglycidyl group, β-ethylglycidyl group, β-propylglycidyl group, β-butylglycidyl group. Among these, a β-methylglycidyl group is preferable from the viewpoint of improving the storage stability of the resin composition for an insulating material and the ease of synthesis.

  As the epoxy compound containing an epoxy group having an alkyl group at the β-position, for example, an epoxy compound derived from a polyhydric phenol compound and a β-alkylepihalohydrin is preferable.

  The β-alkylepihalohydrin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, β-methylepichlorohydrin, β-methylepibromohydrin, β-methylepifluorohydrin, etc. Β-methyl epihalohydrin, β-ethyl epichlorohydrin, β-ethyl epibromohydrin, β-ethyl epihalohydrin, such as β-ethyl epihalohydrin, β-propyl epichlorohydrin, β-propyl epibromohydrin Β-propyl epihalohydrin such as phosphorus and β-propyl epifluorohydrin; β-butyl epihalohydrin such as β-butyl epichlorohydrin, β-butyl epibromohydrin, β-butyl epifluorohydrin; . Among these, β-methylepihalohydrin is preferable from the viewpoint of reactivity with the polyhydric phenol and fluidity.

  The polyhydric phenol compound is not particularly limited as long as it is a compound containing two or more aromatic hydroxyl groups in one molecule, and can be appropriately selected according to the purpose. For example, bisphenol A, bisphenol Carbon number of F, bisphenol compounds such as bisphenol S, biphenol compounds such as biphenol and tetramethylbiphenol, naphthol compounds such as dihydroxynaphthalene and binaphthol, phenol novolac resins such as phenol-formaldehyde polycondensates, cresol-formaldehyde polycondensates C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate such as 1-10 monoalkyl-substituted phenol-formaldehyde polycondensate, xylenol-formaldehyde polycondensate, bisphenol A-formal Hydrate polycondensates such bisphenol compounds of - formaldehyde polycondensates, phenol and copolycondensates of monoalkyl-substituted phenol and formaldehyde having 1 to 10 carbon atoms, and phenolic compounds and polyaddition products of divinylbenzene. Among these, when selecting for the purpose of improving fluidity | liquidity and storage stability, the said bisphenol compound is preferable, for example.

Examples of the epoxy compound containing an epoxy group having an alkyl group at the β-position include di-β-alkyl glycidyl ether of bisphenol A, di-β-alkyl glycidyl ether of bisphenol F, and di-β-alkyl glycidyl of bisphenol S. Di-β-alkyl glycidyl ethers of bisphenol compounds such as ethers; Β-alkyl glycidyl ethers of naphthol compounds such as di-β-alkyl glycidyl ether of dinaphthol, di-β-alkyl glycidyl ether of binaphthol; poly- of phenol-formaldehyde polycondensate β-alkyl glycidyl ether; poly-β-alkyl glycidyl ether of monoalkyl-substituted phenol-formaldehyde polycondensate having 1 to 10 carbon atoms such as poly-β-alkyl glycidyl ether of cresol-formaldehyde polycondensate; xylenol-formaldehyde C1-C10 dialkyl-substituted phenol-formaldehyde polycondensate poly-β-alkyl glycidyl ether such as poly-β-alkyl glycidyl ether of condensate; poly-β-alkyl glycidyl ether of bisphenol A-formaldehyde polycondensate Bisphenol compounds such as poly-β-alkyl glycidyl ethers of formaldehyde polycondensates; poly-β-alkyl glycidyl ethers of polyaddition products of phenol compounds and divinylbenzene; The
Among these, a bisphenol compound represented by the following general formula (C-1), a β-alkyl glycidyl ether derived from a polymer obtained from this compound and epichlorohydrin, and the following general formula (C-2) Poly-β-alkyl glycidyl ether of a phenol compound-formaldehyde polycondensate represented by
However, in said general formula (C-1), R represents either a hydrogen atom and a C1-C6 alkyl group. n represents an integer of 0 to 20.
However, in said general formula (C-2), R represents either a hydrogen atom and a C1-C6 alkyl group. R ″ represents either a hydrogen atom or CH ₃ , and n represents an integer of 0 to 20.
These epoxy compounds containing an epoxy group having an alkyl group at the β-position may be used alone or in combination of two or more. It is also possible to use together an epoxy compound having at least two epoxy groups (oxirane ring) in one molecule and an epoxy compound containing an epoxy group having an alkyl group at the β-position.

  The skeleton of the epoxy compound is preferably at least one selected from a bisphenol type epoxy resin, a novolac type epoxy resin, an alicyclic group-containing type epoxy resin, and a hardly soluble epoxy resin.

  Examples of the epoxy compound having at least two oxetane rings in one molecule include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether and bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether. 1,4-bis [(3-methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) Multifunctionals such as methyl acrylate, (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof In addition to oxetanes, compounds having an oxetane group and novola Resin, poly (p-hydroxystyrene), cardo type bisphenols, calixarenes, calixresorcinarenes, silsesquioxanes and other ether compounds, and other ether compounds. And a copolymer of an unsaturated monomer having an alkyl group and an alkyl (meth) acrylate.

  As content of the said thermal crosslinking agent, 1-50 mass% is preferable with respect to the total solid in the resin composition for insulating materials, and 3-30 mass% is more preferable. When the content is less than 1% by mass, improvement in the film strength of the cured film is not recognized, and when it exceeds 50% by mass, the developability and the exposure sensitivity may be decreased.

(Core-shell type elastomer)
The core-shell type elastomer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the core-shell type elastomer is preferably core-shell fine particles having a primary particle diameter of 150 nm or less.
Specific examples of the core-shell type elastomer component include core-shell fine particles in which the core is a silicone-based elastomer and the shell is an acrylic resin (for example, GENIOPERL series (GENIOPERL P52, GENIOPERL P22) manufactured by Asahi Kasei Wacker Silicone Co., Ltd., manufactured by Mitsubishi Rayon Co., Ltd.) METABLEN S-2001), core-shell fine particles whose core is a butadiene styrene-based elastomer and whose shell is cross-linked polymethyl methacrylate (for example, Kureha Chemical Industry Co., Ltd., Kureha BTA751, Kureha BTA731; Mitsubishi Rayon Co., Ltd. Metabrene C102; Kaneace B52 manufactured by Kaneka Chemical Industry Co., Ltd.), core-shell fine particles whose core is an acrylic elastomer and the shell is cross-linked polymethyl methacrylate (for example, Kureha Chemical Industry Co., Ltd., Kureha M334; METABRENE W-300A manufactured by Mitsubishi Rayon Co., Ltd.), and core-shell fine particles (for example, METABRENE S-2001 manufactured by Mitsubishi Rayon Co., Ltd.) whose core is a silicone elastomer and whose shell is cross-linked polymethyl methacrylate. Can be mentioned.

  Moreover, what contains functional groups, such as an epoxy group and a carboxyl group, can also be used in a shell part. When an epoxy group-containing material (for example, Kureha Paraloid EXL2314, manufactured by Kureha Chemical Industry Co., Ltd.) is used, a toughened cured product is obtained because the interface between the fine particles and the curable resin is chemically bonded. For this reason, it is preferable to use a material containing a carboxyl group in the shell portion (for example, Staphyloid AC3871 manufactured by Takeda Pharmaceutical Co., Ltd.) as the solder resist because the resolution becomes high when developed with an alkaline developer.

(Fluorescent brightener)
As the fluorescent brightening agent, the thickness of the exposed portion of the photosensitive layer is adjusted for the purpose of adjusting exposure sensitivity and photosensitive wavelength in exposure to the photosensitive layer described later, or when exposing and developing the photosensitive layer. It is added from the viewpoint of improving the minimum energy (sensitivity) of the light that is not changed before and after the development. By using the fluorescent brightening agent in combination, for example, the sensitivity of the photosensitive layer can be adjusted very easily to 0.1 to 100 mJ / cm ² .

  The fluorescent whitening agent, also known as a “fluorescent whitening agent”, can absorb light having a wavelength in the vicinity of 300 to 450 nm, which is visible from ultraviolet to shortwave, and near 400 to 500 nm. It is a colorless or weakly colored compound capable of emitting fluorescence having the following wavelength. A description of the physical principles and chemistry of optical brighteners is given in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, Electronic Release, Wiley-VCH 1998. Basically, suitable optical brighteners contain a π-electron system comprising a carbocyclic or heterocyclic nucleus.

The fluorescent brightening agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound having a nonionic nucleus is preferred. The nonionic nucleus is preferably at least one selected from, for example, a stilbene nucleus, a distyrylbenzene nucleus, a distyrylbiphenyl nucleus, a divinylstilbene nucleus, a phenylpyrazoline nucleus, and a styrylpyrazoline nucleus.
The compound having a nonionic nucleus is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include pyrazolines, triazines, stilbenes, distyrylbenzenes, distyrylbiphenyls, and divinyl. Stilbenes, triazinylaminostilbenes, stilbenyltriazoles, stilbenylnaphthotriazoles, bis-triazolestilbenes, benzoxazoles, bisphenylbenzoxazoles, stilbenylbenzoxazoles, bis -Benzoxazoles, furans, benzofurans, bis-benzimidazoles, diphenylpyrazolins, diphenyloxadiazoles, naphthalimides, xanthenes, carbostyrils, pyrenes and 1,3,5-triazinyl -Derivatives etc. . Among these, those having at least one selected from a styryl group, a benzoxazolyl group, and a benzothiazolyl group are preferable, and further, a distyrylbenzene, a distyrylbiphenyl, or an ethenyl group, an aromatic ring group, and a heterocyclic group. Bisbenzoxazoles, bisbenzothiazoles, and the like linked by a divalent linking group consisting of are particularly preferable.
The fluorescent brightening agent may have a substituent. Examples of the substituent include an aliphatic group, an aromatic group, a heterocyclic group, a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, and a carbon number of 30 or less. Alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkylsulfonylaminocarbonyl group having 30 or less carbon atoms, arylsulfonylaminocarbonyl group, alkylsulfonyl group, arylsulfonyl group, having 30 or less carbon atoms Acylaminosulfonyl group, alkoxy group having 30 or less carbon atoms (for example, methoxy group, ethoxy group, benzyloxy group, phenoxyethoxy group, phenethyloxy group, etc.), alkylthio group having 30 or less carbon atoms (for example, methylthio group, ethylthio group) , Methylthioethyl Oethyl group, etc.), aryloxy groups having 30 or less carbon atoms (for example, phenoxy group, p-tolyloxy group, 1-naphthoxy group, 2-naphthoxy group, etc.), nitro groups, alkyl groups having 30 or less carbon atoms, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, acyloxy group having 30 or less carbon atoms (for example, acetyloxy group, propionyloxy group, etc.), acyl group having 30 or less carbon atoms (for example, acetyl group, propionyl group, benzoyl group, etc.), carbamoyl Groups (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group and the like), sulfamoyl groups (for example, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, Peridinosulfonyl group, etc.), 30 or more carbon atoms Aryl groups (for example, phenyl group, 4-chlorophenyl group, 4-methylphenyl group, α-naphthyl group, etc.), substituted amino groups (for example, amino group, alkylamino group, dialkylamino group, arylamino group, diarylamino) Group, acylamino group, etc.), substituted ureido group, substituted phosphono group, and the like.

  Examples of each of the above representative optical brighteners include, for example, those described in Okawara “Dye Handbook”, Kodansha, pages 84 to 145, pages 432 to 439.

As content of the said fluorescent brightening agent, 0.01-4 mass% is preferable with respect to all the components of the said pattern formation material, 0.02-2 mass% is more preferable, 0.05-1 mass% is Particularly preferred.
When the content is less than 0.01% by mass, the sensitivity may decrease, and when the content exceeds 4% by mass, the shape of the pattern may be deteriorated.
In addition to the fluorescent brightener, other sensitizers described below may be added as necessary.

(Sensitizer)
There is no restriction | limiting in particular as said sensitizer, Although it can select suitably from well-known sensitizers, For example, a hetero condensed ring type compound is preferable. The hetero-fused ring compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. Examples of the hetero-fused compound include hetero-fused ketone compounds, quinoline compounds, and acridine compounds.
Specific examples of the hetero-fused ketone compound include acridone compounds such as acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone; 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylami Coumarin, 3- (4-Diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazole-2- Thioxanthone compounds such as ircoumarin, 7-diethylamino-4-methylcoumarin, thioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 1-chloro-4-propyloxythioxanthone, Quantacure QTX, and JP-A-5-19475, JP-A-5-19475 Coumarins such as coumarin compounds described in JP-A No. 7-271028, JP-A No. 2002-363206, JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, and the like; It is. Among these, an acridone compound and a thioxanthone compound are particularly preferable.
Specific examples of the quinoline compound include quinoline, 9-hydroxy-1,2-dihydroquinolin-2-one, 9-ethoxy-1,2-dihydroquinolin-2-one, and 9-dibutylamino- 1,2-dihydroquinolin-2-one, 8-hydroxyquinoline, 8-mercaptoquinoline, quinoline-2-carboxylic acid, and the like.
Specific examples of the acridine compound include 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, acridine orange, chloroflavin, and acriflavine. Among these hetero condensed ring compounds, those containing a nitrogen element in the ring are more preferable. Preferred examples of those containing a nitrogen element in the ring include the acridine compounds, coumarin compounds substituted with amino groups, and acridone compounds. Among these, the acridone, coumarin substituted with an amino group, 9-phenylacridine, and the like are more preferable, and among these, the acridone is particularly preferable.
Also known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbanine) Cyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue, toluidine blue), anthraquinones (for example, anthraquinone), squalium (for example, squalium), and the like.

(Thermal polymerization inhibitor)
The thermal polymerization inhibitor may be added to prevent thermal polymerization or temporal polymerization of the polymerizable compound.
Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine. , Chloranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

(Color pigment)
There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, phthalocyanine green, Victoria pure blue BO (CI. 42595), auramine (CI. 41000), fat Black HB (C.I. 26150), Monolite Yellow GT (C.I. Pigment Yellow 12), Permanent Yellow GR (C.I. Pigment Yellow 17), Permanent Yellow HR (C.I) Pigment Yellow 83), Permanent Carmine FBB (CI Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11) ) Fastel Pink B Supra (CI Pigment Red 1) Monasutoraru Fast Blue (C.I. Pigment Blue 15), mono Light Fast Black B (C.I. Pigment Black 1), carbon, C. I. Pigment red 97, C.I. I. Pigment red 122, C.I. I. Pigment red 149, C.I. I. Pigment red 168, C.I. I. Pigment red 177, C.I. I. Pigment red 180, C.I. I. Pigment red 192, C.I. I. Pigment red 215, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 22, C.I. I. Pigment blue 60, C.I. I. Pigment blue 64 and the like. These may be used alone or in combination of two or more. Moreover, the dye suitably selected from well-known dye can be used as needed.

  The content of the color pigment can be determined in consideration of the exposure sensitivity of the photosensitive layer at the time of permanent pattern formation, resolution, etc., and varies depending on the type of the color pigment, but is generally 0.05 to 10 mass% is preferable and 0.1-5 mass% is more preferable.

(Filler)
Examples of the filler include inorganic pigments and organic fine particles.
The inorganic pigment is not particularly limited and may be appropriately selected from known ones. For example, kaolin, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, vapor phase method silica, amorphous Examples thereof include silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica.
The average particle diameter of the inorganic pigment is preferably less than 10 μm, and more preferably 3 μm or less. When the average particle size is 10 μm or more, resolution may be deteriorated due to light scattering.
There is no restriction | limiting in particular as said organic fine particle, According to the objective, it can select suitably, For example, a melamine resin, a benzoguanamine resin, a crosslinked polystyrene resin etc. are mentioned. Further, silica having an average particle diameter of 1 to 5 μm and an oil absorption of about 100 to 200 m ² / g, spherical porous fine particles made of a crosslinked resin, and the like can be used.

  The amount of the filler added is preferably 5 to 60% by mass. When the addition amount is less than 5% by mass, the linear expansion coefficient may not be sufficiently reduced. When the addition amount exceeds 60% by mass, when the cured film is formed on the photosensitive layer surface, The film quality becomes fragile, and when a wiring is formed using a permanent pattern, the function of the wiring as a protective film may be impaired.

(Adhesion promoter)
Preferred examples of the adhesion promoter include adhesion promoters described in JP-A-5-11439, JP-A-5-341532, JP-A-6-43638, and the like. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, 3-morpholino Methyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione, and 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole Amino group-containing benzotriazole, silane coupling agents, and the like.

  As content of the said adhesion promoter, 0.001-20 mass% is preferable with respect to all the components in the said pattern formation material, 0.01-10 mass% is more preferable, 0.1-5 mass% is Particularly preferred.

[Photosensitive film]
The photosensitive film of the present invention is formed by laminating a photosensitive layer made of a resin composition for an insulating material on a support. Preferably, a protective layer is laminated on the photosensitive layer, and other layers such as a cushion layer and an oxygen barrier layer (PC layer) are laminated as necessary.

  There is no restriction | limiting in particular as a form of the said photosensitive film, According to the objective, it can select suitably, For example, the form which has the said photosensitive layer and the said protective layer in this order on the said support body, A form comprising the PC layer, the photosensitive layer, and the protective layer in this order on the support, and the cushion layer, the PC layer, the photosensitive layer, and the protective layer in this order on the support. And the like. The photosensitive layer may be a single layer or a plurality of layers.

-Photosensitive layer-
There is no restriction | limiting in particular as a location provided in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it laminates | stacks on the said support body.
In the exposure process described later, the photosensitive layer modulates the light from the light irradiating means by means of a light modulating means having n picture elements for receiving and emitting light from the light irradiating means, and then It is preferable that exposure is performed with light passing through a microlens array in which microlenses having aspherical surfaces capable of correcting aberration due to distortion of the exit surface at the portion are arranged.

In the case where the photosensitive layer is exposed and developed, the minimum energy of light used for the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development is preferably 100 mJ / cm ² or less, More preferably, it is 70 mJ / cm ² or less. If the minimum energy of light used for the exposure exceeds 100 mJ / cm ² , the tact time becomes long, which is not preferable.

Here, “the minimum energy of light used in the exposure that does not change the thickness of the exposed portion of the photosensitive layer after the exposure and development” is so-called development sensitivity, for example, when the photosensitive layer is exposed. It can be determined from a graph (sensitivity curve) showing the relationship between the amount of light energy (exposure amount) used for the exposure and the thickness of the cured layer generated by the development process following the exposure.
The thickness of the cured layer increases as the exposure amount increases, and then becomes substantially the same and substantially constant as the thickness of the photosensitive layer before the exposure. The development sensitivity is a value obtained by reading the minimum exposure when the thickness of the cured layer becomes substantially constant.
Here, when the thickness of the cured layer and the thickness of the photosensitive layer before the exposure are within ± 1 μm, it is considered that the thickness of the cured layer is not changed by exposure and development.
A method for measuring the thickness of the cured layer and the photosensitive layer before exposure is not particularly limited and may be appropriately selected depending on the intended purpose. However, a film thickness measuring device, a surface roughness measuring device (for example, Surfcom) 1400D (manufactured by Tokyo Seimitsu Co., Ltd.)) and the like.

There is no restriction | limiting in particular as thickness of the said photosensitive layer, Although it can select suitably according to the objective, For example, 3 micrometers-100 micrometers are preferable, and 5 micrometers-70 micrometers are more preferable.
As the method for forming the photosensitive layer, on the support, the resin composition for insulating material of the present invention is dissolved, emulsified or dispersed in water or a solvent to prepare a resin composition solution for insulating material, The method of laminating | stacking by apply | coating this solution directly and drying is mentioned.

  There is no restriction | limiting in particular as a solvent of the resin composition solution for said insulating materials, According to the objective, it can select suitably, For example, methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, normal- Alcohols such as hexanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone; ethyl acetate, butyl acetate, acetic acid-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate, And esters such as methoxypropyl acetate; aromatic hydrocarbons such as toluene, xylene, benzene, ethylbenzene; carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, chloride Halogenated hydrocarbons such as tylene and monochlorobenzene; ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1-methoxy-2-propanol; dimethylformamide, dimethylacetamide, dimethylsulfoxide, Examples include sulfolane. These may be used alone or in combination of two or more. Moreover, you may add a well-known surfactant.

The application method is not particularly limited and may be appropriately selected depending on the purpose. For example, using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, or the like, it is directly applied to the support. The method of apply | coating is mentioned.
The drying conditions vary depending on each component, the type of solvent, the use ratio, and the like, but are usually about 60 seconds to 110 ° C. for about 30 seconds to 15 minutes.

  In the present invention, the photosensitive layer contains a binder, a polymerizable compound, and a filler, and is formed of a resin composition for an insulating material containing other components as necessary.

-Support-
The support is not particularly limited and may be appropriately selected depending on the intended purpose. However, it is preferable that the photosensitive layer is peelable and has good light transmittance, and further has a smooth surface. Is more preferable.

  The support is preferably made of a synthetic resin and transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose triacetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( (Meth) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride / vinyl acetate copolymer, polytetrafluoroethylene, polytrifluoro Various plastic films, such as ethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is particularly preferable. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in the thickness of the said support body, Although it can select suitably according to the objective, For example, 2 micrometers-150 micrometers are preferable, 5 micrometers-100 micrometers are more preferable, 8 micrometers-50 micrometers are especially preferable. The support may be a single layer or may have a multilayer structure.

  There is no restriction | limiting in particular as a shape of the said support body, Although it can select suitably according to the objective, A long shape is preferable. There is no restriction | limiting in particular in the length of the said elongate support body, For example, the thing of the length of 10m-20,000m is mentioned.

-Protective layer-
The photosensitive film may form a protective layer on the photosensitive layer.
Examples of the protective layer include those used for the support, paper, polyethylene, paper laminated with polypropylene, and the like. Among these, a polyethylene film and a polypropylene film are preferable.
There is no restriction | limiting in particular in the thickness of the said protective layer, Although it can select suitably according to the objective, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially preferable.
Examples of the combination of the support and the protective layer (support / protective layer) include polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene terephthalate, and the like. . Moreover, interlayer adhesion can be adjusted by surface-treating at least one of the support and the protective layer. The surface treatment of the support may be performed in order to increase the adhesive force with the photosensitive layer. For example, coating of a primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow treatment Examples thereof include discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment.

The static friction coefficient between the support and the protective layer is preferably 0.3 to 1.4, and more preferably 0.5 to 1.2.
When the coefficient of static friction is less than 0.3, slipping is excessive, so that winding deviation may occur when the roll is formed, and when it exceeds 1.4, it is difficult to wind into a good roll. Sometimes.

  For example, the photosensitive film is preferably wound around a cylindrical core, wound into a long roll, and stored. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably from the range of 10m-20,000m. Further, slitting may be performed so that the user can easily use, and a long body in the range of 100 m to 1,000 m may be formed into a roll. In this case, it is preferable that the support is wound up so as to be the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. From the viewpoint of protecting the end face and preventing edge fusion during storage, it is preferable to install a separator (especially moisture-proof and desiccant-containing) on the end face, and use a low moisture-permeable material for packaging. It is preferable.

  The protective layer may be surface-treated to adjust the adhesion between the protective layer and the photosensitive layer. In the surface treatment, for example, an undercoat layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, or polyvinyl alcohol is formed on the surface of the protective layer. The undercoat layer can be formed by applying the polymer coating solution to the surface of the protective layer and then drying at 30 to 150 ° C. for 1 to 30 minutes. The drying temperature is particularly preferably 50 ° C to 120 ° C.

-Other layers-
The other layers in the photosensitive film are not particularly limited and may be appropriately selected depending on the purpose. For example, a cushion layer, an oxygen barrier layer (PC layer), a release layer, an adhesive layer, a light absorption layer, You may have layers, such as a surface protective layer. These layers may be used alone or in combination of two or more. Further, a protective layer may be provided on the photosensitive layer.

-Method for producing photosensitive film-
The said photosensitive film can be manufactured as follows, for example.
First, a material contained in the resin composition for an insulating material is dissolved, emulsified or dispersed in water or a solvent to prepare a resin composition solution for an insulating material for a photosensitive film.

  As said solvent, the thing similar to the solvent of the said resin composition solution for insulating materials is mentioned.

  Next, the said resin composition solution for insulating materials is apply | coated on the said support body, it is made to dry and a photosensitive layer is formed, and a photosensitive film can be manufactured.

  Examples of the method for applying the resin composition solution for an insulating material include the methods described above.

  Since the photosensitive film uses the resin composition for an insulating material, it has good plating resistance, sensitivity, developability, and adhesion, and a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern, Can be suitably used for forming various patterns such as color filters, columns, ribs, spacers, liquid crystal structural members such as spacers, partition walls, etc., and for forming patterns such as holograms, micromachines, and proofs. It can be suitably used for forming a permanent pattern on a substrate.

  In particular, since the thickness of the photosensitive film is uniform, even if the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned when forming the permanent pattern, the high acceleration test (HAST ), Dendrite is not generated, and a high-definition permanent pattern excellent in heat resistance and moisture resistance can be obtained.

[Photosensitive laminate]
The photosensitive laminate is formed by laminating at least the photosensitive layer on the substrate and other layers appropriately selected according to the purpose.

-Substrate-
The substrate is a substrate to be processed on which a photosensitive layer is formed or a member to be transferred onto which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and is not particularly limited and may be appropriately selected according to the purpose. For example, it can be arbitrarily selected from those having high surface smoothness to those having an uneven surface. A plate-like substrate is preferable, and a so-called substrate is used. Specific examples include a known printed wiring board production substrate (printed substrate), a glass plate (soda glass plate, etc.) made of glass cloth and epoxy resin, a synthetic resin film, paper, a metal plate, and the like. Among these, the case where the board | substrate for well-known printed wiring boards which consists of glass cloth and an epoxy resin is used as a base | substrate is preferable.

-Method for producing photosensitive laminate-
As a manufacturing method of the said photosensitive laminated body, the method of apply | coating the said resin composition for insulating materials to the surface of the said base | substrate and drying as a 1st aspect is mentioned, As a 2nd aspect, at least in the said photosensitive film Examples of the method include transferring and laminating the photosensitive layer while performing at least one of heating and pressing.

In the method for producing a photosensitive laminate according to the first aspect, a photosensitive layer is formed by applying and drying the resin composition for an insulating material on the substrate.
The method for applying and drying is not particularly limited and can be appropriately selected depending on the purpose. For example, the insulating resin composition is dissolved, emulsified, or dissolved in water or a solvent on the surface of the substrate. A method of laminating by preparing a resin composition solution for an insulating material by dispersing, directly applying the solution, and drying.

  There is no restriction | limiting in particular as said coating method and drying conditions, According to the objective, it can select suitably, It carries out by the same method and conditions as what was used for the said photosensitive film.

In the method for producing a photosensitive laminate of the second aspect, the photosensitive film of the present invention is laminated on the surface of the substrate while performing at least one of heating and pressing. In addition, when the said photosensitive film has the said protective layer, it is preferable to peel this protective layer, and to laminate | stack so that the said photosensitive layer may overlap with the said base | substrate.
There is no restriction | limiting in particular in the said heating temperature, According to the objective, it can select suitably, For example, 15-180 degreeC is preferable and 60-140 degreeC is more preferable.
There is no restriction | limiting in particular in the said pressurization pressure, According to the objective, it can select suitably, For example, 0.1-1.0 MPa is preferable and 0.2-0.8 MPa is more preferable.

  There is no restriction | limiting in particular as an apparatus which performs at least any one of the said heating, According to the objective, it can select suitably, For example, Laminator (For example, Taisei Laminator VP-II, Nichigo Morton VP130) Etc. are preferable.

  Since the photosensitive film and the photosensitive laminate use the resin composition for an insulating material, the sensitivity, developability, and adhesion are good, and a high-definition permanent pattern can be efficiently formed, and a protective film For the formation of various patterns such as permanent patterns such as interlayer insulation films and solder resist patterns, for the production of liquid crystal structural members such as color filters, pillar materials, rib materials, spacers, partition walls, patterns for holograms, micromachines, proofs, etc. It can be suitably used for forming, etc., and can be particularly suitably used for forming a permanent pattern on a printed circuit board.

  In particular, since the photosensitive film has a uniform thickness, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned in the formation of the permanent pattern, in the highly accelerated life test (HAST) Since dendrites are not generated and a high-definition permanent pattern having excellent heat resistance and moisture resistance is obtained, lamination onto a substrate is performed more finely.

(Permanent pattern forming method)
The permanent pattern forming method includes at least an exposure process, and includes other processes such as an appropriately selected development process.
The pattern forming apparatus, which will be clarified through the description of the pattern forming method, includes the photosensitive laminate, and has at least light irradiation means and light modulation means.

-Exposure process-
The said exposure process is a process of exposing with respect to the photosensitive layer in the resin composition for insulating materials of this invention. The resin composition for an insulating material and the base material of the present invention are as described above.

  The exposure target is not particularly limited as long as it is the photosensitive layer in the resin composition for an insulating material, and can be appropriately selected according to the purpose. It is preferably performed on a laminate formed by laminating the resin composition while performing at least one of heating and pressurization.

  The exposure is not particularly limited as long as it is digital exposure, and can be appropriately selected according to the purpose.

  The digital exposure is not particularly limited as long as it is performed without using the photomask. For example, at least one of an exposure head including at least a light irradiation unit and a light modulation unit, and the photosensitive layer is moved. On the other hand, it is preferable that the light emitted from the light irradiation unit is irradiated onto the photosensitive layer from the exposure head while being modulated by the light modulation unit according to pattern information.

  The digital exposure is not particularly limited as long as it is a light source that emits near infrared rays from ultraviolet rays, and can be appropriately selected according to the purpose. For example, (ultra) high pressure mercury lamp, xenon lamp, carbon arc lamp, halogen lamp, A known light source such as a fluorescent tube for a copying machine or a laser is used, but a preferable light source is an (ultra) high pressure mercury lamp or laser, and a more preferable light source is a laser.

  A (super) high-pressure mercury lamp is a discharge lamp in which mercury is sealed in a quartz glass tube or the like, and is a lamp whose mercury vapor pressure is set high to increase luminous efficiency. Among the bright line spectra, a bright line spectrum of only one wavelength may be used using an ND filter or the like, or a light beam having a plurality of bright line spectra may be used.

Laser is an acronym for Light Amplification by Stimulated Emission of Radiation. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplifying and oscillating light waves, utilizing the phenomenon of stimulated emission that occurs in materials with an inverted distribution. Examples of the excitation medium include crystal, glass, liquid, dye, gas, and a known laser such as a solid laser, liquid laser, gas laser, or semiconductor laser can be used in the wavelength region.
Specifically, an Ar ion laser (364 nm, 351 nm), a Kr ion laser (356 nm, 351 nm), a He—Cd laser (325 nm) as a gas laser, a YAG laser, a YVO4 laser (1064 nm), YAG, YVO4 laser second harmonic (532 nm), third harmonic (355 nm), fourth harmonic (266 nm), a combination of a waveguide wavelength conversion element and AlGaAs, InGaAs semiconductor (380 nm to 400 nm), a waveguide wavelength conversion element A combination of AlGaInP and AlGaAs semiconductor (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like can be mentioned. Among these, a suitable laser is an AlGaInN semiconductor laser (commercially available InGaN semiconductor laser 375 nm). Others 405 nm), a high-power 355nm laser in terms of productivity.

The wavelength from the ultraviolet to the near infrared is preferably, for example, 300 to 1,500 nm, more preferably 320 to 800 nm, and particularly preferably 330 to 650 nm.
As a wavelength of the said laser beam, 200-1500 nm is preferable, for example, 300-800 nm is more preferable, 330-500 nm is still more preferable, 350-420 nm is especially preferable.

-Light modulation means-
A typical method of the light modulation means will be described.
One of them is a method having n pixel parts and controlling the pixel parts according to the pattern information. For example, a digital micromirror device (DMD), a MEMS (Micro Electro Mechanical Systems) type spatial light modulator (SLM), an optical element (PLZT element) that modulates transmitted light by an electro-optic effect, a liquid crystal Examples thereof include an optical shutter (FLC), and among these, DMD is preferable.

When the DMD is used, light from a light source is irradiated onto the DMD by an appropriate optical system, and reflected light from each mirror arranged two-dimensionally on the DMD is exposed to light through another optical system. An image of light spots arranged in two dimensions is formed on the layer. In this state, no light is exposed between the light spots. The entire surface of the photosensitive layer can be exposed in such a manner that the light spots in the rear row are exposed between the light spots. An image pattern can be formed by controlling the angle of each mirror of the DMD and turning the light spot on and off. By using such exposure heads having the DMD side by side, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed using a mirror gradation type spatial modulation element.

Moreover, it is preferable that the said light modulation means has a pattern signal generation means which produces | generates a control signal based on the pattern information to form. In this case, the light modulation unit modulates light according to the control signal generated by the pattern signal generation unit.
There is no restriction | limiting in particular as said control signal, According to the objective, it can select suitably, For example, a digital signal is mentioned suitably.

  On the other hand, another representative method of the light modulation means is a method using a polygon mirror. A polygon mirror is a rotating member having a series of planar reflecting surfaces around it. The light from the light source is reflected and irradiated onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. An image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. By using a plurality of light from the light source, the scanning time can be shortened.

For example, the following method can also be applied to the light modulation means of the present invention.
An example of drawing using a polygon mirror described in JP-A-5-150175, an apparatus using a polygon mirror by visually acquiring a part of an image of a lower layer described in JP-T-2004-523101 (WO2002 / 039793) In this example, exposure is performed with the position of the upper layer aligned with the position of the lower layer, an example of exposure with DMD described in JP-A-2004-56080, an exposure apparatus equipped with a polygon mirror described in JP-T-2002-523905, and JP-A-2001-255661. An exposure apparatus including a polygon mirror described in JP-A-2003-50469, an example of a combination of DMD, LD, and multiple exposure described in JP-A-2003-50469, an example of an exposure method that changes an exposure amount depending on a part of a substrate described in JP-A-2003-156893, This is an example of an exposure method for performing misalignment adjustment described in Japanese Patent Application Laid-Open No. 2005-43576.

--Light irradiation means--
There is no restriction | limiting in particular as an irradiation method of light, Although the above-mentioned exposure light source can be suitably selected according to the objective, It is suitable to synthesize | combine and irradiate two or more light from these light sources. It is particularly preferable to irradiate a laser beam (combined laser beam) obtained by synthesizing the above light.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this several laser light source There is a method of forming and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber.

The laser beam diameter is not particularly limited, but from the viewpoint of the resolution of the dark color separation barrier, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
In the present invention, it is preferable to spatially modulate the laser beam according to the image data. For this purpose, it is preferable to use the DMD which is a spatial light modulation element.

  Examples of the exposure apparatus having the light modulating unit and the light irradiating unit are described in Japanese Patent Application Laid-Open Nos. 2005-222039, 2005-258431, and 2006-30966. Although an apparatus can be used, the exposure apparatus in the present invention is not limited to this.

--Development process--
The developing step is a step of forming a permanent pattern by exposing the photosensitive layer by the exposing step, curing the exposed region of the photosensitive layer, and then developing by removing the uncured region.

  There is no restriction | limiting in particular as the removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method etc. which remove using a developing solution are mentioned.

  The developer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkali metal or alkaline earth metal hydroxides or carbonates, bicarbonates, aqueous ammonia, and quaternary ammonium. A salt aqueous solution is preferred. Among these, an aqueous sodium carbonate solution is particularly preferable.

  The developer includes a surfactant, an antifoaming agent, an organic base (for example, benzylamine, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.) May be used in combination with an organic solvent (for example, alcohols, ketones, esters, ethers, amides, lactones, etc.). The developer may be an aqueous developer obtained by mixing water or an alkaline aqueous solution and an organic solvent, or may be an organic solvent alone.

-Curing process-
The curing treatment step is a step of performing a curing treatment on the photosensitive layer in the formed permanent pattern after the development step is performed.

  There is no restriction | limiting in particular as said hardening process, Although it can select suitably according to the objective, For example, a whole surface exposure process, a whole surface heat processing, etc. are mentioned suitably.

Examples of the entire surface exposure processing method include a method of exposing the entire surface of the laminate on which the permanent pattern is formed after the developing step. By the entire surface exposure, curing of the resin in the pattern forming material for forming the photosensitive layer is accelerated, and the surface of the permanent pattern is cured.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface exposure, Although it can select suitably according to the objective, For example, UV exposure machines, such as an ultrahigh pressure mercury lamp, are mentioned suitably.

Examples of the entire surface heat treatment method include a method of heating the entire surface of the laminate on which the permanent pattern is formed after the developing step. By heating the entire surface, the film strength of the surface of the permanent pattern is increased.
As heating temperature in the said whole surface heating, 120-250 degreeC is preferable and 120-200 degreeC is more preferable. When the heating temperature is less than 120 ° C., the film strength may not be improved by heat treatment. When the heating temperature exceeds 250 ° C., the resin in the pattern forming material is decomposed, and the film quality is weak and brittle. There is.
As heating time in the said whole surface heating, 10 to 120 minutes are preferable and 15 to 60 minutes are more preferable.
There is no restriction | limiting in particular as an apparatus which performs the said whole surface heating, According to the objective, it can select suitably from well-known apparatuses, For example, a dry oven, a hot plate, IR heater etc. are mentioned.

When the substrate is a printed wiring board such as a multilayer wiring board, the permanent pattern of the present invention can be formed on the printed wiring board, and further soldered as follows.
That is, the development step forms a hardened layer that is the permanent pattern, and the metal layer is exposed on the surface of the printed wiring board. Gold plating is performed on the portion of the metal layer exposed on the surface of the printed wiring board, and then soldering is performed. Then, a semiconductor or a component is mounted on the soldered portion. At this time, the permanent pattern by the hardened layer exhibits a function as a protective film or an insulating film (interlayer insulating film), and prevents external impact and conduction between adjacent electrodes.

  In the permanent pattern forming method of the present invention, it is preferable to form at least one of a protective film, an interlayer insulating film, and a solder resist pattern. When the permanent pattern formed by the permanent pattern forming method is the protective film, the interlayer insulating film, and the solder resist pattern, the wiring can be protected from external impact and bending, and in particular, the interlayer insulation In the case of a film, it is useful for high-density mounting of semiconductors and components on, for example, a multilayer wiring board and a build-up wiring board.

  Since the permanent pattern forming method of the present invention can form a permanent pattern with high definition and efficiency by suppressing distortion of an image formed on the photosensitive layer, high-definition exposure is required. In particular, it can be suitably used for forming high-definition permanent patterns.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples without departing from the gist thereof. Unless otherwise specified, “part” is based on mass.

(Binder synthesis)
In a 1,000 mL three-necked flask, 159 g of 1-methoxy-2-propanol was placed and heated to 85 ° C. under a nitrogen stream. To this, a solution of 159 g of 1-methoxy-2-propanol containing 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped over 2 hours. After completion of the dropwise addition, the reaction was further continued by heating for 5 hours. Subsequently, the heating was stopped to obtain a copolymer of benzyl methacrylate / methacrylic acid (ratio of 30/70 mol%).

  Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-necked flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and dissolved by stirring. After dissolution, 3.0 g of triphenylphosphine was added and heated to 100 ° C. to carry out an addition reaction. The disappearance of glycidyl methacrylate was confirmed by gas chromatography, and heating was stopped. A solution of binder 1 having a mass average molecular weight of 30,000 and a solid content of 45% by mass was prepared. The resulting binder 1 had a benzyl methacrylate / methacrylic acid / methacrylic acid GMA adduct molar ratio of 30:33:37 and an I / O value of 0.88.

(Preparation of dispersion)
Silica, binder, dicyandiamide, color pigment, and n-propyl acetate were mixed in advance at the following addition amount, and then a motor mill M-250 (manufactured by Eiger) was used with zirconia beads having a diameter of 1.0 mm and a peripheral speed of 9 m. / S for 3 hours.

The above binder 124.2 parts silica (Admafine SO-C2, manufactured by Admatechs)
... 77.3 parts Dicyandiamide (DICY7, manufactured by Japan Epoxy Resin Co., Ltd.) (thermal crosslinking agent)
... 0.9 parts Blue pigment (HELIOGEN BLUE D7086, manufactured by BASF)
・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.3 parts Yellow pigment (Pariotol Yellow D0960, manufactured by BASF)
0.4 parts n-propyl acetate 151.7 parts Total 355.8 parts

(Example 1)
<Preparation of resin composition solution for insulating material>
(Insulating Material Resin Composition Solution 1)
A resin composition solution 1 for an insulating material having the following composition was prepared.
(1) Dispersion liquid 355.8 parts (2) Binder 375.8 parts (3) Monomer (DPHA, Nippon Kayaku Co., Ltd.) 90.6 parts (4) Bisphenol F type epoxy compound (YDF-170, manufactured by Tohto Kasei Co., Ltd.) (thermal crosslinking agent) 45.3 parts (5) Core-shell type elastomer (GENIOPERL P52, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., core: silicone elastomer, shell: acrylic resin, primary particle size 0.12 μm to 0.15 μm)
............ 4.5 parts (6) Fluorosurfactant (Megafac F780F, manufactured by Dainippon Ink and Company)
... 1.3 parts (7) Initiator (compound having the following structural formula C-1)
... 3.8 parts (8) Diethylthioxanthone (Kayacure DETX-S, manufactured by Nippon Kayaku Co., Ltd.)
... 4.0 parts (9) Methyl ethyl ketone (MEK) ... 118.9 parts Total ... 1000.0 parts The monomer (DPHA) is dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.), and the monomer acrylic equivalent is 91.

<Manufacture of photosensitive film>
The obtained resin composition solution 1 for an insulating material was applied with a bar coater onto a PET (polyethylene terephthalate) film having a thickness of 16 μm as a support (manufactured by Toray Industries, Inc., 16FB50), a width of 300 mm, and a length of 200 m. And dried in an 80 ° C. hot air circulation dryer to form a photosensitive layer having a thickness of 30 μm. Next, a polypropylene film (E-200, manufactured by Oji Specialty Paper Co., Ltd.) having a thickness of 20 μm, a width of 290 mm, and a length of 210 m is laminated as a protective film on the photosensitive layer by lamination, and the photosensitive film is coated with the photosensitive film. Manufactured.

<Production of photosensitive laminate>
The substrate was prepared by buffing the surface of a printed circuit board, that is, a copper-clad laminate (copper thickness 12 μm) on which wiring was formed. A vacuum laminator (manufactured by Nichigo Morton Co., Ltd., VP130) was peeled off on the copper clad laminate while peeling off the protective film on the photosensitive film so that the photosensitive layer of the photosensitive film was in contact with the copper clad laminate. A photosensitive laminate was prepared in which the copper-clad laminate, the photosensitive layer, and the polyethylene terephthalate film (support) were laminated in this order.
The pressure bonding conditions were a vacuum drawing time of 40 seconds, a pressure bonding temperature of 70 ° C., a pressure bonding pressure of 0.2 MPa, and a pressure application time of 10 seconds.

<Pattern formation>
The laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). A desired pattern was exposed on the surface of the photosensitive layer of the obtained laminate using INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm). After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed on the entire surface of the photosensitive layer on the copper-clad laminate with a spray pressure of 0.15 MPa. And spray development for 2 to 3 times the shortest development time (or 40 to 60 seconds) to dissolve and remove uncured areas.
Using this sample, the following sensitivity, resolution, and fine line adhesion were evaluated. The results are shown in Table 1.

<Preparation of permanent pattern>
A cured resin pattern is prepared by the same method as the evaluation of the resolution, and then the entire surface is exposed at 200 mJ / cm ² with an ultra-high pressure mercury lamp, and further subjected to heat treatment (post bake) at 170 ° C. for 1 hour to form a solder resist pattern ( Permanent pattern). Using this sample, the following thermal shock characteristics (the number of samples in which cracks occurred in 27 samples) were evaluated. The results are shown in Table 1.

<Evaluation of sensitivity>
The laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). Pattern data of L / S (line / space) = 50 μm / 50 μm was set to 0 on the surface of the photosensitive layer of the obtained laminate using INPREX IP-3000 (manufactured by Fuji Film Co., Ltd., pixel pitch = 1.0 μm). exposed by irradiating light of different light energy from .5MJ / cm ² to 200 mJ / cm ² at ^{2 1/2} times the interval, curing the L / S (line / space) = 50 [mu] m / 50 [mu] m line pattern It was. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spray development was carried out for 40 seconds to dissolve and remove uncured areas. The line width of the L = 50 μm pattern thus obtained was measured using a laser microscope (VK-9500, manufactured by Keyence Corporation; objective lens 50 times), and the exposure amount at which the line width was 50 μm was determined with sensitivity (optimal). Exposure amount).

<Evaluation of resolution>
The laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). Using the INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm), round hole pattern data in increments of 10 μm from 40 μmΦ to 400 μmΦ is applied to the surface of the photosensitive layer of the obtained laminate. Or 40 mJ / cm < ² >) and pattern exposure (DI (digital imaging) exposure) of each hole diameter was performed. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spray development was performed for 40 seconds, and the uncured area was dissolved and removed. The surface of the cured resin pattern thus obtained was observed with an optical microscope, and the minimum round hole diameter free from abnormalities such as tsumari and twist was measured on the cured resin pattern, and this was taken as the resolution. The smaller the numerical value, the better the resolution.

<Fine wire adhesion>
The laminate was allowed to stand for 10 minutes at room temperature (23 ° C., 55% RH). On the surface of the photosensitive layer of the obtained laminate, using INPREX IP-3000 (manufactured by FUJIFILM Corporation, pixel pitch = 1.0 μm), L / S (line / space) = 1/5 and line width of 20 μm. The pattern data in increments of 5 μm from 1 to 100 μm were exposed at the optimum exposure amount to cure the line pattern. After standing at room temperature for 10 minutes, the support was peeled off from the photosensitive laminate, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed onto the entire surface of the photosensitive layer on the copper clad laminate at a spray pressure of 0.15 MPa. Spray development was performed for 40 seconds, and the uncured area was dissolved and removed. The pattern thus obtained was observed using an optical microscope, and the minimum line width at which no line peeling or chipping was observed was defined as the fine line adhesion width.

<Evaluation of thermal shock test>
A photosensitive material was laminated on the glass epoxy substrate from which copper was completely removed by etching a copper-clad laminate having a copper thickness of 18 μm to produce a laminate. The photosensitive layer surface of the obtained laminate was exposed to 27 square patterns of 5 mm × 5 mm square using INPREX IP-3000 (manufactured by Fuji Film Co., Ltd., pixel pitch = 1.0 μm), and then developed. Pattern formation was performed, and then a permanent pattern was prepared. The obtained sample was put into a thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and after applying a thermal cycle of -65 ° C / 30 minutes, 125 ° C / 30 minutes, 300 cycles, The number of squares in which cracks occurred was examined by observing the pattern.

(Example 2)
Insulation in the same manner as in Example 1 except that “GENIOPERL P52” as the core-shell type elastomer was replaced with “GENIOPERL P22 (manufactured by Asahi Kasei Wacker Silicone Co., Ltd., core: silicone elastomer, shell: acrylic resin)” Resin composition solution 2 for materials was prepared.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 2 for insulating material.
In addition, the sensitivity, resolution, and fine line density of the pattern of Example 2 were evaluated in the same manner as Example 1, and the thermal shock characteristics of the permanent pattern of Example 2 were evaluated. The results are shown in Table 1.

(Example 3)
Except that “GENIOPERL P52” as the core-shell type elastomer was replaced with “Metablene S-2001 (manufactured by Mitsubishi Rayon Co., Ltd., core: silicone elastomer, shell: acrylic resin)”, in the same manner as in Example 1, A resin composition solution 3 for an insulating material was prepared.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 3 for insulating material.
Further, in the same manner as in Example 1, the sensitivity, resolution, and fine line density of the pattern of Example 3 were evaluated, and the thermal shock characteristics of the permanent pattern of Example 3 were evaluated. The results are shown in Table 1.

Example 4
A resin composition solution 4 for an insulating material was prepared in the same manner as in Example 1 except that the initiator was changed to “Compound having the following structural formula C-2 (Irgacure 907, manufactured by Ciba Specialty Chemicals)”. did.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 4 for insulating material.
In addition, the sensitivity, resolution, and fine line density of the pattern of Example 4 were evaluated in the same manner as Example 1, and the thermal shock characteristics of the permanent pattern of Example 4 were evaluated. The results are shown in Table 1.

(Example 5)
A resin composition solution 5 for an insulating material was prepared in the same manner as in Example 1 except that the initiator was changed to “Compound having the following structural formula C-3 (Irgacure 819, manufactured by Ciba Specialty Chemicals)”. did.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 5 for insulating material.
In addition, the sensitivity, resolution, and fine line density of the pattern of Example 5 were evaluated in the same manner as Example 1, and the thermal shock characteristics of the permanent pattern of Example 5 were evaluated. The results are shown in Table 1.

(Example 6)
Insulation in the same manner as in Example 1 except that “GENIOPERL P52” as the core-shell type elastomer was replaced with “Kureha BTA751 (manufactured by Kureha Co., Ltd., core: butadiene / styrene elastomer, shell: acrylic resin)”. A resin composition solution 6 for materials was prepared.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 6 for insulating material.
In addition, the sensitivity, resolution, and fine line density of the pattern of Example 6 were evaluated in the same manner as Example 1, and the thermal shock characteristics of the permanent pattern of Example 6 were evaluated. The results are shown in Table 2.

(Comparative Example 1)
A resin composition solution 7 for an insulating material was prepared in the same manner as in Example 1 except that the core-shell type elastomer was not added.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 7 for insulating material.
Further, in the same manner as in Example 1, the sensitivity, resolution, and fine line density of the pattern of Comparative Example 1 were evaluated, and the thermal shock characteristics of the permanent pattern of Comparative Example 1 were evaluated. The results are shown in Tables 1 and 2.

(Comparative Example 2)
Resin composition for insulating material in the same manner as in Example 1 except that “GENIOPERL P52” as the core-shell type elastomer was replaced with non-core-shell type silicone elastomer “GENIOMER 80” (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) A product solution 8 was prepared.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 8 for insulating material.
In addition, the sensitivity, resolution, and fine line density of the pattern of Comparative Example 2 were evaluated in the same manner as in Example 1, and the thermal shock characteristics of the permanent pattern of Comparative Example 2 were evaluated. The results are shown in Table 1.

(Comparative Example 3)
As in Example 1, except that “GENIOPERL P52” as a core-shell type elastomer was replaced with a non-core-shell type butadiene / styrene elastomer “ASAPRENE T-411” (manufactured by Asahi Kasei Corporation). Resin composition solution 9 was prepared.
A photosensitive film, a photosensitive laminate, a pattern, and a permanent pattern were produced in the same manner as in Example 1 except that the resin composition solution 1 for insulating material was replaced with the resin composition solution 9 for insulating material.
Further, in the same manner as in Example 1, the sensitivity, resolution, and fine line density of the pattern of Comparative Example 3 were evaluated, and the thermal shock characteristics of the permanent pattern of Comparative Example 3 were evaluated. The results are shown in Table 2.

From Table 1, Examples 1 to 5 in which a core-shell type elastomer (core: silicone elastomer, shell: acrylic resin) is added to the resin composition are applicable to DI (digital imaging) exposure, and the core-shell type elastomer is used. It was found that the thermal shock characteristics of the permanent pattern (solder resist pattern) are superior to those of Comparative Examples 1 and 2 in which no is added to the resin composition (the number of cracks generated is small).
Further, from Table 2, Example 6 in which a core-shell type elastomer (core: butadiene / styrene elastomer, shell: acrylic resin) was added to the resin composition is applicable to DI (digital imaging) exposure, and the core-shell type It was found that the thermal shock characteristics of the permanent pattern (solder resist pattern) were superior to those of Comparative Examples 1 and 3 where no elastomer was added to the resin composition (the number of cracks generated was small).
As mentioned above, it turns out that the resin composition for insulating materials of Examples 1-6 is applicable to DI (digital imaging) exposure, and can form the permanent pattern (solder resist pattern) excellent in the thermal shock characteristic. It was.

Since the photosensitive film of the present invention maintains developability and improves insulation reliability and can efficiently form a high-definition permanent pattern, a permanent pattern such as a protective film, an interlayer insulating film, and a solder resist pattern Can be suitably used for the formation of various patterns such as color filters, pillar materials, rib materials, spacers, liquid crystal structural members such as spacers, partition walls, holograms, micromachines, proofs, etc., especially for the formation of permanent patterns on package substrates Can be suitably used.
The pattern forming method using the resin composition for an insulating material of the present invention is for forming various patterns such as a protective film, an interlayer insulating film, and a permanent pattern such as a solder resist pattern, a color filter, a pillar material, a rib material, a spacer, It can be suitably used for the production of liquid crystal structural members such as partition walls, the production of holograms, micromachines, and proofs, and can be particularly suitably used for the formation of permanent patterns on package substrates.

Claims (9)

In the resin composition for an insulating material containing a binder, a photopolymerization initiator, a polymerizable compound having at least one unsaturated double bond, and a thermal crosslinking agent,
A resin composition for an insulating material, comprising a core-shell type elastomer.   The resin composition for an insulating material according to claim 1, wherein the shell part of the core-shell type elastomer is an acrylic resin.   The resin composition for an insulating material according to claim 1, wherein the core-shell type elastomer has a core part made of a silicone elastomer.   The resin composition for insulating materials according to any one of claims 1 to 3, wherein the photopolymerization initiator contains an oxime derivative. The resin composition for insulating materials according to claim 4, wherein the oxime derivative is represented by the following general formula (1).
However, in the general formula (1), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹ may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heterocyclic ring. A represents any of 4, 5, 6, and 7-membered rings and may contain a hetero atom. The resin composition for an insulating material according to claim 5, wherein the oxime derivative is represented by the following general formula (2).
However, in the general formula (2), R ¹ represents any of an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R ¹ may further have a substituent. m represents any integer of 0 or more. R ² represents a substituent, and when m is 2 or more, the R ² may be the same or different. Ar represents either an aromatic ring or a heterocyclic ring. X represents one of O and S. A represents either a 5- or 6-membered ring. The resin composition for an insulating material according to claim 6, wherein the oxime derivative is represented by the following general formulas (3) and (4).
However, in the general formulas (3) and (4), R ³ represents an alkyl group, and the alkyl group may further have a substituent. l represents an integer of 0 to 6. R ⁴ represents an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, or an acyloxy group. When l is 2 or more, the R ^{4 s} may be the same or different. May be. X represents either O or S. A represents either a 5- or 6-membered ring.   A photosensitive film comprising a photosensitive layer made of the resin composition for an insulating material according to claim 1 on a support.   A photosensitive laminate comprising a photosensitive layer made of the resin composition for an insulating material according to claim 1 on a substrate.