KR20100014433A

KR20100014433A - Photosensitive resin composition, photosensitive film, method for forming pattern by using the photosensitive film, and printed board

Info

Publication number: KR20100014433A
Application number: KR1020097019360A
Authority: KR
Inventors: 키미 이케다
Original assignee: 후지필름 가부시키가이샤
Priority date: 2007-03-30
Filing date: 2008-02-05
Publication date: 2010-02-10
Also published as: JP2010145425A; WO2008126455A1; CN101652716A

Abstract

An object of this invention is to provide the photosensitive resin composition, the photosensitive film, the pattern formation method using the same, and a printed circuit board which are excellent in plating resistance, a sensitivity, developability, and adhesiveness. The photosensitive resin composition of this invention contains a binder, a polymeric compound, a photoinitiator, an inorganic filler, and an adhesion promoter. It is characterized by the above-mentioned. The photosensitive film of this invention is characterized by laminating | stacking the photosensitive layer which consists of said photosensitive resin composition on a support body. The pattern formation method of this invention contains at least exposure to the photosensitive layer in the said photosensitive film, It is characterized by the above-mentioned. The printed circuit board of the present invention is characterized in that a permanent pattern is formed by the pattern forming method.

Description

Photosensitive resin composition, photosensitive film, pattern formation method and printed board using the same {PHOTOSENSITIVE RESIN COMPOSITION, PHOTOSENSITIVE FILM, METHOD FOR FORMING PATTERN BY USING THE PHOTOSENSITIVE FILM, AND PRINTED BOARD}

The present invention relates to a photosensitive resin composition having good plating resistance and sensitivity, a photosensitive film, a pattern forming method using the same, and a printed circuit board.

Conventionally, in forming permanent patterns, such as a soldering resist, the pattern forming material which formed the photosensitive layer by apply | coating and drying a photosensitive resin composition on a support body is used. As a manufacturing method of the said permanent pattern, the laminated body is formed by laminating | stacking the said pattern formation material on base materials, such as a copper clad laminated board in which the said permanent pattern is formed, for example, and it exposes to the said photosensitive layer in the said laminated body. After the exposure, the photosensitive layer is developed to form a pattern, and then the permanent pattern is formed by performing a curing treatment or the like.

Here, in the said photosensitive resin composition, in order to improve the resolution by giving favorable adhesiveness with the base material of a printed circuit board and the wiring pattern surface, the adhesion promoters, such as a benzimidazole derivative and a benzoxazole derivative, are added, and it is high transparency. The photosensitive film apply | coated on the support body is disclosed (patent document 1).

Moreover, the photosensitive element which added the carboxy benzotriazole derivative for the purpose of being excellent in adhesiveness with the surface of a base material, and plating resistance is disclosed (patent document 2).

However, these photosensitive resin compositions aim at the preparation of the wiring pattern of a printed board, and when the process is complete | finished, it will be removed by the peeling process. Therefore, there is a problem in terms of insulation reliability for use in a permanent pattern such as a solder resist that requires long-term performance stability.

Moreover, the photosensitive resin composition containing a polyamic-acid compound and a benzotriazole derivative is disclosed for the purpose of obtaining the soldering resist excellent in PCT resistance, solder heat resistance, storage stability, etc. (patent document 3).

However, since this photosensitive resin composition is low in sensitivity and needs to be applied directly onto a substrate, the smoothness of the surface of the substrate is inferior to that of the photosensitive film, or voids are generated in the through hole of the substrate, which causes popcorn phenomenon. There was a problem.

Therefore, development of the photosensitive resin composition, the photosensitive film, the pattern formation method using the same, and the printed circuit board which have favorable plating resistance, a sensitivity, insulation reliability, and adhesiveness is desired.

Patent Document 1: Japanese Patent Laid-Open No. 2006-251385

Patent Document 2: Japanese Patent Application Laid-Open No. 2-191955

Patent Document 3: Japanese Patent Application Laid-Open No. 11-24266

This invention is made | formed in view of such a present situation, and makes it a subject to solve the said various problems in the past, and to achieve the following objectives. That is, an object of the present invention is to provide a photosensitive resin composition, a photosensitive film, a pattern formation method using the same, and a printed circuit board having good plating resistance, sensitivity, developability, and adhesion.

Means for solving the above problems are as follows. In other words,

It contains a <1> binder, a polymeric compound, a photoinitiator, an inorganic filler, and an adhesion promoter. It is a photosensitive resin composition characterized by the above-mentioned.

In <1>, the adhesion promoter is a benzimidazole derivative, a benzoxazole derivative, a benzthiazole derivative, a thiotriazole derivative, a thiooxadiazole derivative, an N-substituted indazole derivative, an aromatic substituted indazole derivative. And at least one photosensitive resin composition selected from tetrazole derivatives, quinoline derivatives, carbothioic acid amide derivatives and benzotriazole derivatives.

<3> The photosensitive resin composition as described in <1> or <2> whose inorganic filler is silica.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the photopolymerization initiator is an oxime derivative.

<5> The photosensitive resin composition according to any one of <1> to <4>, further containing a thermal crosslinking agent.

In <5> <5>, a heat crosslinking agent is the photosensitive resin composition which is at least 1 sort (s) chosen from the compound obtained by making a blocking agent react with an epoxy resin compound, an oxetane compound, a polyisocyanate compound, and a polyisocyanate compound.

It is a photosensitive film characterized by laminating | stacking the photosensitive layer which consists of a photosensitive resin composition in any one of <1>-<6> on a <7> support body.

<8> It is the pattern formation method characterized by including exposing to the photosensitive layer in the photosensitive film as described in <7> at least.

<9> In <8>, the exposure modulates the light by the light modulation means, and then the micro-array having an aspherical surface having an aspherical surface capable of correcting the aberration caused by the distortion of the exit surface of the drawing part in the light modulation means. It is a pattern formation method performed through a lens array.

<10> It is a pattern formation method in <8> or <9> which develops a photosensitive layer after exposure is performed.

<11> It is a pattern formation method of hardening of a photosensitive layer after image development is performed in <10>.

<12> It is a printed circuit board in which a permanent pattern is formed by the pattern formation method in any one of <8>-<11>.

ADVANTAGE OF THE INVENTION According to this invention, the conventional problem can be solved and it can provide the photosensitive resin composition, the photosensitive film, and the pattern forming apparatus, pattern formation method, and printed circuit board which are excellent in plating resistance, a sensitivity, developability, and adhesiveness. Can be.

(1) photosensitive resin composition

In the present invention, the photosensitive resin composition contains a binder, a polymerizable compound, a photopolymerization initiator, an inorganic filler, an adhesion promoter, and other components as necessary.

〔bookbinder〕

As said binder, the high molecular compound which contains an acidic group and ethylenically unsaturated bond in a side chain, an epoxy acrylate compound, etc. are used suitably, Among these, the high molecular compound which contains an acidic group and ethylenically unsaturated bond in a side chain is used suitably.

As said acidic group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. are mentioned, A carboxyl group is preferable from the point of a raw material acquisition.

Moreover, as said binder, at least 1 polymerizable double bond in a molecule | numerator, for example, acrylic groups, such as a (meth) acrylate group or a (meth) acrylamide group, vinyl ester of carboxylic acid, vinyl ether, allyl ether, etc. Various polymerizable double bonds of can be used. More specifically, glycidyl esters of unsaturated fatty acids such as cyclic ether group-containing polymerizable compounds, for example, glycidyl acrylate, glycidyl methacrylate, cinnamic acid, in acrylic resins containing carboxyl groups as acidic groups; And compounds obtained by adding an epoxy group-containing polymerizable compound such as an alicyclic epoxy group (for example, an epoxy group such as cyclohexene oxide in the same molecule) and a compound having a (meth) acryloyl group. Moreover, the compound obtained by adding polymeric compounds containing isocyanate groups, such as isocyanate ethyl (meth) acrylate, to the acrylic resin containing an acidic group and a hydroxyl group, hydroxyalkyl (meth) acrylate, etc. to the acrylic resin containing anhydride groups, etc. The compound etc. which are obtained by adding the polymeric compound containing the hydroxyl group of these are also mentioned. Moreover, the compound etc. which are obtained by copolymerizing cyclic ether group containing polymeric compounds, such as glycidyl methacrylate, and vinyl monomers, such as (meth) acryloylalkyl ester, and adding (meth) acrylic acid to a side chain epoxy group are mentioned. have.

Examples of these include Japanese Patent Laid-Open No. 2763775, Japanese Patent Laid-Open No. 3-172301, Japanese Patent Laid-Open No. 2000-232264, and the like.

Among them, the binder includes a polymer compound containing a cyclic ether group (for example, an epoxy group and a group having an oxetane group in a partial structure) added to a part of the acidic group of the polymer compound, and a part of the cyclic ether group of the polymer compound or It is more preferable that it is a high molecular compound selected from either of which the carboxyl group-containing polymeric compound was added to all. At this time, the addition reaction of the compound having an acidic group and a cyclic ether group is preferably carried out in the presence of a catalyst, and in particular, the catalyst is preferably selected from an acidic compound and a neutral compound.

Among them, from the viewpoint of developing stability over time of the photosensitive resin composition, the binder is preferably an aromatic group which may contain a carboxyl group and a heterocycle in the side chain and a high molecular compound containing an ethylenically unsaturated bond in the side chain.

--The aromatic group which may contain a heterocycle--

As an aromatic group which may contain the said heterocycle (henceforth simply an "aromatic group"), for example, a benzene ring, two to three benzene rings, a condensed ring formed, a benzene ring and a 5-membered unsaturated ring are condensed. The thing which formed the ring etc. are mentioned.

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, iso Oxazole ring group, isothiazole ring group, indazole ring group, benzoisoxazole ring group, benzoisothiazole ring group, imidazole ring group, oxazole ring group, thiazole ring group, benzimidazole ring group, benzoxazole ring group, benzothiazole ring group , Pyridine ring, quinoline ring, isoquinoline ring, pyridazine ring, pyrimidine ring, pyrazine ring, phthalazine ring, quinazoline ring, quinoxaline ring, acyldine ring, phenanthridine ring, carbazole ring, purine Ventilation, pyran ring, piperidine ring, piperazine ring, indole ring, indolijin ring, chroman ring, cinnanor ring, acridine ring, phenothiazine ring, tetrazol ring, triazine ring, etc. have. 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, and 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, and a cyano group Alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group etc. which may respectively have a substituent are mentioned.

As said alkyl group, a linear alkyl group of 1-20 carbon atoms, a branched alkyl group, a cyclic alkyl group, etc. are mentioned, for example.

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl and octadecyl. Real 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-methyl Hexyl group, a cyclohexyl group, a cyclopentyl group, 2-norbornyl group, etc. are mentioned. 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.

As a substituent which the said alkyl group may have, the group which consists of monovalent nonmetallic atom groups except a hydrogen atom is mentioned, for example. As such a substituent, for example, a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, an aryloxy group, a mercapto group, an alkylthio group, an arylthio group, an alkyldithio group , Aryldithio 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 , Alkyl sulfoxy group, aryl sulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N '-Aryl ureido group, N', N'- diaryl ureido group, N'-alkyl-N'- aryl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido Pottery, N'-alkyl-N-aryl Ureido group, N ', N'-dialkyl-N-alkylureido group, N', N'-dialkyl-N-arylureido group, N'-aryl-N-alkylureido group, N'-aryl-N -Aryl ureido group, N ', N'- diaryl-N-alkyl ureido group, N', N'- diaryl-N-aryl ureido group, N'-alkyl-N'-aryl-N-alkyl ureido Group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonyl Amino 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 , an aryl sulfonyl group, sulfo group (-SO ₃ H) and its conjugate salt Groups (referred to as sulfonate groups), alkoxysulfonyl groups, aryloxysulfonyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N -Diaryl sulfinamoyl group, N-alkyl-N-aryl sulfinamoyl group, sulfamoyl group, N-alkyl sulfamoyl group, N, N-dialkyl sulfamoyl group, N-aryl sulfamoyl group, N, N- Dia rilsul sulfamoyl, N- alkyl -N- aryl sulfamoyl group, phosphono group (-PO ₃ H ₂₎ and its conjugated salts device (hereinafter referred to as phosphonate group), dialkyl phosphono group (-PO ₃ ( alkyl) ₂ ) (hereinafter "alkyl" means an alkyl group), diaryl phosphono group (-PO ₃ (aryl) ₂ ) (hereinafter "aryl" means an aryl group), alkylaryl phosphono Group (-PO ₃ (alkyl) (aryl)), monoalkylphosphono group (-PO ₃ (alkyl)) and its conjugated base group (referred to as alkylphosphonate group), monoarylphosphono group (-PO ₃ H (aryl)) and its conjugated base group (referred to as arylphosphonate group), phospho Oxy group (-OPO ₃ H ₂₎ and its conjugated salts device (hereinafter referred to as phosphonium carbonate group), dialkyl phosphonate nook group _{(-OPO 3 H (alkyl) 2} ), diaryl phosphono oxy group (-OPO ₃ (aryl) ₂ ), alkylaryl phosphonooxy group (-OPO ₃ (alkyl) (aryl)), monoalkyl phosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (alkyl phosphonate Oxy group), monoaryl phosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base (referred to as aryl phosphonateoxy 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 alkyl group described above.

Specific examples of the aryl group in the substituent include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group and methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group , Phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatephenyl group, phosphonophenyl group, phosphonatephenyl group and the like.

Specific examples of the alkenyl group in the substituent include a vinyl group, 1-propenyl group, 1-butenyl group, cinnammyl group, 2-chloro-1-ethenyl group and the like.

Specific examples of the alkynyl group in the substituent include an ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, and the like.

Examples of R ⁰¹ in the acyl group (R ⁰¹ CO-) in the above substituents may be mentioned a hydrogen atom, an alkyl group of the above, an aryl group, and the like.

Among these substituents, halogen atom (-F, -Br, -Cl, -I), alkoxy group, aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyl jade Period, 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-dialkylsul Pamoyl group, N-aryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosph Phonate groups, monoaryl phosphono groups, aryl phosphonate groups, phosphonooxy groups, phosphonateoxy groups, aryl groups, alkenyl groups and the like are preferable.

Moreover, as a heterocyclic group in the said substituent, a pyridyl group, a piperidinyl group, etc. are mentioned, for example, As a silyl group in the said substituent, a trimethylsilyl group etc. are mentioned.

On the other hand, as an alkylene group in the said alkyl group, what was used as the divalent organic residue except the hydrogen atom on the C1-C20 alkyl group mentioned above, for example is mentioned, for example, a carbon atom Preferred are linear alkylene groups having 1 to 12 carbon atoms, branched alkylene groups having 3 to 12 carbon atoms, cyclic alkylene groups having 5 to 10 carbon atoms, and the like.

As a preferable specific example of the substituted alkyl group obtained by combining such a substituent and an alkylene group, a chloromethyl group, a bromomethyl group, 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, isopropoxymethyl group, butoxymethyl group, s-butoxy Butyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetramethylpiperidinylmethyl 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, allyloxycar Carbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonate butyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl Group, N-methyl-N- (phosphonophenyl) sulfamoyl octyl group, phosphonobutyl group, phosphonate hexyl group, diethyl phosphono butyl group, diphenyl phosphono propyl group, methyl phosphono butyl group, methyl phosph Phonatebutyl group, tolylphosphonohexyl group, tolylphosphonate hexyl group, phosphonooxypropyl group, phosphonateoxy butyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenyl Ethyl group, p-methylbenzyl group, cinnamil group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl Group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. are mentioned.

As said aryl group, the benzene ring, the thing in which two to three benzene rings formed the condensed ring, the thing in which the benzene ring and the 5-membered unsaturated ring formed the condensed ring, etc. are mentioned, for example.

As a specific example of the said aryl group, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, etc. are mentioned, for example. In these, a phenyl group and a naphthyl group are preferable.

The alkyl group may have a substituent, and as an aryl group (hereinafter, also referred to as a "substituted aryl group") having such a substituent, for example, a substituent other than a hydrogen atom as a substituent on the cyclic carbon atom of the aryl group described above. The thing which has group which consists of monovalent nonmetallic atom group is mentioned.

As a substituent which the said aryl group may have, what was shown as the substituent which the above-mentioned alkyl group, substituted alkyl group, and the said alkyl group may have is preferable, for example.

Preferable specific examples of the substituted aryl group include a 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, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, Carbamoylphenyl group, N-methyl carbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfope Nyl) carbamoylphenyl group, sulfophenyl group, sulfonatephenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (force Phonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatephenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatephenyl group, tolylphosphonophenyl group, tolylphosphonatephenyl group, An allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, etc. are mentioned. .

The alkenyl group ^{(-C (R 02) = C} (R 03) (R 04)) and as the alkynyl group (-C≡C (R ^05)), for ^{example, R 02, R 03, R} 04 and R ^The group which ⁰⁵ consists of monovalent nonmetallic atom group is mentioned.

As said R <^02> , R <^03> , R <^04> and R <^05> , a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, etc. are mentioned, for example. As these specific examples, what was shown by the above-mentioned example is mentioned. 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 A tinyl group etc. are mentioned.

As said heterocyclic group, the pyridyl group etc. which were illustrated as a substituent of a substituted alkyl group are mentioned, for example.

Examples of the oxy group (R ⁰⁶ O-) include a group in which R ⁰⁶ is composed of a monovalent nonmetallic atom group excluding a hydrogen atom.

As such an oxy group, an alkoxy group, an aryloxy group, acyloxy group, carbamoyloxy group, N-alkyl carbamoyloxy group, N-aryl carbamoyloxy group, N, N-dialkyl carbamoyl jade, for example A time period, an N, N- diaryl carbamoyloxy group, an N-alkyl-N-arylcarbamoyloxy group, an alkyl sulfoxy group, an aryl sulfoxy group, a phosphonooxy group, a phosphonateoxy group, etc. are preferable.

As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned. In addition, 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, and a substituted aryl group. Among these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an aryl sulfoxy group are more preferable.

Specific examples of the preferred oxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group, phenethyloxy group, Carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, mor Polynoethoxy group, morpholinopropyloxy group, allyloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, methoxyphenyloxy group, ethoxyphenyl Oxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, phenylsulfonyloxy group, phosphonooxy group, phosphonateoxy group, etc. are mentioned.

As amino groups (R ⁰⁸ NH-, (R ⁰⁹ ) (R ⁰¹⁰ ) N-) which may contain an amide group, for example, R ⁰⁸ , R ⁰⁹ and R ⁰¹⁰ are a group consisting of monovalent nonmetallic atom groups excluding hydrogen atoms. Can be mentioned. In addition, R ⁰⁹ and R ⁰¹⁰ may combine with each other 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 and N-alkylacyl Amino 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'-di 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-aryl Ureido group, N'-alkyl-N'-aryl-N-alkylureido group, N'-alkyl-N'-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonyl Amino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, etc. are mentioned. Can be. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned. In addition, an acylamino group, R ⁰⁷ of the acyl N- alkyl amino group, N- aryl acyl (R ⁰⁷ CO-) in the acylamino group are the same as described above. Among these, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, and acylamino group are more preferable.

Specific examples of the preferred amino group 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 a group in which R ⁰¹¹ is a monovalent nonmetallic atom group.

As such a sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, etc. are preferable, for example. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned.

As a specific example of the said sulfonyl group, a butyl sulfonyl group, a phenyl sulfonyl group, a chlorophenyl sulfonyl group, etc. are mentioned.

The sulfonate group (-SO ₃ -) means a conjugated base anion group of a sulfo group (-SO ₃ H) as described above, and is usually preferably used with a counter cation.

As such a counter cation, a generally known one can be appropriately selected and used, for example, oniums (for example, ammoniums, sulfoniums, phosphoniums, iodoniums, adinium, etc.), metal ions ( For example, Na ⁺ , K ⁺ , Ca ²⁺ , Zn ²⁺ and the like) may be mentioned.

Examples of the carbonyl group (R ⁰¹³ -CO-), for example, R ⁰¹³ may be exemplified by the group consisting of a monovalent non-metallic atomic group.

As such a carbonyl group, for example, 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, and the like. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned.

As the carbonyl group, a formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group are preferable. The formyl group, acyl group, alkoxycarbonyl group and aryloxycarbonyl group are more preferable.

Specific examples of the carbonyl group include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, dimethylaminophenylethenylcarbonyl, methoxycarbonylmethoxycarbonyl and N-methylcarbamoyl groups , N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group, etc. are mentioned preferably.

Examples of the sulfinyl group (R ⁰¹⁴ -SO-) include a group in which R ⁰¹⁴ is composed of a monovalent nonmetallic atom 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-dia A ryl sulfinamoyl group, an N-alkyl-N-aryl sulfinamoyl group, etc. are mentioned. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned. Among these, alkylsulfinyl groups and arylsulfinyl groups are preferable.

As a specific example of the said substituted sulfinyl group, a hexyl sulfinyl group, benzyl sulfinyl group, a tolyl sulfinyl group, etc. are mentioned preferably.

The phosphono group means that one to two of the hydroxyl groups on the phosphono group is substituted by another organic oxo group, for example, the above-described dialkyl phosphono group, diaryl phosphono group, alkylaryl phosphono group, Monoalkyl phosphono group, a monoaryl phosphono group, etc. are preferable. In these, a dialkyl phosphono group and a diaryl phosphono group are more preferable.

As a more preferable specific example of the said phosphono group, a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, etc. are mentioned.

The phosphonate group (-PO ₃ H _2- , -PO ₃ H-) is a conjugated base derived from an acid first dissociation or an acid second dissociation of a phosphono group (-PO ₃ H ₂ ) as described above. It means an anionic group. It is usually preferred to use it with counter cations. As such a counter cation, a generally known one can be appropriately selected. For example, various oniums (ammonium, sulfonium, phosphonium, iodonium, adenium, etc.), metal ions (Na ⁺ , K ⁺⁾ , Ca ²⁺ , Zn ²⁺ and the like).

The phosphonate group of the phosphono group, a hydroxyl group-substituted 1-oxo-organic, but may be a conjugate base anion group, such a concrete example of the above monoalkyl phosphono group _{(-PO 3 H (alkyl))} , monoaryl phosphono And conjugated bases of the group (-PO ₃ H (aryl)).

The said aromatic group can manufacture 1 or more types of radically polymerizable compounds containing an aromatic group, and 1 or more types of other radically polymerizable compounds as a copolymerization component as needed by a normal radical polymerization method.

As said radical polymerization method, suspension polymerization method, solution polymerization method, etc. are mentioned generally, for example.

As a radically polymerizable compound containing the said aromatic group, the compound represented by general formula (A-1) and the compound represented by general formula (A-2) are preferable, for example.

However, in said general formula (A-1), R <_1> , R <_2> and R <_3> represent a hydrogen atom or monovalent organic group. L may represent an organic group and may be absent. Ar represents an aromatic group which may contain a heterocyclic ring.

However, in said general formula (A-2), R <_1> , R <_2> and R <_3> and Ar represent the same meaning as the said general formula (A-1).

As said L organic group, it is a polyvalent organic group which consists of a nonmetallic atom, for example, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 The thing which consists of 0 to 100 hydrogen atoms and 0 to 20 sulfur atoms is mentioned.

More specifically, as said organic group of L, the thing comprised by combining the following structural units, polyvalent naphthalene, polyvalent anthracene, etc. are mentioned.

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

In the compound represented by the said General formula (A-1) and the compound represented by the general formula (A-2), the general formula (A-1) is preferable at the point of a sensitivity. Moreover, it is preferable from the point of stability that it has a coupling group in the said general formula (A-1), and as said organic group of L, a C1-C4 alkylene group is preferable at the point of the removable (developability) of a non-image part. Do.

The compound represented by the said general formula (A-1) becomes a compound containing the structural unit of the following general formula (A-3). In addition, the compound represented by the said general formula (A-2) becomes a compound containing the structural unit of the following general formula (A-4). Among these, the structural unit of general formula (A-3) is preferable at the point of storage stability.

However, in said general formula (A-3) and general formula (A-4), R <_1> , R <_2> and R <_3> and Ar have the same meaning as the said general formula (A-1) and general formula (A-2). Indicates.

In the general formulas (A-3) and (A-4), R ₁ and R ₂ are preferably hydrogen atoms, and R ₃ is a methyl group from the viewpoint of removability (developability) of the non-burning portion.

In the formula (A-3), L is preferably an alkylene group having 1 to 4 carbon atoms in view of the removability (developability) of the non-image portion.

Although there is no restriction | limiting in particular as a compound represented by the said General formula (A-1) or a compound represented by General Formula (A-2), For example, the following exemplary compounds (1)-(30) are mentioned. .

Among the exemplary compounds (1) to (30), (5), (6), (11), (14) and (28) are preferred, and among these, (5) and (6) are points of storage stability and developability. More preferred.

Although content in the said binder of the aromatic group which may contain the said heterocycle does not have a restriction | limiting in particular, When the total structural unit of a high molecular compound is 100 mol%, the structural unit represented with the said general formula (A-3) is It is preferable to contain 20 mol% or more, and it is more preferable to contain 30 mol%-45 mol%. When the said content is less than 20 mol%, storage stability may become low, and when it exceeds 45 mol%, developability may fall.

--Ethylenically unsaturated bonds--

There is no restriction | limiting in particular as said ethylenically unsaturated bond, Although it can select suitably according to the objective, For example, it is preferable to represent with following General formula (A-5)-(A-7).

However, in said general formula (A-5)-(A-7), R <_1> -R <_11> represents a monovalent organic group each independently. X and Y each independently represent an oxygen atom, a sulfur atom, or -NR ₄ . Z represents an oxygen atom, a sulfur atom, -NR _4, or a phenylene group. R ₄ represents a hydrogen atom or a monovalent organic group.

In said general formula (A-5), as R <_1> , respectively, a hydrogen atom, the alkyl group which may have a substituent, etc. are preferable each independently, and a hydrogen atom and a methyl group are more preferable at the point with high radical reactivity. .

As said R <_2> and R <_3> , 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, the alkyl group which may have a substituent, and may have a substituent An aryl group, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent may have An arylsulfonyl group etc. are mentioned, A hydrogen atom, a carboxyl group, an alkoxycarbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are more preferable at the point of high radical reactivity.

As said R <_4> , the alkyl group etc. which may have a substituent are preferable, for example, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are more preferable at the point with high radical reactivity. Here, as said substituent which can be introduce | transduced, 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, an alkoxycarbonyl group, sulfone, for example Aeration, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group, etc. are mentioned.

In said general formula (A-6), as R <_4> -R <_8> , 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, a substituent is mentioned, for example. Alkyl group which may have, aryl group which may have substituent, alkoxy group which may have substituent, aryloxy group which may have substituent, alkylamino group which may have substituent, arylamino group which may have substituent, and substituent A preferred alkylsulfonyl group, an arylsulfonyl group which may have a substituent, etc. are preferable, and a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are more preferable.

As said substituent which can be introduced, what was listed in the said general formula (A-5) is illustrated.

In said general formula (A-7), as R <_9> , a hydrogen atom, the alkyl group which may have a substituent, etc. are preferable, for example, and a hydrogen atom and a methyl group are more preferable at the point with high radical reactivity.

As said R <_10> , R <_11> , each independently, 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, the alkyl group which may have a substituent, a substituent An aryl group which may have, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent The arylsulfonyl group which may have etc. is preferable, A hydrogen atom, a carboxyl group, an alkoxycarbonyl group, the alkyl group which may have a substituent, and the aryl group which may have a substituent are more preferable at the point which has high radical reactivity.

Here, the thing enumerated in general formula (A-5) is illustrated as said substituent which can be introduce | transduced.

As said Z, the oxygen atom, the sulfur atom, -NR <_13> -, or the phenylene group which may have a substituent is shown. R <_13> represents the alkyl group etc. which may have a substituent, and a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable at the point with high radical reactivity.

Among the side chain ethylenically unsaturated bonds represented by the above general formulas (A-5) to (A-7), those of the general formula (A-5) have a high polymerization reactivity and a high sensitivity, which is more preferable.

Although content in the said high molecular compound of the said ethylenically unsaturated bond does not have a restriction | limiting in particular, 0.5 meq / g-3.0 meq / g are preferable, 1.0 meq / g-3.0 meq / g are more preferable, 1.5 meq / g 2.8 meq / g is especially preferable. When the said content is less than 0.5 meq / g, since there is little hardening reaction amount, it may become a reduction degree, and when more than 3.0 meq / g, storage stability may deteriorate.

Here, the said content (meq / g) can measure iodine by titration, for example.

Although there is no restriction | limiting in particular as a method of introduce | transducing the ethylenically unsaturated bond represented by the said general formula (A-5) into a side chain, For example, the high molecular compound containing a carboxyl group in a side chain, a compound which has an ethylenically unsaturated bond, and an epoxy group It can obtain by addition reaction.

The high molecular compound which contains a carboxyl group in the said side chain, for example, manufactures 1 or more types of radically polymerizable compounds containing a carboxyl group, and 1 or more types of other radically polymerizable compounds as a copolymerization component as needed by a normal radical polymerization method. As said radical polymerization method, suspension polymerization method, solution polymerization method, etc. are mentioned, for example.

Although there is no restriction | limiting in particular as a compound which has the said ethylenically unsaturated bond and an epoxy group, For example, the compound represented with the following general formula (A-8) and the compound represented with the general formula (A-9) are preferable. .

However, in said general formula (A-8), R <_1> represents a hydrogen atom or a methyl group. L ₁ represents an organic group.

However, in said general formula (A-9), R <_2> represents a hydrogen atom or a methyl group. L ₂ represents an organic group. W represents a 4-7 membered aliphatic hydrocarbon group.

Among the compounds represented by the general formula (A-8) and the compounds represented by the general formula (A-9), the compounds represented by the general formula (A-8) are preferable, and in the general formula (A-8) as well It is more preferable that L <_1> is a C1-C4 alkylene group.

Although there is no restriction | limiting in particular as a compound represented by said general formula (A-8) or a compound represented with general formula (A-9), For example, the following exemplary compounds (31)-(40) are mentioned. .

Examples of the radically polymerizable compound containing the carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxy styrene, and the like, and acrylic acid and methacrylic acid are particularly preferable. Etc. can be mentioned.

Examples of the introduction reaction into the side chain include quaternary ammonium salts such as tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride, pyridine and triphenyl. It can carry out by making it react for several hours-several hours at reaction temperature of 50 degreeC-150 degreeC in an organic solvent using phosphine etc. as a catalyst.

Although there is no restriction | limiting in particular as a structural unit which has an ethylenically unsaturated bond in the said side chain, For example, the structure represented by the following general formula (A-10), the structure represented by general formula (A-11), and these It is preferable to represent by mixing.

However, in said general formula (A-10) and general formula (A-11), Ra-Rc represents a hydrogen atom or a monovalent organic group. R ₁ represents a hydrogen atom or a methyl group. L ₁ represents an organic group which may have a linking group.

20 mol% or more is preferable, as for content in the high molecular compound of the structure represented by the said General formula (A-10)-the structure represented by General formula (A-11), 20 mol%-50 mol% are more preferable, 25 mol % -45 mol% is especially preferable. When the said content is less than 20 mol%, since there is little hardening reaction amount, it may become a reduction degree, and when more than 50 mol%, storage stability may deteriorate.

--Carboxyl group--

In the high molecular compound of this invention, in order to improve various performances, such as a non-image part removal property, you may have a carboxyl group.

The said carboxyl group can be provided to the said high molecular compound by copolymerizing the radically polymerizable compound which has an acidic group.

As an acid group which has such radically polymerizable property, a carboxylic acid, sulfonic acid, a phosphoric acid group, etc. are mentioned, for example, A carboxylic acid is especially preferable.

There is no restriction | limiting in particular as a radically polymerizable compound which has the said carboxyl group, According to the objective, it can select suitably, For example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, incrotonic acid, maleic acid, p-carboxyl Styrene etc. are mentioned, Among these, acrylic acid, methacrylic acid, and p-carboxy styrene are preferable. These may be used individually by 1 type and may use 2 or more types together.

Content in the binder of the said carboxyl group is 1.0 meq / g-4.0 meq / g, and 1.5 meq / g-3.0 meq / g are preferable. When the said content is less than 1.0 meq / g, developability may become inadequate, and when it exceeds 4.0 meq / g, it may become easy to receive the image intensity damage by alkaline water image development.

The polymer compound of the present invention is preferably copolymerized with another radical polymerizable compound in addition to the radical polymerizable compound described above for the purpose of improving various performances such as image intensity.

As said other radically polymerizable compound, the radically polymerizable compound chosen from acrylic acid ester, methacrylic acid ester, styrene, etc. are mentioned, for example.

Specifically, acrylic acid esters such as alkyl acrylate, methacrylates such as aryl acrylate, alkyl methacrylate, styrene methacrylates such as aryl methacrylate, styrene, alkyl styrene, alkoxy styrene, halogen styrene, etc. Can be mentioned.

As said acrylic ester, it is preferable that the number of carbon atoms of an alkyl group is 1-20, For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic acid -t -Octyl, chloroethyl acrylate, 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimetholpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate , Methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

As said aryl acrylate, phenyl acrylate etc. are mentioned, for example.

As said methacrylic acid ester, it is preferable that the carbon atom of an alkyl group is 1-20, 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, trimetholpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, and the like. have.

As said aryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, etc. are mentioned, for example.

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, Trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, and the like.

As said alkoxy styrene, methoxy styrene, 4-methoxy-3-methylstyrene, dimethoxy styrene, etc. are mentioned, for example.

As said halogen styrene, for example, chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromine styrene, dibrom styrene, iodine styrene, fluoro styrene, trifluoro styrene, 2-bromine-4 -Trifluoromethyl styrene, 4-fluoro-3- trifluoromethyl styrene, etc. are mentioned.

These radically polymerizable compounds may be used individually by 1 type, and may use 2 or more types together.

There is no restriction | limiting in particular as a solvent used when synthesize | combining the high molecular compound of this invention, According to the objective, it can select suitably, 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, etc. are mentioned. These may be used individually by 1 type and may mix and use 2 or more types.

10,000 or more are preferable and, as for the molecular weight of the high molecular compound of this invention, 10,000-50,000 are more preferable. When the said mass average molecular weight is less than 10,000, cured film strength may run short, and when it exceeds 50,000, developability will fall.

In addition, the high molecular compound of this invention may contain the unreacted monomer. In this case, 15 mass% or less of content in the said high molecular compound of the said monomer is preferable.

The high molecular compound which concerns on this invention may be used individually by 1 type, and may mix and use 2 or more types. Moreover, you may mix and use other high molecular compounds. In this case, 50 mass% or less is preferable and, as for content in the high molecular compound of the said invention of the said other high molecular compound, 30 mass% or less is more preferable.

The said epoxy acrylate compound is a compound which has a skeleton derived from an epoxy compound, and contains an ethylenically unsaturated double bond and a carboxyl group in a molecule | numerator. Such a compound is obtained by the method of reacting a polyfunctional epoxy compound and a carboxyl group-containing monomer, for example, and further adding polybasic acid anhydride.

As said polyfunctional epoxy compound, the heterocyclic epoxy resin ("TEPIC") which has a bixylenol type or bisphenol-type epoxy resin ("YX4000; the Japan epoxy resin company", etc.), or a mixture thereof, an isocyanurate skeleton etc. Nissan Kagaku Kogyo Co., Ltd., "Araldite PT810; product made by Chiba Specialty Chemicals", bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol no Volac type epoxy resin, cresol novolac type epoxy resin, halogenated phenol novolac type epoxy resin, glycidylamine type epoxy resin (for example, tetraglycidyl diamino diphenylmethane, etc.), hydantoin type epoxy resin, Alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenyrolethane type epoxy resin, glycidyl phthalate Yate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group containing epoxy resin ("ESN-190, ESN-360; product made by Shin-Nitetsu Kagaku Corporation", "HP-4032, EXA-4750, EXA-4700; Dainippon ink) Kagaku Kogyo Kogyo Co., Ltd.), an epoxy resin having a dicyclopentadiene skeleton ("HP-7200, HP-7200H; Dainippon Ink Kagaku Co., Ltd.", etc.); Reactant of the polyphenol compound and epichlorohydrin obtained by condensation reaction of phenol compounds, such as a phenol, o-cresol, a naphthol, and the aromatic aldehyde which has a phenolic hydroxyl group; Reactant of the polyphenol compound obtained by addition reaction of a phenol compound and diolefin compounds, such as divinylbenzene and dicyclopentadiene, and epichlorohydrin; Epoxidation of the ring-opening polymer of 4-vinylcyclohexene-1-oxide with peracetic acid or the like; Epoxy resins having heterocycles such as triglycidyl isocyanurate; Glycidyl methacrylate copolymer type epoxy resin ("CP-50S, CP-50M; product made by NOF Corporation", etc.), copolymerization epoxy resin of cyclohexyl maleimide and glycidyl methacrylate; Epoxy resin which glycidyl-etherized 1 type chosen from phenol and cresol, and p-hydroxybenzaldehyde condensate; Bis (glycidyloxyphenyl) fluorene type epoxy resin; Bis (glycidyloxyphenyl) adamantane type epoxy resin etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the carboxyl group-containing monomers include (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid monoalkyl esters, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyano cinnamic acid, and acrylic acid dimers; In addition, addition reaction products of monomers having hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and cyclic acid anhydrides such as maleic anhydride, phthalic anhydride and cyclohexanedicarboxylic anhydride; The reaction product with a halogen containing carboxylic acid compound, (omega)-carboxy- polycaprolactone mono (meth) acrylate, etc. are mentioned. Moreover, as a commercial item, NK ester CB-1 and CBX- of Aronix M-5300, M-5400, M-5500, and M-5600 by Toagosei Kagaku Kogyo Co., Ltd. make and Shin-Nakamura Kagaku Kogyo Co., Ltd. 1, HOA-MP and HOA-MS by Kyoeisha Yushi Kagaku Kogyo Co., Ltd., biscot # 2100 by Osaka Organic Kagaku Kogyo Co., Ltd., etc. can be used. These may be used individually by 1 type and may use 2 or more types together.

Moreover, as polybasic acid anhydride, for example, succinic anhydride, methyl succinic anhydride, 2,3-dimethyl succinic anhydride, 2,2-dimethyl succinic anhydride, ethyl succinic anhydride, dodecenyl succinic anhydride, nonenyl succinic anhydride, maleic anhydride , Methylmaleic anhydride, 2,3-dimethylmaleic anhydride, 2-chloromaleic anhydride, 2,3-dichloromaleic anhydride, bromomaleic anhydride, itaconic anhydride, citraconic anhydride, cisaconic acid anhydride , Phthalic anhydride, tetrahydro phthalic anhydride, tetrachloro phthalic anhydride, tetrabromo phthalic anhydride, hexahydro phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, endomethylenetetrahydro phthalic anhydride, methyl endomethylene tetrahydro anhydride Dibasic acid anhydrides, such as phthalic acid, chloric anhydride, and 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, Also polybasic acid anhydride of pyromellitic acid, pyromellitic anhydride, 3,3 ', 4,4'-benzophenone, such as non-tetracarboxylic acid can be used. These may be used individually by 1 type and may use 2 or more types together.

Epoxy acrylate is obtained by sequentially reacting each of them, but the ratio of reacting them is 0.8 to 1.2 equivalents, preferably 0.9 to 1.1 equivalents, of the carboxyl group-containing monomer relative to 1 equivalent of the epoxy group of the polyfunctional epoxy compound, and 0.1 to polybasic anhydride. It is 1.0 equivalent, Preferably it is 0.3-1.0 equivalent.

Moreover, the compound etc. which are obtained by adding an acid anhydride to the epoxy acrylate (compound which does not have a carboxyl group) which have a fluorene frame | skeleton of Unexamined-Japanese-Patent No. 5-70528 can also be used as an epoxy acrylate of this invention.

1,000-100,000 are preferable and, as for the molecular weight of the said epoxy acrylate compound, 2,000-50,000 are more preferable. When the said molecular weight is less than 1,000, the adhesiveness of the surface of a photosensitive layer may become strong, and after hardening of the photosensitive layer mentioned later, a film quality may become weak or surface hardness may deteriorate, and when it exceeds 100,000, it will develop. Sex may deteriorate. Moreover, synthesis | combination of resin also becomes difficult.

5-80 mass% is preferable, and, as for solid content in the said photosensitive resin composition of the said binder, 10-70 mass% is more preferable.

5 mass%-80 mass% are preferable, and, as for solid content in the said photosensitive resin composition of the said binder, 10 mass%-70 mass% are 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 adhesion of the surface of the photosensitive layer may deteriorate. When the content of the solid content exceeds 80% by mass, the exposure sensitivity may decrease.

[Polymerizable Compound]

There is no restriction | limiting in particular as said polymeric compound, Although it can select suitably according to the objective, The compound which has at least 1 addition polymerization group in a molecule | numerator, and whose boiling point is 100 degreeC or more at normal pressure is preferable, For example, (meth) acryl At least 1 sort (s) chosen from the monomer which has a group is mentioned preferably. In addition, in this invention, a "polymerizable compound" shall not contain the polymeric compound which may be contained in a binder.

There is no restriction | limiting in particular as a monomer which has the said (meth) acryl group, According to the objective, it can select suitably, For example, polyethyleneglycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl ( Monofunctional acrylates and monofunctional methacrylates such as meth) acrylate; Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimetholethane triacrylate, trimetholpropane triacrylate, trimetholpropane diacrylate, neopentyl glycol di (meth) Acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, Trimetholpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, trimetholol (Meth) acrylate after addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as propane, glycerin, bisphenol, etc. Teuhwa would be, Japanese Patent Publication No. 48-41708 cattle, Japanese Patent Publication No. 50-6034 cattle, urethane acrylates described in each publication such as Japanese Unexamined Patent Publication No. 51-37193 cattle and the like; Polyester acrylates described in each publication such as Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490; Polyfunctional acrylates, methacrylates, etc., such as epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid, are mentioned. Among these, trimethol propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are particularly preferable.

5 mass%-50 mass% are preferable, and, as for solid content in the said photosensitive resin composition solid content of the said polymeric compound, 10 mass%-40 mass% are more preferable. When the solid content is less than 5% by mass, problems such as deterioration of developability and a decrease in exposure sensitivity may occur. When the solid content is more than 50% by mass, the adhesiveness of the photosensitive layer may become too strong, which is not preferable.

[Photoinitiator]

An oxime derivative is used as said photoinitiator. Moreover, you may contain another photoinitiator as needed.

There is no restriction | limiting in particular as said oxime derivative, Although it can select suitably according to the objective, It is preferable that it is a compound which has an aromatic group at least, A compound which has a partial structure represented by either of following general formula (I) and general formula (II). It is more preferable that is. The said oxime derivative may use 2 or more types together.

However, in said general formula (I) and (II), Ar represents either an aromatic group or a heterocyclic group. Y ¹ represents any one of a hydrogen atom and a monovalent substituent, and Y ² represents an aliphatic group, an aromatic group, a heterocyclic group, COY ³ , CO ₂ Y ³ , or CONY ⁴ Y ⁵ . Y ³ , Y ⁴ and Y ⁵ represent any one of an aliphatic group, an aromatic group and a heterocyclic group. m represents an integer of 1 or more.

Examples of the Y ¹ is preferably any one of a hydrogen atom, an aliphatic group and an aromatic group.

Examples of Y ² include an aliphatic group, -CO- (aliphatic group), -CO- (aromatic group), -CO- (heterocyclic group), -CO _2- (aliphatic group), -CO _2- (aromatic group), and- It is preferable that it is either C0 _2- (heterocyclic group).

As said Y <^3> and Y <^4> , it is preferable that they are either an aliphatic group and an aromatic group.

The oxime derivative may be a compound in which two or more structures represented by the general formulas (I) and (II) are bonded via a linking group.

In addition, in said general formula (I) and general formula (II), the said aliphatic group represents the alkyl group, alkenyl group, and alkynyl group which may respectively have a substituent, and the said aromatic group may respectively have a substituent, the aryl group and heterocyclic ring ( Heterocyclic) group, and as the monovalent substituent, 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, and each have a substituent Good alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group is shown.

Examples of the aromatic group include those in which one to three benzene rings form a condensed ring, and those in which the benzene ring and the five-membered unsaturated ring form a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, Indenyl group, acenaphthenyl group, and fluorenyl group are mentioned, Especially, the group which has any one of a phenyl group and a naphthyl group is preferable, and the group which has a naphthyl group is especially preferable.

Moreover, these aromatic groups may have a substituent and the group which consists of monovalent nonmetallic atom groups except a hydrogen atom is mentioned as such a substituent. For example, what was shown as a substituent in the alkyl group, substituted alkyl group, or substituted alkyl group mentioned later, etc. are mentioned.

Moreover, as said heterocyclic (heterocyclic) group, a pyrrole ring group, a furan ring group, a thiophene ring group, a benzopyrrole ring group, a benzofuran ring group, a benzothiophene ring group, a pyrazole ring group, an isoxazole ring group, an isothiazole ring group, an indazole Ventilation, benzoisoxazole ring group, benzoisothiazole 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 group, pyrimidine group, pyrazine group, phthalazine group, quinazoline group, quinoxaline group, acyldine group, phenanthridine group, carbazole group, furin group, pyran group, piperidine group, pipe Razine ring group, morpholine ring, indole ring, indolidine ring, chromen ring, cinnoline ring, acridine ring group, phenothiazine ring, tetrazole ring group, triazine ring group, etc. are mentioned, Among these, furan ring group , Thiophene ring group, imidazole ring group, thiazole ring A group, a benzothiazole ring group, a pyridine ring group, an indole ring group, and an acridine ring group are especially preferable.

Moreover, these heterocyclic groups may have a substituent and the group which consists of monovalent nonmetallic atom groups except a hydrogen atom is mentioned as such a substituent. For example, what was shown as a substituent in the alkyl group, substituted alkyl group, or substituted alkyl group mentioned later is mentioned.

As said monovalent substituent, 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, the alkyl group which may have a substituent, respectively, Alkynyl group, aryl group, and heterocyclic group are preferable.

Moreover, as a monovalent substituent which consists of the said nonmetallic atom, the alkyl group, alkenyl group, alkynyl group, aryl group, and heterocyclic group which may respectively have a substituent are preferable.

Examples of the alkyl group which may have the substituent include linear, branched and cyclic alkyl groups having 1 to 20 carbon atoms, and specific examples thereof 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 And isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Among these, a linear alkyl group having 1 to 12 carbon atoms, a branched phase having 3 to 12 carbon atoms, and a cyclic alkyl group having 5 to 10 carbon atoms are more preferable.

As a substituent of the alkyl group which may have the said substituent, the substituent which consists of monovalent nonmetallic atoms except a hydrogen atom is mentioned, A preferable example is a halogen atom (-F, -Br, -Cl, -I), a hydroxyl group, an alkoxy group, Aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino 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, alkyl sulfoxy group, aryl sulfoxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N'-alkylureido group, N ', N'-dialkylureido group, N'-arylureido group, N', N'- diaryl Ureido 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 (-SO ₃ H) and its conjugated base group (referred to as sulfonate group), alkoxysulfonyl group , Aryloxysulfonyl group, sulfinamoyl group, N-alkyl sulfinamoyl group, N, N-dialkyl sulfinamoyl group, N-aryl sulfinamoyl group, N, N-diaryl sulfinamoyl group, N-alkyl-N -Arylsulfinamoyl group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-aryl Sulfamoyl group, phosphono group (-PO ₃ H ₂ ), and its conjugated base group (referred to as phosphonate group), dialkyl phosphono group (-PO ₃ (alkyl) ₂ ) "alkyl = alkyl group, hereinafter identical" , Diaryl phosphono group (-PO ₃ (aryl) ₂ ) "aryl = aryl group, the same below", alkylaryl phosphono group (-PO ₃ (alkyl) (aryl)), monoalkyl phosphono group (-PO ₃ (alkyl) and its conjugated base group (alkylphosphonate groups) ), Monoaryl phosphono group (-PO ₃ H (aryl)) and its conjugated base group (referred to as aryl phosphonate group), phosphonooxy group (-OPO ₃ H ₂ ) and its conjugated base group (phospho A dialkylphosphonooxy group (-OPO ₃ H (alkyl) ₂ ), a diarylphosphonooxy group (-OPO ₃ (aryl) ₂ ), an alkylarylphosphonooxy group (-OPO ₃₎ (alkyl) (aryl)), monoalkylphosphonooxy group (-OPO ₃ H (alkyl)) and its conjugated base group (referred to as alkylphosphonateoxy group), monoarylphosphonooxy group (-OPO ₃ H (aryl)) and its conjugated base group (referred to as arylphosphonateoxy 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 alkyl groups described above, and specific examples of the aryl group in the substituent include a phenyl group, a biphenyl group, a naphthyl group, a tolyl group, a xylyl group, a mesityl group and a cumenyl group. , Chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylamino Phenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, cyanophenyl group, sulfophenyl group, sulfonatephenyl group, phosphonophenyl group, phosph A phosphate phenyl group etc. are mentioned.

Moreover, as an example of the alkenyl group in the said substituent, a vinyl group, 1-propenyl group, 1-butenyl group, cinnammyl group, 2-chloro-1-ethenyl group, etc. are mentioned, and the alkynyl group in the said substituent is mentioned. As an example, an ethynyl group, 1-propynyl group, 1-butynyl group, trimethylsilylethynyl group, etc. are mentioned.

As a heterocyclic group in the said substituent, a pyridyl group, a piperidinyl group, etc. are mentioned, for example.

Trimethylsilyl group etc. are mentioned as a silyl group in the said substituent.

The substituent may contain an acyl group (R ⁰¹ CO-). Examples of the acyl group include those in which R ⁰¹ is a hydrogen atom, the alkyl group, or an aryl group.

As the acyl group of R ⁰¹ (R ⁰¹ CO-) may be mentioned a hydrogen atom, and the alkyl group, an aryl group. More preferred among these substituents are halogen atoms (-F, -Br, -Cl, -I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N-dialkylamino groups , Acyloxy 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- Dialkyl sulfamoyl group, N-aryl sulfamoyl group, N-alkyl-N-aryl sulfamoyl group, phosphono group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group , Alkyl phosphonate group, monoaryl phosphono group, aryl phosphonate group, phosphonooxy group, phosphonateoxy group, aryl group, alkenyl group Can be mentioned.

On the other hand, as an alkylene group in a substituted alkyl group, what was used as the divalent organic residue except any of the hydrogen atoms on the C1-C20 alkyl group mentioned above, Preferably it is C1-C12 And linear alkyl groups of 3 to 12 carbon atoms and cyclic alkylene groups of 5 to 10 carbon atoms. As a preferable specific example of the substituted alkyl group obtained by combining such a substituent and an alkylene group, a chloromethyl group, a bromomethyl group, 2-chloroethyl group, a trifluoromethyl group, a methoxymethyl group, isopropoxymethyl group, butoxymethyl group, s-butoxy Butyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, pyridylmethyl group, tetramethylpiperidinylmethyl group, N-acetyltetramethylpiperidinylmethyl 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, allyloxycar Carbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonate butyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N-tolylsulfamoylpropyl Group, N-methyl-N- (phosphonophenyl) sulfamoyl octyl group, phosphonobutyl group, phosphonate hexyl group, diethyl phosphono butyl group, diphenyl phosphono propyl group, methyl phosphono butyl group, methyl phosph Phonatebutyl group, tolylphosphonohexyl group, tolylphosphonate hexyl group, phosphonooxypropyl group, phosphonateoxy butyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenyl Ethyl group, p-methylbenzyl group, cinnamil group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl Group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. are mentioned.

Examples of the aryl group include those in which one to three benzene rings form a condensed ring, and those in which the benzene ring and the 5-membered unsaturated ring form a condensed ring, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, Indenyl group, acenaphthenyl group, and fluorenyl group are mentioned, Among these, a phenyl group and a naphthyl group are more preferable.

As said substituted aryl group, what has a group which consists of monovalent nonmetallic atom groups except a hydrogen atom as a substituent on the cyclic carbon atom of the aryl group mentioned above is used. As an example of a preferable substituent, the alkyl group mentioned above, a substituted alkyl group, and the thing shown as a substituent in the substituted alkyl group before are mentioned.

Preferable specific examples of the substituted aryl group include a 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, carboxyphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, Carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group, N-methyl-N- (sulfope Carbamoylphenyl group, sulfophenyl group, sulfonatephenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphono Phenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatephenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl group, methylphosphonophenyl group, methylphosphonatephenyl group, tolylphosphonophenyl group, tolylphosphonatephenyl group, allyl A phenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, etc. are mentioned. .

Examples of the alkenyl group, the substituted alkenyl group, the alkynyl group and the substituted alkynyl group ^{(-C (R 02) = C} (R 03) (R 04) , and ^{-C≡C (R 05)), R} 02, R ^{The group which 03} , ^R04 , R05 ^consists of monovalent nonmetallic atoms can be used.

As R ⁰² , R ⁰³ , R ⁰⁴ , and R ⁰⁵ , a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group are preferable, and examples thereof include those shown in the above examples. Among these, a hydrogen atom, a halogen atom, and a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is more preferable.

Specifically, 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, phenylethynyl group, etc. may be mentioned. .

As a heterocyclic group, the pyridyl group etc. which were illustrated as a substituent of a substituted alkyl group are mentioned.

Examples of the substituted oxy group (R ⁰⁶ O-), R ⁰⁶ a may be selected from a monovalent non-metal atom group consisting of other than hydrogen atom. Preferred substituted oxy groups include alkoxy groups, aryloxy groups, acyloxy groups, carbamoyloxy groups, N-alkylcarbamoyloxy groups, N-aryl carbamoyloxy groups, N, N-dialkylcarbamoyloxy groups, N , N-diarylcarbamoyloxy group, N-alkyl-N-arylcarbamoyloxy group, alkyl sulfoxy group, aryl sulfoxy group, phosphonooxy group, and phosphonateoxy group. Examples of the alkyl group and the aryl group in these include those described above as the alkyl group, the substituted alkyl group and the aryl group, and the substituted aryl group. In addition, 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, and a substituted aryl group. In these substituents, an alkoxy group, an aryloxy group, an acyloxy group, and an aryl sulfoxy group are more preferable. As a specific example of preferable substituted oxy group, a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, a benzyloxy group, an allyloxy group, a phenethyloxy group , Carboxyethyloxy 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, cumenyloxy group, methoxyphenyloxy group, ethoxy Phenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, phenylsulfonyloxy group, phosphonooxy group, phosphonateoxy group, etc. are mentioned.

As a substituted amino group (R ⁰⁸ NH-, (R ⁰⁹ ) (R ⁰¹⁰ ) N-) which an amide group contains, the group which R ⁰⁸ , R ⁰⁹ , R ⁰¹⁰ consists of monovalent nonmetallic atom groups except a hydrogen atom can be used. In addition, R ⁰⁹ and R ⁰¹⁰ may combine with each other to form a ring. Preferred examples of the substituted 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'- dialkyl ureido group, N'-aryl ureido group, N', N'- diaryl ureido group, N'-alkyl- N'-aryl ureido group, N-alkyl ureido group, N-aryl ureido group, N'-alkyl-N-alkyl ureido group, N'-alkyl-N-aryl ureido group, N ', N'-dialkyl- 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, aryloxycar Nylamino group, N-alkyl-N-alkoxycarbonylamino group, N-alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group is mentioned Can be. Examples of the alkyl group and aryl group in these examples include the alkyl group, the substituted alkyl group and the aryl group, and those represented by the substituted aryl group. The acyl group in the acylamino group, N-alkylacylamino group, and N-arylacylamino group (R ⁰⁷⁾ R ⁰⁷ of CO—) is as described above. Among these, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, and acylamino group are mentioned as a more preferable thing. Specific examples of the preferred substituted amino group include methylamino group, ethylamino group, diethylamino group, morpholino group, piperidino group, pyrrolidino group, phenylamino group, benzoylamino group, acetylamino group and the like.

Can be used as the R ⁰¹¹ is a group consisting of a monovalent non-metallic atomic group-substituted sulfonyl group (R ⁰¹¹ -SO _2). As a more preferable example, an alkylsulfonyl group and an arylsulfonyl group are mentioned. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned. As a specific example of such a substituted sulfonyl group, a butyl sulfonyl group, a phenyl sulfonyl group, a chlorophenyl sulfonyl group, etc. are mentioned.

Sulfonate group (-SO ₃ ^-) means a conjugated base anion group of a sulfo group (-SO ₃ H) as described above, and is usually preferably used with a counter cation. Such counter cations are generally known, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, adenium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn). ²⁺ etc.) is mentioned.

As the substituted carbonyl group (R ⁰¹³ -CO-), one in which R ⁰¹³ is made of a monovalent nonmetallic atom can be used. Preferable examples of the substituted carbonyl group include a 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, and N-alkyl-N'-arylcarbamoyl group. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, and aryl group, substituted aryl group is mentioned. Among these, more preferable substituted carbonyl groups include formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group and N-aryl Carbamoyl group is mentioned, A more preferable thing is a formyl group, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. Specific examples of the preferred substituted carbonyl group include formyl, acetyl, benzoyl, carboxyl, methoxycarbonyl, ethoxycarbonyl, allyloxycarbonyl, dimethylaminophenylethenylcarbonyl, methoxycarbonylmethoxycarbonyl and N-methylcarbamo Diary, N-phenylcarbamoyl group, N, N-diethylcarbamoyl group, morpholinocarbonyl group, etc. are mentioned.

As the substituted sulfinyl group (R ⁰¹⁴ -SO-), a group in which R ⁰¹⁴ is composed of a monovalent nonmetallic atom group can be used. Preferred examples include alkylsulfinyl groups, arylsulfinyl groups, sulfinamoyl groups, N-alkylsulfinamoyl groups, N, N-dialkylsulfinamoyl groups, N-arylsulfinamoyl groups, N, N-diarylsulfinamoyl groups, N -Alkyl-N-arylsulfinamoyl group is mentioned. As an alkyl group and an aryl group in these, what was shown as the above-mentioned alkyl group, substituted alkyl group, aryl group, and substituted aryl group is mentioned. Among these, an alkylsulfinyl group and an arylsulfinyl group are mentioned as a more preferable example. As a specific example of such a substituted sulfinyl group, hexyl sulfinyl group, benzyl sulfinyl group, tolyl sulfinyl group, etc. are mentioned.

Substituted phosphono group means that one or two of the hydroxyl groups on the phosphono group is substituted by another organic oxo group, and preferred examples thereof include the above-mentioned dialkyl phosphono group, diaryl phosphono group, alkylaryl phosphono group and monoalkyl A phosphono group and a monoaryl phosphono group are mentioned. In these, a dialkyl phosphono group and a diaryl phosphono group are more preferable. As such a specific example, a diethyl phosphono group, a dibutyl phosphono group, a diphenyl phosphono group, etc. are mentioned.

A phosphonate group _{^{(-PO 3 H 2 -, -PO}} 3 H -) is, as described above, a phosphono group (-PO ₃ H ₂₎ the foremost 1 Li or the acid-conjugated base anion group derived from the second dissociation of the it means. It is usually preferred to use it with counter cations. Such counter cations are generally known, that is, various oniums (ammonium, sulfonium, phosphonium, iodonium, adenium, etc.) and metal ions (Na ⁺ , K ⁺ , Ca ²⁺ , Zn). ²⁺ etc.) is mentioned.

Substituted phosphonate group refers to a substituted phosphono group of the above, a conjugate base anion group of what one hydroxyl group substituted with a one organic oxo, Specific examples of the above monoalkyl phosphono group _{(-PO 3 H (alkyl))} , mono And conjugated bases of arylphosphono groups (-PO ₃ H (aryl)).

As said oxime derivative, the compound represented by either of the following general formula (III) and general formula (IV) is more preferable.

However, in said general formula (III) and general formula (IV), R <_101> represents the same meaning as Y <^1> in general formula (I) and general formula (II), and Y <^12> represents general formula (I) and The same meaning as Y ² in General Formula (II).

As said R <_101> , any one of a hydrogen atom and an aliphatic group is more preferable, and the aliphatic group of 1-10 carbon atoms is especially preferable.

As said aliphatic group, a methyl group, an ethyl group, a propyl group, an octyl group, an allyl group, etc. are mentioned, for example.

As said Y <^12> , -CO- (aliphatic group) is especially preferable. As an aliphatic group in said Y <^12> , the C1-C10 aliphatic group is preferable.

Specifically, for example, methyl group, ethyl group, propyl group, butyl group, octyl group, cyclohexyl group, benzyl group and the like are preferable.

As another specific example of the said oxime derivative, the compound disclosed by Unexamined-Japanese-Patent No. 2001-233842, Unexamined-Japanese-Patent No. 2004-534797, and Unexamined-Japanese-Patent No. 2002-519732, etc., and the compound represented by the following structural formulas are mentioned, for example. Etc. can be mentioned.

In the above structural formula, R represents any one of nC ₃ H ₇ , nC ₈ H ₁₇ , camphor and p-CH ₃ C ₆ H ₄ .

In the above structural formula, R represents any one of n-C3H ₇ and p-CH ₃ C ₆ H ₄ .

As said oxime derivative, the oxime derivative represented by following General formula (5) is also used preferably.

However, in General Formula (V), Y ² and Ar represent the same meanings as those in General Formulas (I) and (II). m represents an integer of 0 or more. Y <^5> represents a substituent and when m is two or more, said Y <^5> may be the same and may differ. A represents any of 4, 5, 6, and 7-membered rings, and these rings may each contain a hetero atom.

Among the oxime derivatives represented by the general formula (V), the compound represented by the following general formula (VI) is more preferable, and the compound represented by any one of the following general formulas (VII) and (VIII) is particularly preferable.

However, in said general formula (8), Y <^2> , Y <^5> , m, and Ar represent the same meaning as the thing in general formula (V). X represents either O and S. A represents either 5 or 6 membered ring.

However, in General Formula (VII) and General Formula (VIII), Y ⁶ represents an alkyl group which may have a substituent. l represents the integer in any one of 0-6. Y <^7> represents either an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, and an acyloxy group, and when l is two or more, said Y <^7> may be the same and may differ. X and A represent the same meaning as General formula (8).

There is no restriction | limiting in particular as a substituent represented by R <^2> in the said General Formula (V) and (VIII), For example, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a sulfonyl group, an acyloxy group, a nitro group And an acylamino group. 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, although the compound represented by the following structural formula (1)-(54) is mentioned as a specific example of the oxime derivative represented by said general formula (V), it is not limited to these in this invention.

However, in said structural formula (1)-(54), Me represents a methyl group. Ph represents a phenyl group. Ac represents an acetyl group.

As for content of the said oxime derivative, 0.1-15 mass% is preferable in conversion of solid content, for example, 0.5-10 mass% is more preferable, 1.0-8.0 mass% is especially preferable. When it is less than 0.1 mass%, a sensitivity may fall, and the cured film of sufficient hardness may become difficult to be obtained, and when more than 15 mass%, not only the adhesiveness at the time of film-forming deteriorates but also Tg will become low, and a cured film It may become embrittlement.

Other photopolymerization initiators

As said other photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of the said polymeric compound, Although it can select suitably from well-known photoinitiators, For example, photosensitivity with respect to the visible light ray from an ultraviolet region is mentioned. It is preferable to have it, and may be an activator which generates an active radical by generating any action with a photoexcited sensitizer, or may be an initiator which initiates cationic polymerization depending on the kind of monomer.

The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm in wavelength. As for the said wavelength, 330 nm-500 nm are more preferable.

As said other photoinitiator, a halogenated hydrocarbon derivative (for example, having a triazine skeleton, an oxadiazole skeleton, etc.), hexaaryl biimidazole, an organic peroxide, a thio compound, a ketone compound , Acridine compounds, metallocenes and the like. Specifically, the compound of Unexamined-Japanese-Patent No. 2005-258431, etc. are mentioned. Among these, a ketone compound and an acridine compound are preferable from a viewpoint of the sensitivity of a photosensitive layer, storage property, and adhesiveness of a photosensitive layer and a board | substrate. The said other photoinitiator may be used individually by 1 type, and may use 2 or more types together.

0.1 mass%-30 mass% are preferable, as for solid content in the said photosensitive resin composition of the said photoinitiator, 0.5 mass%-20 mass% are more preferable, 0.5 mass%-15 mass% are especially preferable.

[Inorganic filler]

Since the said inorganic filler can improve the surface hardness of a permanent pattern, can suppress the linear expansion coefficient low, and can suppress the dielectric constant and dielectric loss tangent of the hardened layer itself, it is preferable for the photosensitive resin composition of this invention. Can be used.

There is no restriction | limiting in particular as said inorganic filler, It can select from a well-known thing suitably, For example, kaolin, barium sulfate, barium titanate, a silicon oxide powder, fine powder silicon oxide, vapor phase silica, amorphous silica, crystalline silica, Fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica and the like.

Less than 3 micrometers is preferable and, as for the average particle diameter of the said inorganic filler, 0.1 micrometer-2 micrometers are more preferable. When the said average particle diameter is 3 micrometers or more, resolution may deteriorate by optical fusion.

5 mass%-75 mass% are preferable, as for the addition amount of the said inorganic filler, 8 mass%-70 mass% are more preferable, 10 mass%-65 mass% are especially preferable. If the added amount is less than 5% by mass, the coefficient of linear expansion may not be sufficiently reduced. If the amount is more than 90% by mass, when the cured film is formed on the surface of the photosensitive layer, the film quality of the cured film becomes weak and a permanent pattern is used. In the case of forming wiring, the function as a protective film of the wiring may be impaired.

Moreover, it is also possible to add organic microparticles | fine-particles as needed. There is no restriction | limiting in particular as preferable organic microparticles | fine-particles, According to the objective, it can select suitably, For example, a melamine resin, benzoguanamine resin, crosslinked polystyrene resin, etc. are mentioned. Moreover, the spherical porous microparticles | fine-particles which consist of silica of about 0.1 micrometer-2 micrometer of average particle diameters, oil absorption of about 100 m <2> / g-200 m <2> / g, crosslinking resin, etc. can be used.

Since the inorganic filler contains particles having an average particle diameter of 0.1 μm to 2 μm, even when the permanent pattern is thinned to a thickness of 5 μm to 20 μm according to the thickness of the printed wiring board, both sides of the inorganic filler particles are both front and back of the permanent pattern. As a result, no ion migration occurs in the high acceleration test (HAST) and as a result, a permanent pattern excellent in heat resistance and moisture resistance can be obtained.

[Adhesion promoter]

In order to improve the adhesiveness between each layer, or the adhesiveness of a photosensitive layer and gas, a well-known so-called adhesion promoter can be used for each layer.

As said adhesion promoter, the adhesion promoter described in Unexamined-Japanese-Patent No. 5-11439, Unexamined-Japanese-Patent No. 5-341532, Unexamined-Japanese-Patent No. 6-43638, etc. are mentioned preferably, for example. Specifically, benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl -Triazole-2-thione, 3-morpholinomethyl-5-phenyl-oxadiazole-2-thione, 5-amino-3-morpholinomethyl-thiadiazole-2-thione and 2-mercapto -5-methylthio thiadiazole, triazole, tetrazole, benzotriazole, carboxy benzotriazole, amino group containing benzotriazole, a silane coupling agent, etc. are mentioned. Among these, benzotriazole and benzotriazole derivatives (for example, carboxy benzotriazole and amino group containing benzotriazole) are the most preferable.

0.001 mass%-20 mass% are preferable with respect to the whole component of the said photosensitive layer, as for content of the said adhesion promoter, 0.01 mass%-10 mass% are more preferable, 0.1 mass%-5 mass% are especially preferable.

[Thermal crosslinking agent]

There is no restriction | limiting in particular as said thermal crosslinking agent, According to the objective, in order to improve the film strength after hardening of the photosensitive layer formed using the said photosensitive film, in the range which does not adversely affect developability etc. For example, an epoxy compound having at least two oxirane groups in one molecule and an oxetane compound having at least two oxatanyl groups in one molecule can be used, and an epoxy having an oxirane group described in JP 2007-47729A. And compounds obtained by reacting a blocking agent with an isocyanate group of a compound, an epoxy compound having an alkyl group at the β-position, an oxetane compound having an oxetanyl group, a polyisocyanate compound, a polyisocyanate, and derivatives thereof.

In addition, a melamine derivative may be used as the thermal crosslinking agent. Examples of the melamine derivatives include metyrolmelamine, alkylated metyrolmelamine (compounds obtained by etherification of a methylol group with methyl, ethyl, butyl, and the like), and the like. These may be used individually by 1 type and may use 2 or more types together. Among them, alkylated methirolmelamine is preferred, and hexamethylated methirolmelamine is particularly preferable because of its good storage stability, and the effect of improving the surface hardness of the photosensitive layer or the film strength itself of the cured film.

1 mass%-50 mass% are preferable, and, as for solid content in the said photosensitive resin composition solid content of the said thermal crosslinking agent, 3 mass%-30 mass% are more preferable. When the said solid content flow rate is less than 1 mass%, the improvement of the film strength of a cured film is not recognized, and when it exceeds 50 mass%, developability and exposure sensitivity may arise.

[Other components]

As said other component, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a coloring agent (colored pigment or dye), etc. are mentioned, For example, other preparations (for example, electroconductive particle, Fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, flavoring agents, surface tension modifiers, chain transfer agents, and the like. By containing these suitably, properties, such as stability, a photographic property, and film | membrane property of the target photosensitive film, can be adjusted.

-Sensitizer-

As said photosensitive resin composition, you may contain the sensitizer.

When the said sensitizer exposes and develops the said photosensitive layer, it is used together from a viewpoint of improving the minimum energy (sensitivity) of the said light which does not change the thickness of the exposed part of the said photosensitive layer after the said exposure and image development. Particularly preferred.

As said sensitizer, it can select suitably according to the said light irradiation means (for example, visible light, an ultraviolet light, a visible light laser, etc.).

The sensitizer is excited by an active energy ray, and interacts with other substances (e.g., radical generators, acid generators, etc.) (e.g., energy transfer, electron transfer, etc.) It is possible to generate useful groups such as these.

As said sensitizer, it contains at least 1 sort (s) chosen from a cyclic compound, an aminophenyl ketone type compound, polynuclear aromatics, having an acidic nucleus, having a basic nucleus, and having a fluorescent brightener nucleus, Therefore, you may contain other sensitizers. As a sensitizer, a heterocyclic ring compound and an aminobenzo phenone type compound are preferable at the point of a sensitivity improvement, and especially a heterocyclic ring compound is preferable.

--Cyclic compound--

Among the above-mentioned compounds, a heterocyclic ring compound is preferable as the compound (cyclic ring compound) in which an aromatic ring or a heterocycle is condensed. The heterocyclic ring-based compound means a polycyclic compound having a hetero element in the ring, and preferably contains a nitrogen atom in the ring. As said heterocyclic ring-type compound, a heterocyclic ring-type ketone compound is mentioned, for example. Among the heterocyclic ring-type ketone compounds, an acridon compound and a thioxanthone compound are more preferable, and a thioxanthone compound is particularly preferable among these.

As said heterocyclic ring-type ketone compound, specifically, such as acridon, chloroacridone, N-methyl acridon, N-butyl acredon, N-butyl- chloro acredon, etc. are mentioned, for example. Cridon compounds; Thioxanthone compounds such as thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 1-chloro-4-propyloxythioxanthone and QuantacureQTX; 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-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzo Triazole-2-ylcoumarin, 7-diethylamino-4-methylcoumarin, and Japanese Patent Laid-Open No. Hei 5-19475, Japanese Patent Laid-Open No. Hei 7-271028, Japanese Patent Laid-Open 2002-363206, Japanese Patent Laid-Open Coumarins, such as the coumarin compound described in 2002-363207, Unexamined-Japanese-Patent No. 2002-363208, Unexamined-Japanese-Patent No. 2002-363209, etc .; Etc. can be mentioned.

In addition, well-known polynuclear aromatics (for example, pyrene, perylene, triphenylene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), and cyanines (for example, For example, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanine (for example, merocyanine, carbomerocyanine), thiazines (for example, thionine, methylene blue , Toluidine blue), anthraquinones (for example, anthraquinone), squaryliums (for example, squarylium), etc. are mentioned.

0.01 mass%-4 mass% are preferable with respect to the total solid of the said photosensitive resin composition, as for content of the said sensitizer, 0.02 mass%-2 mass% are more preferable, 0.05 mass%-1 mass% are especially preferable.

When the said content becomes less than 0.01 mass%, a sensitivity may fall, and when it exceeds 4 mass%, the shape of a pattern may deteriorate.

The mass ratio of the content of the sensitizer and the photopolymerization initiator in the photosensitive resin composition is preferably [(sensitizer) / (oxime derivative)] = 1 / 0.1 to 1/100, preferably 1/1 to 1/50 It is more preferable that is.

When mass ratio of content of the said sensitizer and content of the said photoinitiator is out of the said range, a sensitivity may fall and the aging change of a sensitivity may worsen.

Thermal polymerization inhibitor

You may add the said thermal polymerization inhibitor in order to prevent thermal superposition | polymerization or time-lapse superposition | polymerization of the said polymeric compound in the said photosensitive layer.

Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, and 4-methoxy-2- Hydroxybenzophenone, cuprous chloride, phenothiazine, chloranyl, naphthylamine, β-naphthol, 2,6-di-t-butyl-4-cresol, 2,2'-methylenebis (4-methyl- 6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate and phenothiazine, nitroso compound, nitroso compound and Al Chelates; and the like.

0.001 mass%-5 mass% are preferable with respect to the said polymeric compound, 0.005 mass%-2 mass% are more preferable, and, as for content of the said thermal polymerization inhibitor, 0.01 mass%-1 mass% are especially preferable.

When the said content is less than 0.001 mass%, stability at the time of storage may fall, and when it exceeds 5 mass%, the sensitivity with respect to an active energy ray may fall.

Plasticizer

The plasticizer may be added in order to control the film properties (flexibility) of the photosensitive layer.

Examples of the plasticizer include dimethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, diisodecyl phthalate, and diphenyl phthalate. Phthalic acid esters such as diallyl phthalate and octyl capryl phthalate; Glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, dimethyl glycophthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, and triethylene glycol dicaprylic acid ester ; Phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate; Amides such as 4-toluenesulfonamide, benzenesulfonamide, N-n-butylbenzenesulfonamide and N-n-butylacetamide; Aliphatic dibasic acid esters such as diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dibutyl sebacate, dioctyl sebacate, dioctyl azelate and dibutyl maleate; Glycols such as polyethylene glycol and polypropylene glycol, such as triethyl citrate, tributyl citrate, glycerin triacetyl ester, butyl laurate, and 4,5-diepoxycyclohexane-1,2-dicarboxylic acid dioctyl Can be mentioned.

0.1 mass%-50 mass% are preferable with respect to the all components of the said photosensitive resin composition, as for content of the said plasticizer, 0.5 mass%-40 mass% are more preferable, 1 mass%-30 mass% are especially preferable.

-Pigmentation Pigment-

There is no restriction | limiting in particular as said coloring pigment, According to the objective, it can select suitably, For example, Victoria pure blue BO (CI42595), Oramine (CI41000), Fat black HB (CI26150), Monolight yellow GT (CI pigment yellow 12), permanent yellow GR (CI pigment yellow 17), permanent yellow HR (CI pigment yellow 83), permanent carmine FBB (CI pigment red 146), host balm red ESB (CI pigment Violet 19), Permanent Ruby FBH (CI Pigment Red 11), Pastel Pink B Splicer (CI Pigment Red 81), Monastral First Blue (CI Pigment Blue 15), Monolight First Black B (CI Pigment Black) 1), carbon, CI pigment red 97, CI pigment red 122, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 177, CI Pigment Red 180, CI Pigment Red 192, CI Pigment Red 215, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Blue 15: 1, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 22, CI Pigment Blue 60, CI Pigment Blue 64 and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, the dye suitably selected from well-known dye can be used as needed.

The solid content in the photosensitive resin composition of the colored pigment can be determined in consideration of the exposure sensitivity, resolution, and the like of the photosensitive layer at the time of forming the permanent pattern, and varies depending on the type of the colored pigment, but is generally 0.01% by mass to 10 Mass% is preferable and 0.05 mass%-5 mass% are more preferable.

(2) photosensitive film

In the photosensitive film of this invention, the photosensitive layer which consists of a photosensitive resin composition is laminated | stacked on the support body. 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, The said PC layer on the said support body The form which has the said photosensitive layer and the said protective layer in this order, the form which has the said cushion layer, the said PC layer, the said photosensitive layer, and the said protective layer in this order on the said support body, etc. are mentioned. 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 formed in the said photosensitive film of the said photosensitive layer, Although it can select suitably according to the objective, Usually, it is laminated | stacked on the said support body.

The photosensitive layer is modulated with light from the light irradiation means by the light modulating means having n drawing portions that receive and emit light from the light irradiation means in the exposure step to be described later. It is preferable to be exposed to light having passed through a microlens array in which microlenses having aspherical surfaces capable of correcting aberrations due to distortion of the exit face of?

When exposing and developing the said photosensitive layer, it is preferable that the minimum energy of the light used for the said exposure which does not change the thickness of the exposed part of the said photosensitive layer after the said exposure and image development is 100 mJ / cm <2> or less, and 70 mJ / It is more preferable that it is 2 cm <2> or less. When the minimum energy of the light used for the exposure exceeds 100 mJ / cm 2, the tact time becomes long, which is not preferable.

Here, "the minimum energy of the light used for the said exposure which does not change the thickness of the exposed part of the said photosensitive layer after the said exposure and image development" is what is called image development sensitivity, For example, the said at the time of exposing the said photosensitive layer It can obtain | require from the graph (sensitivity curve) which shows the relationship between the energy amount (exposure amount) of the light used for exposure, and the thickness of the said hardened layer produced | generated by the said developing process following the said exposure.

The thickness of the cured layer increases as the exposure amount increases, and thereafter, becomes substantially the same as and roughly constant with the thickness of the photosensitive layer before the exposure. The said developing sensitivity is a value calculated | required by reading the minimum exposure amount when the thickness of the said hardened layer becomes substantially constant.

Here, when the thickness of the said hardened layer and the thickness of the said photosensitive layer before the said exposure are within +/- 1micrometer, it is considered that the thickness of the said hardened layer is not changed by exposure and image development.

There is no restriction | limiting in particular as a measuring method of the thickness of the said hardened layer and the said photosensitive layer before the said exposure, Although it can select suitably according to the objective, A film thickness measuring apparatus and a surface roughness measuring instrument (for example, Surfcom 1400D (Tokyo Seimitsu) Company)) etc., and the method of measuring is mentioned.

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 a formation method of the said photosensitive layer, the photosensitive resin composition of this invention is melt | dissolved, emulsified, or disperse | distributed in water or a solvent on the said support body, the photosensitive resin composition solution is prepared, and the said solution is apply | coated directly and dried and laminated | stacked. Can be mentioned.

There is no restriction | limiting in particular as a solvent of the said photosensitive resin composition solution, According to the objective, it can select suitably, For example, Alcohol, such as methanol, ethanol, normal-propanol, isopropanol, normal-butanol, secondary butanol, and normal-hexanol ; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diisobutyl ketone; Esters such as ethyl acetate, butyl acetate, acetate-normal-amyl, methyl sulfate, ethyl propionate, dimethyl phthalate, ethyl benzoate and methoxypropyl acetate; Aromatic hydrocarbons such as toluene, xylene, benzene and ethylbenzene; Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride and monochlorobenzene; Ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and 1-methoxy-2-propanol; Dimethylformamide, dimethylacetamide, dimethyl sulfooxide, sulfolane and the like. These may be used individually by 1 type and may use 2 or more types together. Moreover, you may add a well-known surfactant.

There is no restriction | limiting in particular as said coating method, According to the objective, it can select suitably, For example, apply | coating directly to the said support body using a spin coater, a slit spin coater, a roll coater, a die coater, a curtain coater, etc. The method can be mentioned.

As said drying conditions, although it changes also with each component, a kind of solvent, a use ratio, etc., it is about 30 to 15 minutes normally at the temperature of 60 degreeC-110 degreeC.

In this invention, the said photosensitive layer is formed of the photosensitive resin composition containing a binder, a polymeric compound, a photoinitiator, an inorganic filler, an adhesion promoter, and other components as needed.

There is no restriction | limiting in particular as said support body, Although it can select suitably according to the objective, it is preferable that the said photosensitive layer can be peeled off, and that light transmittance is favorable, and that surface smoothness is more preferable.

The support is made of synthetic resin and is preferably transparent. For example, polyethylene terephthalate, polyethylene naphthalate, polypropylene, polyethylene, cellulose acetate, cellulose diacetate, poly (meth) acrylic acid alkyl ester, poly ( Meta) acrylic acid ester copolymer, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide, polyimide, vinyl chloride vinyl acetate copolymer, polytetrafluoroethylene, poly Various plastic films, such as a trifluoroethylene, a cellulose film, and a nylon film, are mentioned, Among these, polyethylene terephthalate is especially preferable. These may be used individually by 1 type and may use 2 or more types together.

Although the thickness of the said support body does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 2 micrometers-150 micrometers are preferable, 5 micrometers-100 micrometers are more preferable, 8 micrometers-50 micrometers are especially preferable. Do. 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, 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 length 10m-20,000m is mentioned.

The said photosensitive film may form a protective layer on the said photosensitive layer.

As said protective layer, what is used for the said support | support, paper, polyethylene, the paper laminated | stacked polypropylene, etc. are mentioned, for example, Among these, a polyethylene film and a polypropylene film are preferable.

Although the thickness of the said protective layer does not have a restriction | limiting in particular, According to the objective, it can select suitably, For example, 5 micrometers-100 micrometers are preferable, 8 micrometers-50 micrometers are more preferable, 10 micrometers-30 micrometers are especially desirable.

As the combination (support / protective layer) of the support and the protective layer, for example, polyethylene terephthalate / polypropylene, polyethylene terephthalate / polyethylene, polyvinyl chloride / cellophane, polyimide / polypropylene, polyethylene terephthalate / polyethylene tere Phthalate etc. are mentioned. Moreover, the interlayer adhesive force can be adjusted by surface-treating at least one of a support body and a protective layer. The surface treatment of the support may be carried out in order to increase the adhesive strength with the photosensitive layer. For example, coating of the primer layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency irradiation treatment, glow discharge irradiation treatment, active Plasma irradiation treatment, laser beam irradiation treatment, and the like.

Moreover, 0.3-1.4 are preferable and, as for the static friction coefficient of the said support body and the said protective layer, 0.5-1.2 are more preferable.

When the said static friction coefficient is less than 0.3, winding shift may generate | occur | produce in the case of making it into roll shape, when it is too slippery, and when it exceeds 1.4, it may become difficult to wind up to a favorable roll shape.

It is preferable that the said photosensitive film is wound up by the cylindrical core and is long, it is wound in roll shape, and is stored. There is no restriction | limiting in particular in the length of the said elongate photosensitive film, For example, it can select suitably in the range of 10m-20,000m. In addition, the slit may be processed so that the user can easily write, and the long body in the range of 100 m to 1,000 m may be rolled. In this case, the support is preferably wound up to the outermost side. Moreover, you may slit the said roll-shaped photosensitive film in a sheet form. In storage, from the viewpoint of protecting the end face and preventing edge fusion, it is preferable to provide a separator (particularly moisture-proof and containing a desiccant) on the end face, and to use a material having low packing moisture permeability.

The protective layer may be surface treated in order to adjust the adhesion between the protective layer and the photosensitive layer. The surface treatment, for example, forms a primer layer made of a polymer such as polyorganosiloxane, fluorinated polyolefin, polyfluoroethylene, polyvinyl alcohol, etc. on the surface of the protective layer. Formation of the said primer layer can be formed by apply | coating the coating liquid of the said polymer on the surface of the said protective layer, and drying at 30 degreeC-150 degreeC for 1 minute-30 minutes. As for the temperature at the time of the said drying, 50 degreeC-120 degreeC is especially preferable.

There is no restriction | limiting in particular as another layer in the said photosensitive film, According to the objective, it can select suitably, For example, a cushion layer, an oxygen barrier layer (PC layer), a peeling layer, an adhesive layer, a light absorption layer, a surface protective layer You may have a layer, such as a back. You may have these layers individually by 1 type, and may have 2 or more types. Moreover, you may have a protective layer on the said photosensitive layer.

[Production Method of Photosensitive Film]

The said photosensitive film can be manufactured as follows, for example.

First, the material contained in the said photosensitive resin composition is melt | dissolved, emulsified, or disperse | distributed in water or a solvent, and the photosensitive resin composition solution for photosensitive films is prepared.

As said solvent, the same thing as the solvent of the said photosensitive resin composition solution is mentioned.

Next, the said photosensitive resin composition solution is apply | coated on the said support body, it can be dried, a photosensitive layer can be formed, and a photosensitive film can be manufactured.

The method mentioned above is mentioned as a coating method of the said photosensitive resin composition solution.

Since the said photosensitive film of this invention uses the said photosensitive resin composition, it is excellent in gold resistance, sensitivity, developability, and adhesiveness, and is suitable for forming various patterns, such as permanent patterns, such as a protective film, an interlayer insulation film, and a soldering resist pattern, and a color filter. Can be suitably used for the production of liquid crystal structural members such as pillars, ribs, spacers, partitions, for forming patterns such as holograms, micromachines, proofs, and the like. have.

In particular, since the photosensitive film of the present invention has a uniform thickness, the ion migration is performed in the high acceleration test (HAST) even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned in the formation of the permanent pattern. Since a high-precision permanent pattern excellent in heat resistance and moisture resistance is obtained, the lamination to the base material is carried out more precisely.

(Photosensitive laminated body)

The said photosensitive laminated body has at least the said photosensitive layer on a base material, and is laminated | stacked by the other layer suitably selected according to the objective.

<Gas>

The substrate is a target substrate on which the photosensitive layer is formed, or a transfer body to which at least the photosensitive layer of the photosensitive film of the present invention is transferred, and there is no particular limitation, and the base can be appropriately selected according to the purpose, for example, surface smoothness. It can select arbitrarily from this high thing to the thing with the uneven surface. Plate-like gases are preferred, and so-called substrates are used. Specifically, the board | substrate (print board | substrate) for manufacturing a well-known printed wiring board, a glass plate (such as a soda glass plate), a synthetic resin film, paper, a metal plate, etc. are mentioned.

[Manufacturing Method of Photosensitive Laminate]

As a manufacturing method of the said photosensitive laminated body, the method of apply | coating the said photosensitive resin composition to the surface of the said base material as a 1st aspect, and drying is mentioned, As a 2nd aspect, at least the photosensitive layer in the photosensitive film of this invention is heated. And a method of transferring and laminating while performing at least one of pressurization.

The manufacturing method of the photosensitive laminated body of a said 1st aspect apply | coats and dries the said photosensitive resin composition on the said base | substrate, and forms a photosensitive layer.

There is no restriction | limiting in particular as said coating and drying method, According to the objective, it can select suitably, For example, the photosensitive resin composition solution is made to melt | dissolve, emulsify, or disperse | distribute the said photosensitive resin composition in water or a solvent in the surface of the said base | substrate. The method of preparing, laminating | stacking by applying the said solution directly and drying is mentioned.

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

The manufacturing method of the photosensitive laminated body of a said 2nd aspect is laminated | stacked on the surface of the said base | substrate, performing at least any one of heating and pressurization of the photosensitive film of this invention. Moreover, when the said photosensitive film has the said protective layer, it is preferable to peel off the said protective layer, and to laminate | stack so that the said photosensitive layer may be piled up on 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 pressure of the said pressurization, 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 one of the said heating, According to the objective, it can select suitably, For example, a laminator (for example, VP-II by Onari Laminator Co., Ltd. and VP130 by Nichigo Moton Co., Ltd. make). ) And the like can be mentioned as appropriate.

The photosensitive film and the photosensitive laminate of the present invention have good sensitivity, developability and adhesion in order to use the photosensitive resin composition of the present invention, and can efficiently form a high-definition permanent pattern, and include a protective film, an interlayer insulating film, and a solder. It can be suitably used for forming various patterns such as permanent patterns such as resist patterns, for producing liquid crystal structural members such as color filters, pillars, ribs, spacers, partition walls, for forming patterns such as holograms, micro machines, and proofs, and the like. In particular, it can use suitably for the permanent pattern formation of a printed board.

In particular, since the photosensitive film of the present invention has a uniform thickness, in the formation of a permanent pattern, even when the permanent pattern (protective film, interlayer insulating film, solder resist, etc.) is thinned, generation of ion migration occurs in the high accelerated life test (HAST). There is no, and a high-definition permanent pattern excellent in heat resistance and moisture resistance is obtained, so that the lamination to the substrate is performed in more detail.

(3) pattern forming apparatus and pattern forming method

The pattern forming apparatus of the present invention includes the photosensitive laminate, and includes at least light irradiation means and light modulating means.

The pattern formation method of this invention contains an exposure process at least and includes other processes, such as a image development process suitably selected.

In addition, the pattern forming apparatus of the present invention is revealed through the description of the pattern forming method of the present invention.

[Exposure process]

The said exposure process is a process of exposing to the photosensitive layer of this invention. The material of the photosensitive layer and base of the present invention is as described above.

There is no restriction | limiting in particular as long as it is the said photosensitive layer as an object of the said exposure, Although it can select suitably according to the objective, For example, as above-mentioned, carrying out at least any one of heating and pressurizing a photosensitive resin composition on a base material. It is preferable to carry out with respect to the photosensitive layer in the photosensitive laminated body formed by laminating | stacking.

There is no restriction | limiting in particular as said exposure, According to the objective, it can select suitably, Although digital exposure, an analog exposure, etc. are mentioned, Digital exposure is preferable among these.

There is no restriction | limiting in particular as said analogue exposure, According to the objective, it can select suitably, For example, the method of exposing with a (ultra) high pressure mercury lamp, a xenon lamp, a halogen lamp etc. through the photomask which has a predetermined pattern is mentioned. Can be.

There is no restriction | limiting in particular if it carries out without using the said photo mask as said digital exposure, Although it can select suitably according to the objective, For example, the exposure head provided with at least the light irradiation means and the light modulation means, and at least among the said photosensitive layer It is preferable to irradiate the light emitted from the light irradiating means with respect to the photosensitive layer while moving either from the exposure head while modulating in accordance with the pattern information by the light modulating means.

The light source used in the digital exposure is not particularly limited as long as it is a light source that generates near-infrared light 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 Although well-known light sources, such as a fluorescent tube for copiers or laser beams, are used, Among these, a (ultra) high pressure mercury lamp and a laser beam are preferable, and a laser beam is more preferable.

The ultra-high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube or the like, and the luminous efficiency of the mercury is increased by setting the vapor pressure of mercury high. Among the linear spectrums, a linear spectrum of only one wavelength may be used using an ND filter or the like, or light rays having a plurality of linear spectrums may be used.

The "laser" of the laser beam is an acronym for Light Amplification by Stimulated Emission of Radiation. As the apparatus for generating the laser light, an oscillator and an amplifier suitable for producing monochromatic light having a higher coherence and directivity by amplification and oscillation of light waves using the phenomenon of induced emission occurring in a material having an inversion distribution are suitable.

Examples of the excitation medium for the laser beam include crystals, glass, liquids, pigments, and gases, and known lasers such as solid lasers, liquid lasers, gas lasers, and semiconductor lasers can be used from these media.

Specifically, Ar ion laser (364 nm, 351 nm), Kr ion laser (356 nm, 351 nm), He-Cd laser (325 nm) are mentioned as gas laser, YAG laser, YVO ₄ laser (1,064 nm) as a solid-state laser ), Double wave (532nm), triple wave (355nm), quadruple wave (266nm) of YAG laser or YVO ₄ laser, combination of waveguide wavelength conversion element and AlGaAs and InGaAs semiconductor (380nm to 400nm), waveguide wave conversion element And AlGaInP or AlGaAs semiconductor t (300 nm to 350 nm), AlGaInN (350 nm to 470 nm), and the like. Among them, suitable laser light includes a 355 nm laser whose AlGaInN semiconductor laser (commercially available InGaN-based semiconductor laser 375 nm or 405 nm) has high power in terms of productivity.

For example, the wavelength of the laser beam is preferably 200 nm to 1,500 nm, more preferably 300 nm to 800 nm, still more preferably 330 nm to 500 nm, and particularly preferably 350 nm to 420 nm.

Light modulation means

As said optical modulation means, the method which has n drawing parts and controls the drawing part according to the said pattern information is mentioned as a typical method. Specifically, a digital micromirror device (DMD), a spatial light modulator (SLM) of MEMS (Micro Electro Mechanical Systems) type, an optical element (PLZT element) that modulates transmitted light by an electro-optic effect, and a liquid crystal Optical shutters (FLC) and the like, and among these, DMD can be mentioned suitably.

When the DMD is used, the light from the light source is irradiated onto the DMD by a suitable optical system, and the light spots reflected from each mirror arranged in two dimensions on the DMD in two dimensions on the photosensitive layer via another optical system or the like. Form the phase of. In this state, the light spot and the light spot are not exposed, but when the image of the light spot arranged in two dimensions is moved in a slightly inclined direction with respect to the two-dimensional array direction, the light spot of the rear row is exposed between the light spot of the first row and the light spot. By doing so, the entire surface of the photosensitive layer can be exposed. The DMD may form an image pattern by controlling the angle of each mirror and controlling the light spot on-off. By arranging and using the exposure head which has the said DMD, it can respond to the board | substrate of various widths.

In the DMD, the brightness of the light spot is only two gray scales of ON and OFF, but exposure of 256 gray scales can be performed by using a mirror gray scale spatial modulation element.

The light modulating means preferably has pattern signal generating means for generating a control signal based on the pattern information to be formed. In this case, the light modulating means modulates light in accordance with the control signal generated by the pattern signal generating means.

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, as another typical method of the light modulating means, a method of using a polygon mirror is mentioned. Here, a polygon mirror is a rotating member having a series of plane reflective surfaces around it. In the polygon mirror, the light from the light source is reflected and irradiated onto the photosensitive layer, but the light spot of the reflected light is scanned by the rotation of the plane mirror. The entire surface of the photosensitive layer on the substrate can be exposed by moving the substrate at right angles to the scanning direction. And an image pattern can be formed by controlling the intensity of the light from a light source in ON-OFF or halftone by a suitable method. At this time, scanning time can be shortened by making multiple light from a light source.

As the light modulating means of the present invention, in addition, an example of drawing using the polygon mirror described in JP-A-5-150175, the lower layer described in JP-A-2004-523101 (Patent No. 2002/039793 pamphlet) Example of visually acquiring a part of an image of an image, and exposing the position of the upper layer to the position of the lower layer with a device using a polygon mirror, exposing with the DMD described in Japanese Patent Laid-Open No. 2004-56080, Japanese Patent Publication 2002-523905 Exposure apparatus with polygon mirror as described in Japanese Unexamined Patent Document, exposure apparatus with polygon mirror as described in Japanese Unexamined Patent Publication No. 2001-255661, combination example of DMD, LD, and multiple exposure described in Japanese Patent Laid-Open No. 2003-50469; Example of exposure method which changes exposure amount according to the site | part of board | substrate of 2003-156853, the position shift adjustment of Unexamined-Japanese-Patent No. 2005-43576 Examples of the exposure method for performing the step may be cited.

Light irradiation means

There is no restriction | limiting in particular as said light irradiation means, ie, the irradiation method of light, Although the above-mentioned exposure light source can be selected suitably according to the objective, it is suitable to synthesize | combine and irradiate two or more lights from these light sources, and it is 2 or more It is especially suitable to irradiate laser light (synthesis laser light) which synthesize | combined light.

There is no restriction | limiting in particular as a irradiation method of the said harmonic laser beam, Although it can select suitably according to the objective, The laser beam irradiated from a some laser light source, a multimode optical fiber, and the said several laser light source is condensed, and it is made to the said multimode optical fiber. The method of constructing and irradiating a haptic laser beam by the aggregation optical system to combine is mentioned suitably.

The beam diameter of the laser beam is not particularly limited and may be appropriately selected according to the purpose. However, from the viewpoint of the resolution of the deep color separation wall, 5 µm to 30 µm is preferable as the 1 / e ² value of the Gaussian beam, and 7 µm to 20 µm. Is more preferable.

In the present invention, it is preferable to modulate the laser light according to the image data. Therefore, it is preferable to use the above DMD which is a spatial light modulator for this purpose.

As an exposure apparatus which has the said light modulation means and the said light irradiation means, it is described in Unexamined-Japanese-Patent No. 2005-222039, Unexamined-Japanese-Patent No. 2005-258431, Unexamined-Japanese-Patent No. 2006-30966, etc., for example. Although the apparatus can be used, the exposure apparatus in this invention is not limited to this.

[Developing process]

The development is performed by removing the unexposed portion of the photosensitive layer.

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

There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, For example, an alkaline aqueous solution, an aqueous developing solution, an organic solvent, etc. are mentioned, Among these, a weakly alkaline aqueous solution is preferable. As a base component of the weak alkaline aqueous solution, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, pyrroline acid Sodium, potassium pyrrolate, borax and the like.

For example, the pH of the weakly alkaline aqueous solution is preferably about 8 to 12, and more preferably about 9 to 11. As said weakly alkaline aqueous solution, 0.1 mass%-5 mass% of sodium carbonate aqueous solution or potassium carbonate aqueous solution, etc. are mentioned, for example.

Although the temperature of the said developing solution can be suitably selected according to the developability of the said photosensitive layer, about 25 degreeC-40 degreeC is preferable, for example.

The developer may be a surfactant, an antifoaming agent, an organic base (for example, ethylenediamine, ethanolamine, tetramethylammonium hydroxide, diethylenetriamine, triethylenepentamine, morpholine, triethanolamine, etc.), or development. In order to make it, it may use together with an organic solvent (for example, alcohol, ketones, ester, ether, amide, lactone, etc.). The developer may be an aqueous developer in which water or an aqueous alkali solution and an organic solvent are mixed, or may be an organic solvent alone.

In formation of the said pattern, the hardening process process, an etching process, a plating process, etc. may be included, for example. These may be used individually by 1 type and may use 2 or more types together.

Curing Treatment Step

The pattern forming method is a permanent pattern such as a protective film, an interlayer insulating film, a solder resist pattern, or a permanent pattern forming method for forming a color filter, and a curing treatment step of performing a curing treatment on the photosensitive layer after the developing step. It is preferable to provide.

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

As a method of the said front surface exposure process, the method of exposing the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development is mentioned, for example. Hardening of resin in the photosensitive resin composition which forms the said photosensitive layer by the said front surface exposure is accelerated | stimulated, and the surface of the said permanent pattern is hardened.

There is no restriction | limiting in particular as an apparatus which performs the said front surface exposure, Although it can select suitably according to the objective, For example, the UV exposure machine, such as an ultrahigh pressure mercury lamp, the exposure machine using a xenon lamp, a laser exposure machine, etc. are mentioned suitably. The exposure amount is usually 10 mJ / cm 2 to 2,000 mJ / cm 2.

As a method of the said front surface heat processing, the method of heating the whole surface on the said laminated body in which the said permanent pattern was formed after the said image development is mentioned. The film strength of the surface of the permanent pattern is improved by the front heating.

120 degreeC-250 degreeC is preferable, and, as for the heating temperature in the said front surface heating, 120 degreeC-200 degreeC is more preferable. When the said heating temperature is less than 120 degreeC, the improvement of the film strength by heat processing may not be obtained, and when it exceeds 250 degreeC, decomposition | disassembly of resin in the said photosensitive resin composition may arise, and film | membrane quality may become weak.

10 minutes-120 minutes are preferable, and, as for the heat time in the said front heating, 15 minutes-60 minutes are more preferable.

There is no restriction | limiting in particular as an apparatus which performs said whole surface heating, It can select suitably from a well-known apparatus according to the objective, For example, a dry oven, a hotplate, an IR heater, etc. are mentioned.

The pattern formation method can be used for the formation of various patterns that require the prevention of deterioration of the sensitivity of the photosensitive layer by oxygen in direct drawing by laser exposure at 405 nm, and for the formation of a pattern having both high density and high productivity. It can use suitably.

In the permanent pattern forming method, if the permanent pattern formed by the permanent pattern forming method is the protective film or the interlayer insulating film, wiring can be protected by an impact or bending from the outside, and in particular, in the case of the interlayer insulating film, For example, it is useful for high density mounting of a semiconductor and components in a multilayer wiring board, a buildup wiring board, etc.

The method for forming a permanent pattern of the present invention is for forming various patterns such as a permanent pattern such as a protective film, an interlayer insulating film and a solder resist pattern in order to use the photosensitive resin composition of the present invention, a color filter, a pillar material, a rib material, and a spacer. It can be used suitably for manufacture of liquid crystal structural members, such as a partition and a hologram, a micromachine, a proof, etc., and can use especially for formation of the permanent pattern of a printed circuit board.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example, unless the acclaim is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

Example 1

Production of Photosensitive Film

The photosensitive resin composition solution which consists of the following composition was apply | coated and dried on the polyethylene terephthalate film (16FB50 by Toray Industries, Ltd.) of thickness 16micrometer as a support body, and the photosensitive layer of thickness 30micrometer was formed on the said support body. A photosensitive film was prepared by laminating a polypropylene film (Al-O E To 200, manufactured by Oshi Tokushu Co., Ltd.) having a thickness of 20 μm as a protective layer on the photosensitive layer.

Composition of <photosensitive resin composition solution>

Solution of Binder 1 100 parts by mass

Dipentaerythritol hexaacrylate... 13 parts by mass

Photoinitiator represented by the following Formula I-1. 5.0 parts by mass

Sensitizer represented by the following formula S-1: 0.8 parts by mass

Efototo YD-8125 (epoxy equivalence 170 g / eq. Made by Toto Kasei Co., Ltd., bisphenol A epoxy resin)... 8 parts by mass

Dicyandiamide ... 0.5 parts by mass

Pigment Dispersion ... 80.21 parts by mass

Mega Pack F-780F (made by Dainippon Ink Co., Ltd.) 30 mass%

Methyl ethyl ketone solution. 0.2 parts by mass

Methyl ethyl ketone 12 parts by mass

1,2,3-benzotriazole. 1.0 parts by mass

In addition, the said pigment dispersion liquid is 30 mass parts of barium sulfate (made by Sakai Kagaku Co., Ltd., B30), 50 mass parts of solutions of the said binder 1, 0.07 mass part of phthalocyanine blue, and anthraquinone type yellow pigment (PY24) 0.04 After mixing a mass part beforehand, it disperse | distributed and prepared for 3 hours at circumferential speed of 9 m / s using zirconia beads of diameter 1.0mm with motor mill M-250 (made by the company).

Synthesis Example 1 Synthesis of Binder 1

159 g of 1-methoxy-2-propanol was put into a 1,000 mL three neck flask, and it heated to 85 degreeC under nitrogen stream. 63.4 g of benzyl methacrylate, 72.3 g of methacrylic acid, and 4.15 g of V-601 (manufactured by Wako Pure Chemical) were added dropwise over 2 hours to 1-methoxy-2-propanol. After completion of the dropwise addition, the mixture was heated and reacted for another 5 hours. Next, heating was stopped and the copolymer of benzyl methacrylate / methacrylic acid (30/70 mol% ratio) was obtained.

Next, 120.0 g of the copolymer solution was transferred to a 300 mL three-neck flask, and 16.6 g of glycidyl methacrylate and 0.16 g of p-methoxyphenol were added and stirred to dissolve. After dissolution, 3.0 g of triphenylphosphine was added, followed by heating to 100 ° C. for addition reaction. It was confirmed by gas chromatography that glycidyl methacrylate disappeared, and heating was stopped. 38 g of 1-methoxy-2-propanol were added to prepare a solution of Binder 1 having an acid value of 112 mgKOH / g, a mass average molecular weight of 15,000, and a solid content of 30 mass%.

Lamination to gas

As the base, a chemical polishing treatment was performed on the surface of a copper clad laminate (without through hole and copper thickness of 12 µm) to prepare. On the copper clad laminate, the photosensitive layer of the photosensitive film is brought into contact with the copper clad laminate, and the protective film in the photosensitive film is peeled off and laminated using a vacuum laminator (manufactured by Nichigo Motor Co., Ltd., VP130). The laminated body in which the said copper clad laminated board, the said photosensitive layer, and the said polyethylene terephthalate film (support) were laminated | stacked in this order was prepared.

The crimping conditions were 40 seconds of vacuum processing time, 70 degreeC of crimping temperature, 0.2MPa of crimping pressure, and 10 second of pressurization time.

About the said laminated body, the sensitivity was evaluated as follows.

The laminate was allowed to stand at room temperature (23 ° C, 55% RH) for 10 minutes. 0.5 mJ / cm 2 of pattern data of L / S (line / space) = 50 μm / 50 μm was used for INPREX IP-3000 (manufactured by Fujifilm, pixel pitch = 1.0 μm) on the surface of the obtained laminate. Light energy amounts of up to 500 mJ / cm 2 at different intervals of 2 ^1/2 times were irradiated and exposed, and the line pattern of L / S (line / space) = 50 micrometers / 50 micrometers was hardened. 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 at 0.15 MPa on the entire surface of the photosensitive layer on the copper clad laminate at 2-3 times the shortest developing time. Spray development was carried out for a time (or 40 to 60 seconds), and the uncured area was dissolved and removed. The line width of the pattern of L = 50 micrometers obtained in this way was measured using the laser microscope (VK-9500, Gence Corporation; objective lens 50 times), and the exposure amount which a line width becomes 50 micrometers was made into the sensitivity (optimal exposure amount).

Development and hardening treatment

The polyethylene terephthalate film (support) was peeled from the said laminated body, the 1 mass% sodium carbonate aqueous solution of 30 degreeC was sprayed at the pressure of 0.15 Mpa for 60 second, and the uncured area | region was melt | dissolved and removed on the whole surface of the said photosensitive layer. Thereafter, the mixture was washed with water and dried to form a permanent pattern.

About the said permanent pattern, plating resistance was evaluated as follows.

The cured resin pattern was immersed in an acidic degreasing solution (manufactured by Ebara Yujilite Co., Ltd., PB242D 10% diluent) for 3 minutes, and then washed with water.

Subsequently, 30 seconds in 30 degreeC soft etching liquid (made by Mertex Co., Ltd., AD485 10% dilution liquid), 25 degreeC in 10% sulfuric acid aqueous solution at 25 degreeC, 25 degreeC activator liquid (Okuno Seiyaku Kogyo Co., Ltd., ICP) Immersion in 15% diluent). Moreover, water washing was performed between each process so far. Subsequently, electroless Ni plating (20% dilution of S-810 manufactured by Nihon Kanizen Co., Ltd.) was performed at 80 ° C for 40 minutes, and after washing with water, substitution gold plating (Kojima Kagaku Yakuching ( Ltd.), OL2000 20% dilution liquid) was performed. Surface observation was performed using the cured resin pattern after plating, About the evaluation board | substrate which has no problem in surface observation, the peeling test was done with reference to JISK5600-5-6 again, and the following references | standards evaluated.

○… No abnormality after peeling test.

? Although there was no problem in surface observation, peeling was observed at the peeling test.

×… Submersion of the pattern or peeling of the pattern was observed by surface observation.

Example 2

In Example 1, except not adding an epoxy resin compound, a laminated body and a permanent pattern were produced like Example 1, and it carried out similarly to Example 1, and evaluated the sensitivity and plating resistance. The results are shown in Table 1.

Example 3

In Example 1, a laminate and a permanent pattern were produced in the same manner as in Example 1 except that barium sulfate was changed to silica (SO-C2, manufactured by Admatech Co., Ltd.), and the sensitivity and plating resistance were the same as in Example 1. Was done evaluation. The results are shown in Table 1.

Example 4

In Example 1, a laminate and a permanent pattern were produced in the same manner as in Example 1 except that barium sulfate was changed to silica (SO-C2 manufactured by Admatech Co., Ltd.) and no epoxy resin was added. In the same manner, sensitivity and plating resistance were evaluated. The results are shown in Table 1.

Example 5

In Example 1, a laminated body and a permanent pattern were produced like Example 1 except having changed 5 weight part of photoinitiators represented by I-1 into 2 weight part of photoinitiators represented by following formula I-2, In the same manner as in Example 1, sensitivity and plating resistance were evaluated. The results are shown in Table 1.

Example 6

In Example 5, except not adding an epoxy resin compound, a laminated body and a permanent pattern were produced like Example 1, and it carried out similarly to Example 5, and evaluated the sensitivity and plating resistance. The results are shown in Table 1.

Example 7

In Example 5, except having changed barium sulfate into silica (SO-C2 by Admatecs company), it carried out similarly to Example 5, and manufactured a laminated body and a permanent pattern, and carried out similarly to Example 1, and a sensitivity. And plating resistance were evaluated. The results are shown in Table 1.

Example 8

In Example 5, a laminated body and a permanent pattern were produced like Example 5 except having changed barium sulfate into silica (SO-C2 by Admatecs Co., Ltd.), and not adding an epoxy resin. In the same manner as in 1, the sensitivity and the plating resistance were evaluated. The results are shown in Table 1.

(Comparative Example 1)

In Example 1, the laminated body and the permanent pattern were produced like Example 1 except not having added an adhesion promoter, and it carried out similarly to Example 1, and evaluated the sensitivity and plating resistance. The results are shown in Table 1.

(Comparative Example 2)

In Example 1, a laminate and a permanent pattern were produced in the same manner as in Example 1, except that barium sulfate was changed to silica (SO-C2, manufactured by Admatech Co., Ltd.) without adding an adhesion promoter. In the same manner as in 1, the sensitivity and the plating resistance were evaluated. The results are shown in Table 1.

(Comparative Example 3)

In Example 1, except that barium sulfate and an epoxy resin compound were not added, a laminate and a permanent pattern were produced in the same manner as in Example 1, and the sensitivity and the plating resistance were evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 4)

In Example 1, except not adding barium sulfate, a laminated body and a permanent pattern were produced like Example 1, and it carried out similarly to Example 1, and evaluated the sensitivity and plating resistance. The results are shown in Table 1.

Table 1

From the results of Table 1, it turned out that in Examples 1-4, the pattern excellent in the sensitivity and plating resistance is formed compared with Comparative Examples 1-4. Moreover, it was confirmed that it is preferable that an inorganic filler is silica, and it is preferable to contain a thermal crosslinking agent.

Since the photosensitive film of the present invention has good plating resistance, sensitivity, developability and adhesion, and can efficiently form a high-definition permanent pattern, various patterns, such as permanent patterns such as a protective film, an interlayer insulating film and a solder resist pattern, and color It can use suitably for manufacture of liquid crystal structural members, such as a filter, a pillar material, a rib material, a spacer, a partition, a hologram, a micromachine, a proof, etc., and can use especially for the formation of the permanent pattern of a printed board.

Since the pattern formation method of this invention uses the said photosensitive resin composition, liquid crystal structures, such as a color filter, a pillar material, a rib material, a spacer, a partition, for forming various patterns, such as a permanent pattern, such as a protective film, an interlayer insulation film, and a soldering resist pattern, etc. It can use suitably for manufacture of a member, a hologram, a micromachine, a manufacture of a proof, etc., and can use especially for formation of the permanent pattern of a printed circuit board.

Claims

A binder, a polymeric compound, a photoinitiator, an inorganic filler, and an adhesion promoter are contained, The photosensitive resin composition characterized by the above-mentioned.

The method of claim 1, wherein the adhesion promoter is benzimidazole derivatives, benzoxazole derivatives, benzthiazole derivatives, thiotriazole derivatives, thiooxadiazole derivatives, N-substituted indazole derivatives, aromatic substituted indazole derivatives, tetra A photosensitive resin composition, which is at least one selected from a sol derivative, a quinoline derivative, a carbothioic acid amide derivative, and a benzotriazole derivative.

The photosensitive resin composition according to claim 1 or 2, wherein the inorganic filler is silica.

The photosensitive resin composition according to any one of claims 1 to 3, wherein the photopolymerization initiator is an oxime derivative.

The photosensitive resin composition of any one of Claims 1-4 which further contains a thermal crosslinking agent.

The photosensitive resin composition according to claim 5, wherein the thermal crosslinking agent is at least one selected from an epoxy resin compound, an oxetane compound, a polyisocyanate compound, a compound obtained by reacting a blocking agent with a polyisocyanate compound, and a melamine derivative.

The photosensitive layer which consists of a photosensitive resin composition of any one of Claims 1-6 is laminated | stacked on the support body, The photosensitive film characterized by the above-mentioned.

At least exposure to the photosensitive layer in the photosensitive film of Claim 7 is included, The pattern formation method characterized by the above-mentioned.

The micro-array according to claim 8, wherein the exposure modulates the light by the light modulation means, and then the micro-array having an aspherical surface capable of correcting the aberration caused by the distortion of the exit surface of the drawing part in the light modulation means. A pattern forming method characterized in that it is carried out through a lens array.

The pattern forming method according to claim 8 or 9, wherein the photosensitive layer is developed after the exposure is performed.

The pattern formation method of Claim 10 which performs hardening of the said photosensitive layer after the said image development is performed.

The permanent pattern is formed by the pattern formation method in any one of Claims 8-11, The printed circuit board characterized by the above-mentioned.