JP2001305731A - Photosensitive resin composition and photosensitive film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in flexibility and resistance to the heat of soldering, developable with a dilute alkali solution and suitable for an etching resist and a cover lay and to provide a photosensitive film using the composition. SOLUTION: The photosensitive resin composition contains a carboxyl- containing polyamide oligomer (A) obtained by reacting a diamine compound (a) with a compound (b) having one acid anhydride group and one carboxyl group in one molecule, a (meth)acrylate (c) having one epoxy group in one molecule, a polybasic acid anhydride (d) having two acid anhydride groups in one molecule as an arbitrary component and a polyol compound (e) as an arbitrary component, a diluent (B) and a photopolymerization initiator (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a resin composition and its use. More specifically, the present invention relates to a photosensitive resin composition suitable for forming an etching resist or a protective film (cover lay) which can be used for manufacturing a flexible printed wiring board and the like, and a photosensitive film using the same.

[0002]

2. Description of the Related Art Conventionally, in the production of printed wiring boards, liquid or film-shaped photosensitive resin compositions have been used. For example, as a resist for etching a copper foil of a copper-clad laminate, a printed wiring board on which wiring is formed is used for limiting a soldering position, protecting wiring, and the like.
2. Description of the Related Art Some printed wiring boards have a film shape that can be folded and incorporated into a small device such as a camera, and this is called an FPC. This FPC also requires a resist for limiting the soldering position and protecting the wiring, which is called a coverlay or a covercoat. The coverlay is formed by punching polyimide or polyester having an adhesive layer into a predetermined mold, and then by thermocompression bonding on an FPC.The cover coat is formed by printing and curing a thermosetting or photocurable ink. Formed.

In these resists used for the purpose of limiting the soldering position of the FPC and protecting the wiring, flexibility is a particularly important characteristic, and therefore, a polyimide coverlay excellent in flexibility is often used. . However, this coverlay requires an expensive mold for die cutting,
In addition, due to the manual bonding of the die-cut film and the sticking-out of the adhesive, the yield is low and the manufacturing cost is high, which is an obstacle to the expansion of the FPC market. It is difficult to respond.

Accordingly, a photosensitive resin composition for forming a highly accurate and highly reliable coverlay excellent in dimensional accuracy and resolution by a photographic development method (a method of forming an image by a phenomenon following image exposure), In particular, the appearance of a photosensitive film has been desired. For this purpose, attempts have been made to use a photosensitive resin composition for forming a solder mask. For example, photosensitive resin compositions containing an acrylic polymer and a photopolymerizable monomer as main components (JP-A-53-56018 and JP-A-54-56018).
As a photosensitive resin composition having good heat resistance, a composition mainly composed of a photosensitive epoxy resin having a chalcone group in a main chain and an epoxy resin curing agent (JP-A-54-82073) JP-A-58-62636), a composition mainly composed of a novolak-type epoxy acrylate containing an epoxy group and a photopolymerization initiator (JP-A-61-272, etc.), safety and economy As a photosensitive resin composition for forming a solder mask that can be developed with an alkaline aqueous solution, a carboxyl group-containing polymer,
Compositions comprising a monomer, a photopolymerization initiator and a thermosetting resin as main components (JP-A-48-73148, JP-A-57-73148)
178237, JP-A-58-42040,
JP-A-59-151152, etc.), but all have insufficient flexibility.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks of the prior art, and provides a photosensitive resin composition which is excellent in workability, excellent in flexibility, solder heat resistance and the like. To provide a photosensitive film.

[0006]

The present invention relates to (1) a diamine compound (a), a compound (b) having one acid anhydride group and one carboxyl group in one molecule, and one compound in a molecule.
(Meth) acrylate (c) having two epoxy groups,
A carboxyl group-containing polyamide oligomer (A) obtained by reacting a polyol compound (e) with a polybasic acid anhydride (d) having two acid anhydride groups in the molecule as an optional component, a diluent (B) and light A photosensitive resin composition comprising a polymerization initiator (C), (2) a compound (b) having one acid anhydride group and one carboxyl group in one molecule, and trimellitic anhydride (3) an epoxy resin having two or more epoxy groups in one molecule, (f) a photosensitive resin composition according to (1),
And ethylenically unsaturated group-containing monocarboxylic acid compound (g)
(1) The photosensitive resin composition according to (1) or (2), comprising a polycarboxylic acid resin (D) containing an unsaturated group, which is a reaction product of a polybasic acid anhydride (h) and (4) a support film (5) A photosensitive film obtained by laminating a layer of the photosensitive resin composition according to (1) to (3), (5) a cured product of the resin composition according to (1) to (3), (6) ( The present invention also relates to a cured product of the photosensitive film described in 4) and an article having the cured product described in (7), (5) or (6).

[0007]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail. The carboxyl group-containing polyamide oligomer (A) used in the present invention comprises a diamine compound (a), a compound (b) having one acid anhydride group and one carboxyl group in one molecule, and one epoxy compound in the molecule. It can be obtained by reacting a (meth) acrylate (c) having a group, a polybasic acid anhydride (d) having two acid anhydride groups in the molecule as an optional component, and a polyol compound (e).

The diamine compound (a) is not particularly restricted but includes, for example, aromatic diamines and aliphatic diamines.

Specific examples of the aromatic diamine that can be used include, for example, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 2,2-bis- [3- (4-
Aminophenoxy) phenyl] propane, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis-
[4- (3-aminophenoxy) phenyl] sulfone,
2,2-bis- [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis- [4-
(4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] biphenyl, bis [4- (3-aminophenoxy)] biphenyl, bis [1- (4-aminophenoxy)] Biphenyl, bis [1- (3-aminophenoxy)] biphenyl, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4- Aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy)] benzophenone, bis [4- (3-
Aminophenoxy) phenyl] benzophenone, bis [4- (4-aminophenoxy) phenyl] benzanilide, bis [4- (3-aminophenoxy) phenyl]
Benzanilide, 9,9-bis [4- (4-aminophenoxy) phenyl] fluorene, 9,9-bis [4-
(3-aminophenoxy) phenyl] fluorene, 4,
4'- (or 3,4'-, 3,3'-, 2,4'-,
2,2 ′-) diaminodiphenyl ether, 4,4 ′
(Or 3, 4'-, 3, 3'-, 2, 4'-, 2,
2 ') diaminodiphenylmethane, 4,4'- (or 3,4'-, 3,3'2, 4'-, 2,2'-) diaminodiphenylsulfone, 4,4'- (or 3,4') −,
3,3 '-, 2,4'-, 2,2 '-) diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, o-tolidine, o- Trizine sulfone,
4,4′-methylene-bis- (2,6-diethylaniline), 4,4′-methylene-bis- (2,6-diisopropylaniline), 2,4-diaminomesitylene,
5-diaminonaphthalene, 4,4′-benzophenonediamine 1,1,1,3,3,3-hexafluoro-2,
2-bis (4-aminophenyl) propane, 3,3'-
Dimethyl-4,4'-diaminodiphenylmethane, 3,
3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl)
Propane, benzidine, 2,6-diaminopyridine,
3,3′-dimethoxybenzidine, 1,4-bis (4-
Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′ [1,4-phenylenebis (1-methylethylidene)] bisaniline,
Aromatic diamines such as 4 '-[1,3-phenylenebis (1-methylethylidene)] bisaniline, 3,5-diaminobenzoic acid, ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2-diaminocyclohexane and the like; No.

Similarly, specific examples of the aliphatic diamine include:
Ethylenediamine, tetramethylenediamine, hexamethylenediamine, 1,2-diaminocyclohexane, diaminopolysiloxane, ATBN1300 × 16 (manufactured by Ube Industries, Ltd.) Jeffamine D-230 (hereinafter, manufactured by Sun Techno Chemical Co., Ltd.), D- 400, D-200
0, D-4000, ED-600, ED-900, ED
-2001, EDR-148 and the like. These can be used alone or in combination of two or more.

As the compound (b) having one acid anhydride group and one carboxyl group in one molecule, trimellitic anhydride is preferably used.

The (meth) acrylate (c) having one epoxy group in the molecule includes, for example, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and the like. A mixture of more than one species can be used.

As the carboxyl group-containing polyamide oligomer (A) used in the present invention, a polybasic acid anhydride (d) having two acid anhydride groups in one molecule and a polyol compound (e) are used as optional components. can do. As the polybasic acid anhydride (d) having two acid anhydride groups in one molecule, for example, a carboxylic acid anhydride is preferable, for example, pyromellitic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid Acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3 ′, 3,4′-biphenyltetracarboxylic acid, 3,3 ', 4,4'-diphenylethertetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid , 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid, m-terphenyl-3,3', 4,4'-
Tetracarboxylic acid, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane, 2,2-bis (2,3- Or 3,4-dicarboxyphenyl) propane, 2,2-bis [4 ′-(2,3- or 3,4-dicarboxylphenoxy) phenyl] propane, 1,1,1,3,3,3
-Hexafluoro-2,2-bis [4 '-(2,3- or 3,4-dicarboxyphenoxy) phenylpropane, 2,3,6,7-anthracenetetracarboxylic acid,
1,2,7,8-phenanthrenetetracarboxylic acid,
4,4'-bis (2,3-dicarboxyphenoxy) diphenylmethane, dianhydride of aromatic tetracarboxylic acid such as ethylene glycol bis (anhydrotrimellitate), the following general formula (1)

[0014]

Embedded image

(Wherein R ₁ and R ₂ are monovalent hydrocarbon groups,
Preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms (phenyl group, tolyl group, naphthyl group);
Each of which may be the same or different, and n is an integer of 1 or more), an aromatic tetracarboxylic dianhydride, cyclobutenetetracarboxylic acid, butanetetracarboxylic acid, 2,3,5,6- Pyridinetetracarboxylic acid,
Aliphatic tetracarboxylic dianhydrides such as 3,4,9,10-pesolenetetracarboxylic acid;
A mixture of more than one species can be used.

Further, as the polyol compound (e),
For example, alkyl polyol, polyester polyol,
Examples thereof include polyether polyol, acrylic polyol, polybutadiene polyol, phenolic polyol, and / or flame retardant polyol.

Examples of the alkyl polyol include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanedimethanol, trimethylolpropane, and pentaerythritol.

Examples of the polyester polyol include a condensation type polyester polyol, an addition polymerization type polyester polyol, and a polycarbonate polyol.
Examples of the condensed polyester polyol include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, neopentyl glycol, and 3-methyl Diol compounds such as -1,5-pentanediol, 1,4-hexanedimethanol, dimer acid diol, and polyethylene glycol, and adipic acid, isophthalic acid, terephthalic acid,
It is obtained by a condensation reaction with an organic polybasic acid such as sebacic acid, and preferably has a molecular weight of 100 to 100,000.

Examples of the addition-polymerized polyester polyol include polycaprolactone having a molecular weight of 100 to 100.
100,000 is preferred. Polycarbonate polyol is synthesized by direct phosgenation of polyol, transesterification with diphenyl carbonate, and the like, and preferably has a molecular weight of 100 to 100,000.

As the polyether polyol, PEG
, PPG-based, and PTG-based polyols. P
The EG-based polyol is obtained by subjecting ethylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000. PP
The G-based polyol is obtained by subjecting propylene oxide to addition polymerization using a compound having active hydrogen as a reaction initiator, and preferably has a molecular weight of 100 to 100,000. PT
The G-based polyol is synthesized by cationic polymerization of tetrahydrofuran, and preferably has a molecular weight of 100 to 100,000.

Examples of the polyether polyol other than the above-mentioned polyether polyol include an ethylene oxide adduct or a propylene oxide adduct of bisphenol A, and the molecular weight is preferably 100 to 100,000.

Other polyols are (meth) acrylate polyols, which are copolymers of hydroxyl group-containing (meth) acrylates and other (meth) acrylates, and copolymers of butadiene at the ends. Polybutadiene polyol which is a homo- or copolymer having a hydroxyl group, phenolic polyol containing a phenol molecule in the molecule, epoxy polyol, a flame-retardant polyol containing a phosphorus atom, a halogen atom and the like, and a molecular weight of 100 to 100, 000 is preferred. These polyol compounds can be used alone or in combination of two or more.

The carboxyl group-containing polyamide oligomer (A) used in the present invention can be synthesized, for example, as follows. First, the diamine compound (a) and 1
A compound (b) having one acid anhydride group and one carboxyl group in the molecule is reacted to prepare a terminal carboxylic acid polyamide prepolymer, and then a (meth) acrylate having one epoxy group in the molecule (C) is reacted. When a polybasic acid anhydride (d) having two acid anhydride groups in one molecule and a polyol compound (e) are used as optional components, first, a diamine compound (a) or a polyol compound (e) is used. A polybasic acid anhydride (d) having two acid anhydride groups in the molecule is reacted to prepare a terminal acid anhydride compound, and then a diamine compound (a)
Are further reacted, and then a compound (b) having one acid anhydride group and one carboxyl group in one molecule is reacted. Finally, it is obtained by reacting (meth) acrylate (c) having one epoxy group in the molecule.

The terminal carboxylic acid polyamide prepolymer is based on 1 equivalent of the amino group of the diamine compound (a).
It is preferable to react 0.9 to 1.3 equivalents (as acid anhydride equivalents) of the compound (b) having one acid anhydride group and one carboxyl group in one molecule. The reaction temperature of this amidation reaction is preferably from 0 to 80 ° C, and the reaction time is preferably from 1 to 10 hours.

Next, the carboxylic acid-terminated polyamide prepolymer has one (epoxy) group in the molecule (meth)
The acrylate (c) is reacted to obtain a carboxyl group-containing polyamide oligomer (A). It is preferable to react 0.05 to 0.95 equivalents of the epoxy group of (meth) acrylate (d) having one epoxy group in the molecule with respect to 1 equivalent of the carboxyl group of the terminal carboxylic acid polyamide prepolymer. Preferably, particularly preferably 0.1 to 0.8
Is equivalent. The reaction temperature is usually from 60 to 150 ° C, preferably from 80 to 120 ° C. Reaction time is 5-60
Time is preferred. In order to prevent gelation due to radical polymerization during this reaction, it is usually preferable to add 50 to 2000 ppm of a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol and p-benzoquinone. Although the reaction between the carboxyl group and the epoxy group proceeds without a catalyst, a basic compound such as triethylamine or triphenylphosphine may be added as a catalyst.

During or after the reaction, the reactive diluent (B-1) or the organic solvent (B-2) described below may be used alone or as a mixture of two or more.

When the polybasic acid anhydride (d) having two acid anhydride groups in the molecule and the polyol compound (e) are used as optional components, first, one equivalent of the amino group of the diamine compound (a) or The polybasic acid anhydride (d) having two acid anhydride groups in the molecule is defined as an acid anhydride equivalent of 1.1 to 1 equivalent of the hydroxyl group of the polyol compound (e).
It is preferable to make 2.1 equivalent reaction. In the case of an amidation reaction, the reaction temperature is preferably 0 to 80 ° C., and the reaction time is preferably 1 to 10 hours. In the case of the esterification reaction, the reaction temperature is 60 to 1
50 ° C, more preferably 80 to 100 ° C. The reaction time is preferably 1 to 10 hours.

Next, the terminal acid anhydride group compound is reacted with the diamine compound (a). It is preferable to react 1.1 to 2.0 equivalents as the amino group equivalent of the diamine compound (a) with respect to 1 equivalent of the acid anhydride group of the terminal acid anhydride group compound. The reaction temperature is preferably 0 to 80 ° C, and the reaction time is preferably 1 to 10 hours. Next, the compound (b) having one acid anhydride group and one carboxyl group in one molecule and the (meth) acrylate (c) having one epoxy group in the molecule are reacted. Same as the method.

In the present invention, a diluent (B) is used. Specific examples of the component (B) that can be used in the present invention include, for example,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, hydroxyl group-containing (meth) acrylate (for example, 2 Acid anhydrides of -hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.) and polycarboxylic acid compounds (for example, succinic anhydride, maleic anhydride, Half ester, which is a reaction product of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc., polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acyl. Rate, trimethylolpropane polyethoxytri (meth) acrylate, glycenepolypropoxytri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of hydroxypivalate neopenglycol (for example, Nippon Kayaku Co., Ltd. )
KAYARAD HX-220, HX-620,
Etc.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and ε-caprolactone, dipentaerythritol poly (meth) acrylate, mono- or polyglycidyl compounds (for example, butyl glycidyl ether, phenyl Glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl hexahydrophthalate,
Reactivity of glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc.) and epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid Diluent (B-1), γ-butyrolactone, γ-
Lactones such as valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε-caprolactone; dioxane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether,
Ethers such as diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; ethylene carbonate, propylene carbonate Carbonates such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone; phenols;
Phenols such as cresol and xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; toluene,
Hydrocarbons such as xylene, diethylbenzene and cyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene; organic solvents such as petroleum solvents such as petroleum ether and petroleum naphtha (B-
2) and the like. These diluents may be used alone or as a mixture of two or more.

In the present invention, a photopolymerization initiator (C) is used. Specific examples of the photopolymerization initiator that can be used include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone. , 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl Acetophenones such as phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone , 2-Amil anthra Anthraquinones, such as non; 2,4-diethyl thioxanthone, 2-isopropylthioxanthone, thioxanthone such as 2-chlorothioxanthone; acetophenone dimethyl ketal,
Ketals such as benzyldimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4'-methyldiphenylsulfide and 4,4'-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2 ,
And phosphine oxides such as 4,6-trimethylbenzoyl) -phenylphosphine oxide.

These can be used alone or as a mixture of two or more. Further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoate It can be used in combination with an accelerator such as a benzoic acid derivative such as acid isoamyl ester.

In the present invention, an unsaturated group-containing polycarboxylic acid resin (D) may be used. The unsaturated group-containing polycarboxylic acid resin (D) includes an epoxy resin (f) having two or more epoxy groups in one molecule, an ethylenically unsaturated group-containing monocarboxylic acid compound (g), and a polybasic acid anhydride. (H).

Examples of the epoxy resin (f) having two or more epoxy groups in one molecule include bisphenol type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, and trisphenol methane. Ethers such as epoxy resin, brominated epoxy resin, biphenyl-type epoxy resin, biphenol-type epoxy resin; 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; diglycidyl phthalate, tetrahydric Phthalic acid diglycidyl ester,
Glycidyl esters such as dimer acid glycidyl ester; glycidylamines such as tetraglycidyldiaminophenylmethane; heterocyclic epoxy resins such as triglycidyl isocyanurate; Epicoat series (Epicoat 1009, 1031: Yuka Shell Epoxy Co., Ltd.)
Manufactured), Epicron series (Epiclon N-3050,
N-7050: manufactured by Dainippon Ink and Chemicals, Inc.), DE
R series (DER-642U, DER-673MF:
Bisphenol A type epoxy resins such as Dow Chemical Co., Ltd.) and YDF series (YDF-2004, 200
7: manufactured by Toto Kasei Co., Ltd.) and an epoxy resin obtained by reacting an alcoholic hydroxyl group of a bisphenol F type epoxy resin with an epihalohydrin such as epichlorohydrin.

The reaction between the alcoholic hydroxyl group of the epoxy resin and epihalohydrin is preferably carried out in the presence of dimethyl sulfoxide. The amount of epihalohydrin used is determined based on the amount of alcoholic hydroxyl group 1 in the starting epoxy compound.
What is necessary is just to use 1 equivalent or more with respect to equivalent. However, when the amount exceeds 15 equivalents to 1 equivalent of the alcoholic hydroxyl group, the effect of increasing the amount is almost negligible, but the volumetric efficiency deteriorates.

In carrying out the reaction, an alkali metal hydroxide is used. As the alkali metal hydroxide, for example, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferable. It is sufficient to use approximately 1 equivalent of the alkali metal hydroxide with respect to 1 equivalent of the alcoholic hydroxyl group to be epoxidized in the raw material epoxy compound. When the total amount of the alcoholic hydroxyl groups of the starting epoxy compound is epoxidized, an excess amount may be used. However, if the amount exceeds 2 equivalents relative to 1 equivalent of the alcoholic hydroxyl groups, the polymer tends to be slightly polymerized.

The reaction temperature is preferably from 30 to 100 ° C.
When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long-time reaction is required. If the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable. After completion of the reaction, excess epihalohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and then the resulting resin is dissolved in an organic solvent, and a dehydrohalogenation reaction can be performed with an alkali metal hydroxide.

The epoxy resin (f) is reacted with the ethylenically unsaturated group-containing monocarboxylic acid compound (g) to obtain an epoxy (meth) acrylate compound. It is preferable to react 0.3 to 1.2 equivalents of the total amount of the carboxyl group of the component (g) with respect to 1 equivalent of the epoxy group of the epoxy resin, more preferably 0.9 to 1.05 equivalent. One or more of the above-mentioned diluents (B) can be used during or after the reaction.

Furthermore, a catalyst can be used to promote the reaction. Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, triphenylstilbin, triphenylphosphine and the like. The amount used is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, based on the reaction raw material mixture.

During the reaction, a polymerization inhibitor is preferably used to prevent polymerization of the ethylenically unsaturated group. Examples of the polymerization inhibitor include methoquinone, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount used is preferably from 0.01 to 1% by weight, more preferably from 0.05 to 0.5% by weight, based on the reaction raw material mixture. The reaction temperature is 60-150 ° C, and furthermore, 8
0-120 ° C is preferred. The reaction time is preferably 5 to 60 hours.

Next, the polybasic acid anhydride (h) is reacted. Examples of the polybasic acid anhydride (h) include succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methyl-
Examples thereof include tetrahydrophthalic anhydride and 4-methyl-hexahydrophthalic anhydride. The amount of the polybasic anhydride (f) to be used is 0.05 to 1.0 per equivalent of the hydroxyl group in the epoxy (meth) acrylate.
It is preferable to react at zero equivalent. The reaction temperature is 60 to 1
50 ° C, more preferably 80 to 100 ° C.

The amount of the unsaturated group-containing polycarboxylic acid (D) to be used is preferably 0 to 400 parts by weight, more preferably 30 to 300 parts by weight, per 100 parts by weight of the component (A).

The photosensitive resin composition of the present invention comprises (A)
It can be prepared by dissolving, mixing and kneading the components (B), (C) and (D). The use ratio of each component can be as follows (% is% by weight).
The amount of the component (A) or the component (A) + (D) used is 30 to
90%, the amount of the component (B-1) used is 5 to 65%,
The amount of the component (C) used is 5 to 30%. The amount of the organic solvent (B-2) can be used in any ratio for the purpose of adjusting the viscosity and the like suitable for using the composition of the present invention.

In the present invention, a thermosetting component (E) can be used. By using this, solder heat resistance and electrical characteristics can be further improved. Examples of the thermosetting component (E) include an epoxy resin, a melamine compound, an oxazoline compound, a phenol compound, and a compound containing a dihydrobenzoxazine ring. Specific examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, trisphenolmethane epoxy resin, brominated epoxy resin, and biphenol epoxy resin. Glycidyl ethers such as epoxy resins; 3,4-epoxy-6
-Methylcyclohexylmethyl-3,4-epoxy-6
-Methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,
Alicyclic epoxy resins such as 4-epoxycyclohexane; glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate and glycidyl dimer; glycidyl amines such as tetraglycidyl diaminodiphenylmethane; triglycidyl isocyanurate And the like. Among them, an epoxy resin having a melting point of 50 ° C. or more is preferable because a tack-free photopolymerizable film can be formed after drying.

Examples of the melamine compound include melamine and a melamine resin which is a polycondensate of melamine and formalin. Examples of the urea compound include urea and urea resins which are polycondensates of urea and formalin.

Examples of the oxazoline compound include 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 5-methyl-2-phenyl-2-oxazoline,
2,4-diphenyloxazoline and the like.

Examples of the phenol compound include phenol, cresol, chilenol, catechol, resorcin, hydroquinone, pyrogallol, resol and the like.

Examples of the dihydrobenzoxazine ring-containing compound include, for example, a mixture of 1 equivalent of a hydroxyl group of a compound having a phenolic hydroxyl group and about 1 equivalent of an amino group of a primary amine in 1 to 5 mol of formaldehyde heated to 70 ° C. or more. At 70 to 110 ° C., preferably 90 to 10 ° C.
It can be synthesized by reacting at 0 ° C. for 20 to 120 minutes and then drying under reduced pressure at a temperature of 120 ° C. or less.
All of the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group react with the primary amine and formaldehyde,
Those which form a dihydrobenzoxazine ring are preferred. The compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include compounds such as bisphenol A, bisphenol F, biphenol, trisphenol, and tetraphenol, and phenol resins. Examples of the phenolic resin include a novolak resin obtained by reacting a phenolic compound such as a monovalent phenolic compound such as phenol or an alkylphenol such as xylenol, t-butylphenol and octylphenol, a polyhydric phenol compound such as resorcinol and bisphenol A with formaldehyde. Alternatively, there are a resol resin, a phenol-modified xylene resin, a melamine phenol resin, and a polybutadiene-modified phenol resin. 1
The secondary amine is not particularly limited, and examples thereof include methylamine, cyclohexylamine, aniline, and substituted aniline. Formaldehyde may be used in the form of formalin or polyformaldehyde.

The compound containing a dihydrobenzoxazine ring can be prepared by a known method (for example, DE 2217099).
No. H. Ishida, J. et al. Polym. Sci. , P
artA32, 1121 (1994)).

When an epoxy resin is used as the thermosetting component (E), it is preferable to use a curing accelerator. Specific examples of the curing accelerator for the epoxy resin include 2-methylimidazole and 2-methylimidazole. Imidazole compounds such as ethyl-3-methylimidazole, 2-undecylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-undecylimidazole, etc .; melamine, guanamine, acetoguanamine, benzoguanamine , Ethyldiaminotriazine, 2,4-diaminotriazine, 2,4
Triazine derivatives such as -diamino-6-tolyltriazine and 2,4-diamino-6-xylyltriazine; tertiary amines such as trimethylamine, triethanolamine, N, N-dimethyloctylamine, pyridine and m-aminophenol Polyphenols and the like.
These curing accelerators can be used alone or in combination.

In the present invention, various additives and the like can be further added as needed. As various additives,
For example, fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, aluminum oxide, silica, clay,
Thixotropic agents such as Aerosil, phthalocyanine blue, phthalocyanine green, coloring agents such as titanium oxide, silicone, fluorine-based leveling agents and defoamers, dyes, hydroquinone, p-methoxyphenol,
And polymerization inhibitors such as hydroquinone monotyl ether.

The photosensitive resin composition and the photosensitive film of the present invention are obtained by dissolving, mixing, mixing the components (A), (B), (C), (D), (E) and various additives. It can be prepared and manufactured by kneading.

The photosensitive film of the present invention can be produced by laminating a layer of the photosensitive resin composition of the present invention on a support film. Examples of the support include a polymer film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene and the like. Among them, a polyethylene terephthalate film is preferable. Since these polymer films must be removed from the photosensitive layer later, they must not be surface-treated or made of a material that cannot be removed. The thickness of these polymer films is 5 to 10
The thickness is preferably 0 μm, more preferably 10 to 30 μm. These polymer films can be laminated on both sides of the photosensitive layer as a support film for one photosensitive layer and another as a protective film for the photosensitive layer.

After the resin composition prepared as described above is uniformly coated on the polymer film of the support film, the solvent is removed by heating and / or blowing with hot air.
It can be a dry film. The thickness of the dry film is not particularly limited, and is preferably 10 to 100 μm,
More preferably, the thickness is 20 to 60 μm.

The photosensitive film of the present invention comprising two layers, the photosensitive layer and the polymer film, obtained as described above, may be used as it is or by further laminating a protective film on the other surface of the photosensitive layer to form a roll. It can be wound up and stored.

The photosensitive resin composition and the photosensitive film of the present invention are particularly useful as resists such as etching resists and solder resists for flexible printed wiring boards, and can also be used as paints, coating agents, adhesives and the like. .

A printed wiring board to which the photosensitive resin composition or the photosensitive film of the present invention is applied can be obtained, for example, as follows. That is, when a liquid resin composition is used, the present invention is applied to a substrate for printed wiring with a film thickness of 5 to 160 μm by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method, and a curtain coating method. By applying the resin composition of (1) and drying the coating film at a temperature of 60 to 110 ° C, preferably 60 to 100 ° C, a tack-free coating film can be formed. Then, a photomask with an exposure pattern, such as a negative film, is brought into direct contact with the coating (or placed on top of the coating without contact),
Ultraviolet rays are irradiated at an intensity of about 10 to 2000 mJ / cm ² , and the unexposed portions are developed using a developing solution described later, for example, by spraying, rocking immersion, brushing, scrubbing, or the like. Then, if necessary, further irradiate ultraviolet rays, then 100 to 200 ° C., preferably 140 to 18
By performing a heat treatment at a temperature of 0 ° C., the flexibility is excellent, and the heat resistance, solvent resistance, acid resistance, adhesion,
A printed wiring board having a permanent protective film satisfying various characteristics such as electric characteristics can be obtained.

Examples of the organic solvent used for the development include halogens such as trichloroethane, aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; 1,4-dioxane and tetrahydrofuran. Ethers such as methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; lactones such as γ-butyrolactone; glycol derivatives such as butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; alicyclic hydrocarbons such as cyclohexanone and cyclohexanol; And petroleum solvents such as petroleum ether and petroleum naphtha, water and alkaline aqueous solutions include alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines. Can be used. or,

As a method for producing a photoresist image using the photosensitive film of the present invention, when the protective film is present, the protective film is removed and then the photosensitive layer is press-bonded to the substrate while heating. By doing so, they can be laminated. At this time, it is preferable that the layers are stacked under reduced pressure. The surface to be laminated is not particularly limited, and is preferably an FPC on which wiring is formed by etching or the like. The heating temperature of the photosensitive layer is not particularly limited,
The temperature is preferably set to 90 to 130 ° C. The pressure for pressing is not particularly limited, and it is preferable that the pressing be performed under reduced pressure.

The photosensitive layer thus completed in lamination is
A photomask on which an exposure pattern such as a negative film is formed is brought into direct contact with the film (or placed on the coating in a state where the film is not in contact with the film), and ultraviolet rays are irradiated at 10 to 2000 mJ / c.
irradiation with m ² medium strong. At this time, if the polymer film present on the photosensitive layer is transparent, it can be exposed as it is, but if it is opaque, it needs to be removed. From the viewpoint of protecting the photosensitive layer, the polymer film is transparent, and it is preferable to expose the polymer film while leaving the polymer film remaining. Irradiation light sources for photocuring include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps,
An ultra-high pressure mercury lamp, a xenon lamp or a metal halide lamp is suitable. In addition, a laser beam or the like can be used as the active light for exposure.

Next, after exposure, if a polymer film is present on the photosensitive layer, the polymer film is removed, and then, using the developing solution, a known method such as spraying, rocking immersion, brushing, etc. Thus, the unexposed portion can be removed and development can be performed. Then, if necessary, further irradiate ultraviolet rays, then 100 to 200 ° C., preferably 140 to 18
By performing a heat treatment at a temperature of 0 ° C., the flexibility is excellent, and the heat resistance, solvent resistance, acid resistance, adhesion,
A printed wiring board having a permanent protective film satisfying various characteristics such as electric characteristics can be obtained.

[0061]

The present invention will be described in more detail with reference to the following examples. It goes without saying that the present invention is not limited to the following examples. In the following, “parts” means “parts by weight” unless otherwise specified.

Synthesis Example 1 (Synthesis of carboxyl group-containing polyamide oligomer (A) 1) Trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., acid value: 876) was placed in a round bottom flask equipped with an agitator and a condenser.
mgKOH / g) 384.3 g, γ-butyrolactone 1
After charging 169 g and dissolving, 200.2 g of 3,4′-diaminophenyl ether was added to γ-butyrolactone 1
A solution dissolved in 169 g was slowly added dropwise over about 30 minutes. After the addition, the reaction was carried out at room temperature for about 2 hours and at 40 ° C. for about 5 hours, and a terminal carboxyl group polyamide prepolymer (solid acid value: 384 mg KOH / g) I got Next, 284.3 g of glycidyl methacrylate and 0.87 g of p-methoxyphenol were charged and reacted at 95 ° C. for 10 hours. The acid value of the solid was 130 mg KOH / g, the weight average molecular weight was about 2000 (by the GPC method), 27% of a carboxyl group-containing polyamide oligomer (A-1) was obtained.

Synthesis Example 2 (Synthesis 2 of carboxyl group-containing polyamide oligomer (A) 2) A round bottom flask equipped with a stirring device and a condenser was charged with 3-
Methyl-1,5-pentanediol terephthalate (manufactured by Kuraray Co., Ltd., Kuraray polyol P-520, hydroxyl value: 228 mgKOH / g, molecular weight: 500) 246
g, pyromellitic anhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd., acid value: 1029 mg KOH / g), 218 g, and γ-butyrolactone, 116 g, were reacted at 85 ° C. for about 10 hours,
A terminal acid anhydride compound having a solid content of 80% and a solid content acid value of 362.6 mgKOH / g was obtained. Next, a solution in which 200.2 g of 3,4′-diaminophenyl ether was dissolved in 800.8 g of γ-butyrolactone was slowly added dropwise over about 30 minutes. After the addition, the reaction was carried out at room temperature for about 2 hours and at 40 ° C. for about 5 hours. This gave a terminal amine compound. Then, trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd., acid value: 876 mgK)
OH / g) 192.2 g, γ-butyrolactone.
2 g was charged and reacted at 40 ° C. for about 5 hours to obtain a carboxyl group-terminated polyamide prepolymer (solid content acid value: 260
mg KOH / g). Then 142.2 g of glycidyl methacrylate and 2.1 g of p-methoxyphenol
g, and reacted at 95 ° C. for 10 hours. The acid value of the solid was 165 mgKOH / g, and the weight average molecular weight was about 3000.
A carboxyl group-containing polyamide oligomer (A-2) having a solid content of 47% (by GPC) was obtained.

Synthesis Example 3 (Synthesis of Unsaturated Group-Containing Polycarboxylic Acid Resin (D)) In a round bottom flask equipped with a stirring device and a condenser, a bisphenol F type epoxy resin (epoxy equivalent: 310 g /
(eq, softening point: 69 ° C), 310 g, and 251 g of carbitol acetate were charged and dissolved by heating at 90 ° C with stirring. The obtained solution was cooled to 60 ° C., added with 60 g of acrylic acid, 97 g of dimer acid, 0.8 g of methylhydroquinone, and 2.5 g of triphenylphosphine, heated and dissolved at 80 ° C., reacted at 98 ° C. for 35 hours, and solidified. 0.3 m
An epoxy acrylate having gKOH / g and a solid content of 65% was obtained. Then, the epoxy acrylate 718.5
g, succinic anhydride 100 g, carbitol acetate 5
4 g, and reacted at 90 ° C. for 6 hours.
An unsaturated group-containing polycarboxylic acid resin (D-1) having 9 mgKOH / g and a solid content of 65% was obtained.

Examples and Comparative Examples A photosensitive resin composition containing the materials shown in Table 1 was applied to a printed circuit board (a copper foil laminated on an imide film) by screen printing and dried at 80 ° C. for 20 minutes. .
Thereafter, a negative film is applied to the substrate, and the substrate is irradiated with ultraviolet light at an integrated exposure amount of 500 mJ / cm 2 using an exposure machine according to a predetermined pattern, and the organic solvent or 1 wt% Na ₂ C
The test substrate was prepared by developing with an O ₃ aqueous solution and heat curing at 150 ° C. for 50 minutes. With respect to the obtained test substrate, characteristics such as alkali developability, solder heat resistance, flexibility, heat deterioration resistance, and electroless gold plating resistance were evaluated.

Table 1 Amounts (parts by weight) Example Comparative Example 1 2 3 4 1 A-1 370 185 A-2 213 106 D-1 77 77 154 DPCA-60 * 1 30 30 30 30 30 DETX-S * 2 2.0 2.0 2.0 2.0 2.0 2.0 Irg907 * 3 20 20 20 20 20 γ-butyrolactone 3.6 33 Developability ○ ○ ○ ○ Solder heat resistance ○ ○ ○ ○ Flexible ○ ○ ○ × Heat deterioration ○ ○ ○ ○ × Electroless gold plating resistance ○ ○ ○ ○ ○

Note) * 1: DPCA-60; KAYAR, manufactured by Nippon Kayaku Co., Ltd.
AD DPCA-60 (ε- of dipentaerythritol
* 2: DETX-S; KAYACU manufactured by Nippon Kayaku Co., Ltd.
RE DETX-S (diethylthioxanthone) * 3: Irg907; manufactured by Ciba Specialty Chemicals, Irgacure 907 (2-methyl-1 [4
-(Methylthio) phenyl] -2-morpholinopropan-1-one)

(Developability) The coating film was dried at 80 ° C. for 60 minutes, and the developability by spray development with a 1% aqueous sodium carbonate solution at 30 ° C. was evaluated.・: No residue is visually observed. ×: There is a residue visually.

(Solder Heat Resistance) A rosin-based flux was applied to a test substrate, immersed in molten solder at 260 ° C. for 10 seconds, and evaluated by the state of the cured film when peeled off with a cellophane adhesive tape. ○ ・ ・ ・ ・ ・ ・ No abnormality. ×: There is peeling.

(Flexibility) Judgment was made in a state where the test board was solidly bent at 180 degrees. ○ ・ ・ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slight cracks. C: Cracks were formed in the bent portion and the cured film was separated.

(Heat-Resistant Deterioration Resistance) The test substrate was left at 125 ° C. for 5 days, and then evaluated in a state of 180 ° solid bending. ○ ・ ・ ・ ・ ・ ・ No cracks. △ ・ ・ ・ ・ Slight cracks. C: Cracks were formed in the bent portion and the cured film was separated.

(Electroless Gold Plating Resistance) Judgment was made in a state where the test substrate was plated with gold and peeled off with a cellophane adhesive tape as described below. ○ ・ ・ ・ ・ ・ ・ No abnormality. Δ: Some peeling was observed. ×: No peeling.

Electroless gold plating method: A test substrate was subjected to an acidic degreasing solution at 30 ° C. (Metex, manufactured by Nippon MacDermid Corporation).
(5% aqueous solution of L-5B) for 3 minutes to degrease, then dipped in running water for 3 minutes and washed with water. Next, the test substrate was placed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 hours.
Then, it was immersed in running water for 3 minutes and then washed with water. After the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was immersed in a 30 ° C. catalyst solution (a 10 vol% aqueous solution of a metal plate activator 350 manufactured by Meltex Co., Ltd.) for 7 minutes to give a catalyst, and then a 3 vol% aqueous solution in running water, pH 4.0.
6) for 20 minutes to perform electroless nickel plating. After the test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute, it was immersed in running water for 30 seconds to 1 minute and washed with water. Next, the test substrate was placed in a 95 ° C. gold plating solution (aqueous solution of 15 vol% of Aurolectroles UP and 3 vol% of potassium gold cyanide, manufactured by Meltex Co., Ltd., pH 6).
After immersion in electroless gold plating for 3 minutes, immersion in running water for 3 minutes and washing with water, and immersion in warm water at 60 ° C. for 3 minutes and washing with hot water. After sufficient washing with water, the water was thoroughly removed, dried, and a test substrate plated with electroless gold was obtained.

As is clear from the above results, the photosensitive resin composition of the present invention exhibits good alkali developability, or has poor heat resistance, flexibility, heat deterioration resistance and electroless gold plating resistance. Provides excellent cured film.

[0075]

The photosensitive resin composition of the present invention has good workability, excellent flexibility and excellent solder heat resistance, and is suitable for an etching resist for FPC and a photosensitive film for coverlay.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 501 G03F 7/004 501 512 512 7/028 7/028 H05K 3/06 H05K 3/06 H 3/28 3/28 DF term (reference) 2H025 AA00 AA07 AA10 AA14 AA20 AB11 AB15 AC01 AD01 BC14 BC31 BC68 BC74 CA01 CA20 CA27 CA28 CA35 CC03 FA03 FA17 FA29 FA30 4J011 QA01 QA03 QA13 QA23 QA24 QB01 SA06 SA06 SA31 SA51 SA63 SA64 SA84 WA01 4J027 AB03 AB10 AB28 AC03 AC04 AC06 AD02 AE02 AE03 AE04 AE05 BA04 BA08 BA13 BA25 CA10 CA14 CA16 CA18 CA29 CA34 CA36 CD08 CD09 CD10 5E314 AA27 AA32 BB02 CC15 FF06 GG03 CE01 GG08 CCG CE19 CF15 DD04

Claims (7)

[Claims] 1. A diamine compound (a), a compound (b) having one acid anhydride group and one carboxyl group in one molecule, and a (meth) acrylate (c) having one epoxy group in one molecule. A carboxyl group-containing polyamide oligomer (A) obtained by reacting a polyol compound (e) with a polybasic acid anhydride (d) having two acid anhydride groups in the molecule as an optional component, a diluent (B) and A photosensitive resin composition comprising a photopolymerization initiator (C). 2. The photosensitive resin composition according to claim 1, wherein the compound (b) having one acid anhydride group and one carboxyl group in one molecule is trimellitic anhydride. 3. A reaction product of an epoxy resin (f) having two or more epoxy groups in one molecule, a monocarboxylic acid compound containing an ethylenically unsaturated group (g), and a polybasic anhydride (h). 3. The photosensitive resin composition according to claim 1, which contains a polycarboxylic acid resin (D) containing an unsaturated group. 4. A photosensitive film obtained by laminating a layer of the photosensitive resin composition according to claim 1 on a support film. 5. A cured product of the resin composition according to claim 1. 6. A cured product of the photosensitive film according to claim 4. 7. An article having the cured product according to claim 5 or 6.