TW202033600A - Unsaturated group-containing polycarboxylic acid resin, photosensitive resin composition, cured product, substrate, and article having excellent sensitivity to active energy rays, developability, heat resistance, and adhesion after being left at high temperature - Google Patents

Abstract

The invention provides an active energy ray curable resin composition having excellent sensitivity to active energy rays, development, heat resistance, and adhesion after being left at high temperature. An unsaturated group-containing polycarboxylic acid resin (A) is obtained from the reaction of a reaction product (R) of an epoxy compound (a) with two or more glycidyl groups in the molecule and a monocarboxylic acid compound (b) with one or more ethylenically unsaturated groups in the molecule with the polybasic acid anhydride (d) represented by the following formula (1). (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

Description

Polycarboxylic acid resin containing unsaturated group, photosensitive resin composition, cured product, substrate and article

The present invention relates to an unsaturated group-containing polycarboxylic acid resin, a photosensitive resin composition containing the unsaturated group-containing polycarboxylic acid resin, and a cured product thereof.

Printed wiring boards are aimed at reducing the size and weight of portable devices or improving the communication speed, and require high precision and high density. Along with this, the requirements for solder resist covering the circuit itself are also increasing. Compared with the requirements, it is required to maintain heat resistance and thermal stability while being able to withstand the performance of substrate adhesion, high insulation, and electroless gold plating, and a material for film formation with stronger hardening properties is required .

As these materials, carboxylic acid ester compounds obtained by reacting carboxylic acids, compounds with hydroxyl groups and acrylic acid together with general epoxy resins are known as materials with low acid value and excellent developability, as examples of them A composition using a resin obtained by reacting a reaction product of a phenol novolak type epoxy resin or a cresol type epoxy resin with an unsaturated monobasic acid with an acid anhydride has been proposed (Patent Document 1, Patent Document 2, and Patent Document 3) .

On the other hand, research is underway to improve the heat resistance or developability after curing by changing the type of acid anhydride that reacts with the reaction product of the epoxy compound and the unsaturated monobasic acid (Patent Document 4). When the printed wiring board is installed near an internal combustion engine or battery mounted in a vehicle, etc., it is sometimes required for the cured coating film to adhere to the printed circuit board without cracks even after being left at a high temperature. Current research The solder mask (solder mask) cannot adequately cope with these requirements. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 7-67008 [Patent Document 2] Japanese Patent Publication No. 7-17737 [Patent Document 3] Japanese Patent No. 2598346 [Patent Document 4] Japanese Patent Laid-Open No. 2018-188623

[The problem to be solved by the invention] The object of the present invention is to provide a resin composition and a cured product thereof. The resin composition is excellent in photosensitivity to active energy rays so as to form a fine image that can meet the high functions of today's printed wiring boards. The development of the alkaline aqueous solution forms a pattern, and the obtained cured film satisfies the heat resistance required for the solder mask and the adhesion after being left at high temperature. [Technical means to solve the problem]

In order to solve the above-mentioned problems, the present inventors conducted intensive studies and found that a resin composition containing a specific unsaturated group-containing polycarboxylic acid resin provides curing with excellent adhesion and thermal decomposition resistance after being left at high temperature.物, thus completed the present invention. That is, the present invention provides:

（式中，X表示氫原子或碳數1～3的烷基） 所表示的多元酸酐（c）反應而獲得； （2）一種含有不飽和基的聚羧酸樹脂（A'），其為使分子中具有2個以上縮水甘油基的環氧化合物（a）、分子中具有1個以上乙烯性不飽和基的單羧酸化合物（b）、分子中具有至少2個羥基的單羧酸化合物（d）反應而獲得的反應性環氧羧酸酯化合物（R'）與下述式（1） [化2]

（式中，X表示氫原子或碳數1～3的烷基） 所表示的多元酸酐（c）反應而獲得； （3）一種含有不飽和基的聚羧酸樹脂（B），其為使所述含有不飽和基的聚羧酸樹脂（A）與分子中具有乙烯性不飽和基與縮水甘油基的化合物（e）反應而獲得； （4）一種含有不飽和基的聚羧酸樹脂（B'），其為使所述含有不飽和基的聚羧酸樹脂（A'）與分子中具有乙烯性不飽和基與縮水甘油基的化合物（e）反應而獲得； （5）根據所述（1）至（4）中任一項所述的含有不飽和基的聚羧酸樹脂，其中所述分子中具有2個以上縮水甘油基的環氧化合物（a）為下述式（2）所表示的環氧樹脂（f）； [化3]

（式中，n表示平均值，表示0～20的值）； （6）根據所述（1）至（4）中任一項所述的含有不飽和基的聚羧酸樹脂，其中所述環氧化合物為下述式（3）所表示的環氧樹脂（g）； [化4]

（式中，Ar分別獨立地為（I）或（II）中的任一者，（I）與（II）的莫耳比率為（I）/（II）=1～3；G表示縮水甘油基；m是重複數的平均值，是0>m≦5的正數）； （7）根據所述（1）至（6）中任一項所述的含有不飽和基的聚羧酸樹脂，其中固體成分酸值為40 mg･KOH/g～160 mg･KOH/g）。 （8）一種感光性樹脂組成物，其特徵在於含有根據所述（1）至（7）中任一項所述的含有不飽和基的聚羧酸樹脂（A）、（A'）、（B）或（B'）、光聚合起始劑（C）、交聯劑（D）及硬化劑（E）。 （9）一種硬化物，其為根據所述（8）所述的感光性樹脂組成物的硬化物。 （10）一種基材，具有根據所述（9）所述的硬化物的層。 （11）一種物品，具有根據所述（10）所述的基材。 [發明的效果](1) An unsaturated group-containing polycarboxylic acid resin (A), which is an epoxy compound having two or more glycidyl groups in the molecule (a) and a monomer having one or more ethylenically unsaturated groups in the molecule The reactive epoxy carboxylate compound (R) obtained by reacting the carboxylic acid compound (b) with the following formula (1) [formation 1]

(In the formula, X represents a hydrogen atom or an alkyl group with 1 to 3 carbon atoms) The polybasic acid anhydride represented by (c) is obtained by reaction; (2) An unsaturated group-containing polycarboxylic acid resin (A'), which is Epoxy compounds having two or more glycidyl groups in the molecule (a), monocarboxylic acid compounds having one or more ethylenically unsaturated groups in the molecule (b), and monocarboxylic acid compounds having at least two hydroxyl groups in the molecule (D) The reactive epoxy carboxylate compound (R') obtained by the reaction and the following formula (1) [formation 2]

(In the formula, X represents a hydrogen atom or an alkyl group with 1 to 3 carbon atoms) The polybasic acid anhydride (c) represented by the reaction is obtained; (3) An unsaturated group-containing polycarboxylic acid resin (B), which is obtained by making The unsaturated group-containing polycarboxylic acid resin (A) is obtained by reacting with a compound (e) having an ethylenic unsaturated group and a glycidyl group in the molecule; (4) A polycarboxylic acid resin containing an unsaturated group ( B'), which is obtained by reacting the unsaturated group-containing polycarboxylic acid resin (A') with a compound (e) having an ethylenic unsaturated group and a glycidyl group in the molecule; (5) According to the above (1) The unsaturated group-containing polycarboxylic acid resin according to any one of (1) to (4), wherein the epoxy compound (a) having two or more glycidyl groups in the molecule is the following formula (2) The represented epoxy resin (f); [化3]

(In the formula, n represents an average value and represents a value from 0 to 20); (6) The unsaturated group-containing polycarboxylic acid resin according to any one of (1) to (4), wherein The epoxy compound is an epoxy resin (g) represented by the following formula (3); [化4]

(In the formula, Ar is independently one of (I) or (II), and the molar ratio of (I) to (II) is (I)/(II) = 1 to 3; G represents glycidol Group; m is the average of the number of repetitions, which is a positive number of 0>m≦5); (7) The unsaturated group-containing polycarboxylic acid resin according to any one of (1) to (6), Among them, the solid acid value is 40 mg･KOH/g～160 mg･KOH/g). (8) A photosensitive resin composition characterized by containing the unsaturated group-containing polycarboxylic acid resin (A), (A'), (A) according to any one of (1) to (7). B) or (B'), photopolymerization initiator (C), crosslinking agent (D) and hardener (E). (9) A cured product that is a cured product of the photosensitive resin composition according to (8). (10) A substrate having a layer of the cured product described in (9). (11) An article having the substrate according to (10). [Effects of the invention]

It contains the unsaturated group-containing polycarboxylic acid resin (A), (A'), (B) or (B') of the present invention, photopolymerization initiator (C), crosslinking agent (D) and hardener The photosensitive resin composition characterized by (E) is excellent in photosensitivity, can be patterned by development with an aqueous alkali solution, and is excellent in heat resistance and adhesion after being left at high temperature.

Epoxy compound (a) having two or more glycidyl groups in the molecule used to produce the unsaturated group-containing polycarboxylic acid resin (A), (A'), (B) or (B') of the present invention Especially desirable is an epoxy compound (a) having an epoxy equivalent of 100 g/equivalent to 900 g/equivalent. When the epoxy equivalent is less than 100, the obtained polycarboxylic acid resin containing unsaturated groups ((A), (A'), (B) or (B')) has a small molecular weight and is difficult to form a film. It is possible that flexibility may not be sufficiently obtained, and when the epoxy equivalent exceeds 900, the introduction rate of the monocarboxylic acid compound (b) having an ethylenically unsaturated group may decrease, and the photosensitivity may decrease.

Specific examples of epoxy compounds (a) having two or more glycidyl groups in the molecule include phenol novolac type epoxy resins, cresol novolac type epoxy resins, and trihydroxyphenylmethane type epoxy resins. , Dicyclopentadiene phenol epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, biphenol epoxy resin, bisphenol-A novolak epoxy resin, containing naphthalene Skeleton epoxy resin, glyoxal epoxy resin, heterocyclic epoxy resin, etc.

Examples of phenol novolac epoxy resins include: EPICLON N-770 (manufactured by DIC Co., Ltd.), DEN438 (manufactured by Dow Chemical Co., Ltd.), Epikote (Epikote) ) 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, RE-306 (manufactured by Nippon Kayaku Corporation), etc. Examples of cresol novolac type epoxy resins include: EPICLON N-695 (manufactured by DIC Co., Ltd.), EOCN-102S, EOCN-103S, and EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.) ), UVR-6650 (manufactured by Union Carbide Corporation), ESCN-195 (manufactured by Sumitomo Chemical Industry Co., Ltd.), etc.

Examples of trihydroxyphenylmethane type epoxy resins include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), Epikote (Epikote) E1032H60 (manufactured by Mitsubishi Chemical Co., Ltd.), etc. As the dicyclopentadiene phenol type epoxy resin, for example, EPICLON EXA-7200 (manufactured by DIC Co., Ltd.), TACTIX-556 (manufactured by Dow Chemical Co., Ltd.) and the like can be cited.

Examples of bisphenol-type epoxy resins include: Epikote 828, Epikote 1001 (manufactured by Mitsubishi Chemical), and UVR-6410 (manufactured by Union Carbide Corporation) , DER-331 (manufactured by Dow Chemical Company), YD-8125 (manufactured by Nippon Chemical Epoxy Co., Ltd.), NER-1202, NER-1302 (manufactured by Nippon Kayaku), etc. Type epoxy resin, UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Nippon Kayaku Co., Ltd.), NER-7403, NER-7604 (manufactured by Nippon Kayaku) And other bisphenol-F type epoxy resin.

Examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000, NC-3000-H, NC-3500 (manufactured by Nippon Kayaku Co., Ltd.), and YX-4000 (Mitsubishi Chemical Co., Ltd.) ) Manufactured by xylenol epoxy resin, YL-6121 (manufactured by Mitsubishi Chemical Co., Ltd.), etc. As a bisphenol A novolak type epoxy resin, Epiclon N-880 (made by DIC Co., Ltd.), Epikote E157S75 (made by Mitsubishi Chemical Co., Ltd.), etc. are mentioned, for example.

Examples of epoxy resins containing a naphthalene skeleton include NC-7000 (manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by DIC Co., Ltd.), and the like. As a glyoxal-type epoxy resin, GTR-1800 (manufactured by Nippon Kayaku) etc. are mentioned, for example. As an alicyclic epoxy resin, EHPE-3150 (made by Daicel (stock)) etc. are mentioned, for example. As a heterocyclic epoxy resin, TEPIC (manufactured by Nissan Chemical Co., Ltd.) etc. are mentioned, for example.

Among these, as the epoxy compound (a) having two or more glycidyl groups in the molecule, an epoxy resin represented by the following formula (2) or the following formula (3) has good heat resistance and is therefore preferable.

（式中，n表示平均值，表示0～20的值）[化5]

(In the formula, n represents the average value and represents a value from 0 to 20)

（式中，Ar分別獨立地為（I）或（II）中的任一者，（I）與（II）的莫耳比率為（I）/（II）=1～3；G表示縮水甘油基；m是重複數的平均值，是0>m≦5的正數）[化6]

(In the formula, Ar is independently one of (I) or (II), and the molar ratio of (I) to (II) is (I)/(II) = 1 to 3; G represents glycidol Base; m is the average of the number of repetitions, which is a positive number of 0>m≦5)

Monocarboxylic acid having at least one ethylenically unsaturated group in the molecule used for the production of the unsaturated group-containing polycarboxylic acid resin (A), (A'), (B) or (B') The compound (b) includes, for example, acrylic acid or crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction product of a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound. As acrylics, for example, (meth)acrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, saturated or unsaturated dibasic acid anhydrides and (meth)acrylates having one hydroxyl group per molecule The half esters of the isomolar reaction products of derivatives, the half esters of the isomolar reaction products of saturated or unsaturated dibasic acid and monoglycidyl (meth)acrylate derivatives, etc., are made into photosensitive In terms of sensitivity at the time of the resin composition, (meth)acrylic acid, a reaction product of (meth)acrylic acid and ε-caprolactone, or cinnamic acid is particularly preferable.

As specific examples of the monocarboxylic acid compound (d) having at least two hydroxyl groups in the molecule used for the production of the unsaturated group-containing polycarboxylic acid resin (A') or (B') of the present invention, for example, two Polyhydroxycarboxylic acids such as methylol propionic acid, dimethylol butyric acid, dimethylol acetic acid, dimethylol butyric acid, dimethylol valeric acid, and dimethylol caproic acid. As particularly preferable ones, for example, dimethylol propionic acid, dimethylol butyric acid and the like can be cited.

As a specific example of the compound (e) having an ethylenic unsaturated group and a glycidyl group used for the production of the unsaturated group-containing polycarboxylic acid resin (B) or (B') of the present invention, for example: ( Glycidyl meth)acrylate, glycidyl etherate of 3-hydroxypropyl (meth)acrylate, glycidyl etherate of 4-hydroxybutyl (meth)acrylate, glycidyl etherate of pentaerythritol triacrylate, Glycidyl esters of maleiminocaproic acid, glycidyl esters of cinnamic acid, etc., particularly preferably glycidyl (meth)acrylate and glycidyl etherate of 4-hydroxybutyl (meth)acrylate As commercially available products, glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.) and the like can be cited.

The reaction between the epoxy compound (a) having two or more glycidyl groups in the molecule and the monocarboxylic acid compound (b) having one or more ethylenically unsaturated groups in the molecule, and the reaction of having two or more glycidol groups in the molecule The reaction between the epoxy compound (a) and the monocarboxylic acid compound (b) having one or more ethylenically unsaturated groups in the molecule and the monocarboxylic acid compound (d) having at least two hydroxyl groups in the molecule can be achieved by Solvents or organic solvents, specifically, ketones such as acetone, ethyl methyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethyl benzene; ethylene glycol dimethyl ether, ethylene glycol Alcohol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers, ethyl acetate, butyl acetate, methyl cellosolve acetic acid Ester, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, hexamethylene Esters such as dialkyl acid esters; cyclic esters such as γ-butyrolactone; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; crosslinking agent (D), etc. described later It is obtained by reacting in an organic solvent alone or in a mixture.

An epoxy compound (a) having two or more glycidyl groups in the molecule is reacted with a monocarboxylic acid compound (b) having one or more ethylenically unsaturated groups in the molecule to obtain a reactive epoxy carboxylate compound ( In the reaction of R), the addition ratio of the monocarboxylic acid compound (b) having one or more ethylenically unsaturated groups in the molecule is preferably 1 equivalent to the epoxy compound (a) having two or more glycidyl groups in the molecule, It is 0.8 equivalent to 1.2 equivalent. If it is out of the above range, there is a possibility that gelation may occur during the reaction, or the thermal stability of the unsaturated group-containing polycarboxylic acid resin (A) finally obtained may be low.

An epoxy compound (a) having two or more glycidyl groups in the molecule, a monocarboxylic acid compound having one or more ethylenically unsaturated groups in the molecule (b), and a monocarboxylic acid having at least two hydroxyl groups in the molecule In the reaction of the compound (d) to obtain the reactive epoxy carboxylate compound (R'), the monocarboxylic acid compound (b) having at least one ethylenic unsaturated group in the molecule and at least two hydroxyl groups in the molecule The addition ratio of the monocarboxylic acid compound (d) is preferably: a monocarboxylic acid compound having one or more ethylenically unsaturated groups in the molecule with respect to 1 equivalent of the epoxy compound (a) having two or more glycidyl groups in the molecule The total of (b) and the monocarboxylic acid compound (d) having at least two hydroxyl groups in the molecule is 80 equivalent% to 120 equivalent%. Furthermore, the ratio of the monocarboxylic acid compound (b) having at least one ethylenically unsaturated group in the molecule to the monocarboxylic acid compound (d) having at least two hydroxyl groups in the molecule is preferably in the range of 5:95 to 95:5 . If it is out of the above range, there is a possibility that gelation may occur during the reaction, or the thermal stability of the unsaturated group-containing polycarboxylic acid resin (A) finally obtained may be low.

During the reaction, in order to suppress the thermal polymerization reaction, it is preferable to add a thermal polymerization inhibitor, relative to the epoxy compound (a) having two or more glycidyl groups in the molecule, and the monocarboxylic acid having one or more ethylenically unsaturated groups in the molecule The total amount of the reaction product of the compound (b) and the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule added according to the situation and the solvent is 0.1 to 10 parts by mass. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-p-cresol, and the like.

Moreover, during the reaction, in order to promote the reaction, it is preferable to use a catalyst. The amount of the catalyst used is relative to the epoxy compound (a) having two or more glycidyl groups in the molecule, and the one having one or more ethylenically unsaturated groups in the molecule. The total 100 parts by mass of the reaction product of the monocarboxylic acid compound (b), the monocarboxylic acid compound (d) having at least two hydroxyl groups in the molecule added, and the solvent is 0.1 to 10 parts by mass. The reaction temperature at this time is 60°C to 150°C, and the reaction time is preferably 3 hours to 60 hours. The catalyst used in this reaction includes, for example, dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethyl Ammonium iodide, triphenylphosphine, triphenyl antimonide, methyl triphenyl antimonide, chromium 2-ethylhexanoate, chromium octoate, zinc 2-ethylhexanoate, zinc octoate, zirconium octoate, Dimethyl sulfide, diphenyl sulfide, etc.

The reaction preferably proceeds until the acid value (solid content acid value) becomes 3 mg·KOH/g or less. The solid content acid value is the amount of potassium hydroxide (mg) required to neutralize the acidity of the carboxylic acid in 1 g of resin, and the acid value is the amount of potassium hydroxide required to neutralize 1 g of the resin-containing solution ( mg), in accordance with Japanese Industrial Standards (JIS) K 0070, measured by the usual neutralization titration method. Furthermore, if the concentration of the resin in the solution is known, the solid content acid value can also be calculated from the acid value of the solution.

As a reactive epoxy carboxylate compound obtained by reacting an epoxy compound having two or more glycidyl groups in the molecule (a) and a monocarboxylic acid compound having one or more ethylenically unsaturated groups in the molecule (b) (R) Or epoxy compounds (a) having two or more glycidyl groups in the molecule, monocarboxylic acid compounds having one or more ethylenic unsaturated groups in the molecule (b), and at least two hydroxyl groups in the molecule The preferred molecular weight range of the reactive epoxy carboxylate compound (R') obtained by the reaction of the monocarboxylic acid compound (d), the weight average molecular weight of polystyrene in gel permeation chromatography (GPC) It is in the range of 500 to 50,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000.

Among the polybasic acid anhydrides (c) represented by the following formula (1) used for the production of the unsaturated group-containing polycarboxylic acid resin (A), (A'), (B) or (B') of the present invention Examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, and propyl.

（式中，X表示氫原子或碳數1～3的烷基）[化7]

(In the formula, X represents a hydrogen atom or an alkyl group with 1 to 3 carbon atoms)

Among these, the compound represented by the following formula (4) is preferred, which can be obtained as a commercially available product, for example, Allyl succinic acid anhydride (ASA) manufactured by Fuji Photo Film Wako Pure Chemical Industries, Ltd. .

[化8]

The polybasic acid anhydride (c) may be used alone, but it may also be used in combination with other polybasic acid anhydrides for the purpose of adjusting the developability and blocking generation of the photosensitive resin composition of the present invention. As a combination with other polybasic acid anhydrides, for example, any compound having an acid anhydride structure in the molecule can be used, but particularly preferred are succinic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, which are excellent in aqueous alkali solution developability, heat resistance, and hydrolysis resistance. Hydrogen phthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride or maleic anhydride.

The addition reaction of the polybasic acid anhydride (c) can be achieved by obtaining an epoxy compound having two or more glycidyl groups in the molecule (a) and a monocarboxylic acid compound having one or more ethylenically unsaturated groups in the molecule (b) ) And, if necessary, adding polybasic acid anhydride (c) to the reaction solution of the reaction product of the monocarboxylic acid compound (d) having at least two hydroxyl groups in the molecule. The amount of addition is preferably added so that the solid acid value of the finally obtained unsaturated group-containing polycarboxylic acid resin (A) becomes a calculated value of 40 mg･KOH/g to 160 mg･KOH/g. When the solid acid value at this time is less than 40 mg･KOH/g, the alkali aqueous solution developability of the photosensitive resin composition of the present invention is significantly reduced, and in the worst case, development may not be possible, and the solid content When the acid value exceeds 160 mg･KOH/g, the developability may become too high and patterning may not be possible. The reaction temperature is, for example, 60°C to 150°C, and the reaction time is preferably 2 hours to 8 hours.

In the photosensitive resin composition of the present invention, a photopolymerization initiator (C) can be used as necessary. As specific examples of the photopolymerization initiator (C), for example, 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- Phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane 1-ketone and other acetophenones; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone and other anthraquinones; 2,4-diethyl thio Thioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone and other thioxanthones; acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals; benzophenone, Benzophenones such as 4-benzyl-4'-methyl diphenyl sulfide and 4,4'-dimethylaminobenzophenone; 2,4,6-trimethyl benzophenone Phosphine oxides such as diphenylphosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, etc.

These can be used alone or in the form of a mixture of two or more, and can be used with tertiary amines such as triethanolamine and methyldiethanolamine, N,N-dimethylamino ethyl benzoate, and N,N-dimethyl A combination of accelerators such as benzoic acid derivatives such as isoamyl aminobenzoate and the like is used.

In the photosensitive resin composition of this invention, a crosslinking agent (D) can be used as needed. Specific examples of the crosslinking agent (D) include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,4-butanediol mono(meth)acrylic acid Ester, carbitol (meth)acrylate, acrylomorpholine, as hydroxyl-containing (meth)acrylate (for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 1,4-butanediol mono(meth)acrylate, etc.) and anhydrides of polycarboxylic acid compounds (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydro Phthalic anhydride, etc.) of the reaction product half ester, polyethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane The bis(meth)-caprolactone adduct of methylol propane polyethoxy tri(meth)acrylate, glycerol polypropoxy tri(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol Base) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., Kayarad (KAYARAD) HX-220, HX-620, etc.), pentaerythritol tetra(meth)acrylate, dipentaerythritol and ε-caprolactone The reaction product of poly(meth)acrylate, dipentaerythritol poly(meth)acrylate, as a monoglycidyl compound or polyglycidyl compound (such as butyl glycidyl ether, phenyl glycidyl ether, polyethylene two Alcohol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalate diglycidyl ether, glycerol polyglycidyl ether, glycerol polyethoxyglycidyl ether , Trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxy polyglycidyl ether, etc.) and (meth)acrylic acid reaction product epoxy (meth)acrylate, etc.

In the photosensitive resin composition of the present invention, a curing agent (E) can be used as necessary. Examples of the curing agent (E) include epoxy compounds and oxazine compounds. The curing agent (E) is particularly preferably used when it is heated to react with the carboxyl group or the hydroxyl group remaining in the resin coating film after light curing to obtain a cured coating film with stronger chemical resistance.

Specific examples of the epoxy compound as the curing agent (E) include: phenol novolak type epoxy resin, cresol novolak type epoxy resin, trihydroxyphenylmethane type epoxy resin, and dicyclopentadiene phenol type Epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, biphenol epoxy resin, bisphenol-A novolak epoxy resin, glyoxal epoxy resin, containing naphthalene Skeleton epoxy resin, heterocyclic epoxy resin, etc.

Examples of phenol novolac epoxy resins include: EPICLON N-770 (manufactured by DIC Co., Ltd.), DEN438 (manufactured by Dow Chemical Co., Ltd.), Epikote (Epikote) ) 154 (manufactured by Mitsubishi Chemical Co., Ltd.), RE-306 (manufactured by Nippon Kayaku Co., Ltd.), etc. Examples of cresol novolac type epoxy resins include: EPICLON N-695 (manufactured by DIC Co., Ltd.), EOCN-102S, EOCN-103S, and EOCN-104S (manufactured by Nippon Kayaku Co., Ltd.) ), UVR-6650 (manufactured by Union Carbide Corporation), ESCN-195 (manufactured by Sumitomo Chemical Industry Co., Ltd.), etc.

Examples of trihydroxyphenylmethane type epoxy resins include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), and TACTIX-742 (manufactured by Dow Chemical) , Epikote (Epikote) E1032H60 (manufactured by Mitsubishi Chemical Corporation), etc. As the dicyclopentadiene phenol type epoxy resin, for example, EPICLON EXA-7200 (manufactured by DIC Co., Ltd.), TACTIX-556 (manufactured by Dow Chemical Co., Ltd.) and the like can be cited.

Examples of bisphenol-type epoxy resins include Epikote 828, Epikote 1001 (manufactured by Mitsubishi Chemical Co., Ltd.), and UVR-6410 (Union Carbide Corporation (Union Carbide Corporation) ) Manufacturing), DER-331 (manufactured by Dow Chemical), YD-8125 (manufactured by Nippon Kayaku Co., Ltd.), NER-1202, NER-1302 (manufactured by Nippon Kayaku Co., Ltd.) ) And other bisphenol-A epoxy resins, UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Nippon Chemical Epoxy Co., Ltd.), NER-7403, NER-7604 (Nippon Kayaku Co., Ltd.) and other bisphenol-F epoxy resins.

Examples of biphenol-type epoxy resins include biphenol-type epoxy resins such as NC-3000 and NC-3000H (manufactured by Nippon Kayaku Co., Ltd.), and Lianji of YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.) Cresol type epoxy resin, YL-6121 (manufactured by Mitsubishi Chemical Corporation), etc. As the bisphenol A novolak type epoxy resin, for example, EPICLON N-880 (manufactured by DIC Co., Ltd.), Epikote E157S75 (manufactured by Mitsubishi Chemical Co., Ltd.), and the like can be cited.

Examples of epoxy resins containing a naphthalene skeleton include NC-7000, NC-7300 (all manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by DIC Co., Ltd.), and the like. Examples of the glyoxal-type epoxy resin include GTR-1800 (manufactured by Nippon Kayaku Co., Ltd.). As an alicyclic epoxy resin, EHPE-3150 (made by Daicel (stock)) etc. are mentioned, for example. As a heterocyclic epoxy resin, TEPIC-L, TEPIC-H, TEPIC-S (all manufactured by Nissan Chemical Co., Ltd.) etc. are mentioned, for example.

Specific examples of the oxazine compound as the curing agent (E) include, for example, B-m-type benzoxazine, P-a-type benzoxazine, and B-a-type benzoxazine (all manufactured by Shikoku Chemical Industry Co., Ltd.).

Regarding the amounts of the (A), (A') or (B), (C), (D) and (E) components contained in the photosensitive resin composition of the present invention, the amount of the photosensitive resin composition When the volatile component is set to 100% by weight, the component (A), (A') or (B) is 10% to 80% by weight, the component (C) is 0% to 40% by weight, and the component (D) 0 wt% to 70 wt%, (E) component is 0 wt% to 40 wt%, (C) component is preferably 0.5 wt% to 30 wt%, and (D) component is preferably 5 wt% to 60 wt% %, (E) component is preferably 5% by weight to 30% by weight.

Furthermore, various additives such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, alumina, silica, clay, etc. can be added for the purpose of improving various properties of the composition as needed. Agents; AEROSIL and other thixotropic agents; colorants such as phthalocyanine blue, phthalocyanine green, and titanium oxide; silicone, fluorine-based leveling agents or defoamers; hydroquinone, terephthalate Polymerization inhibitors such as phenol monomethyl ether.

In addition, the curing agent (E) may be mixed in advance with the photosensitive resin composition of the present invention, or may be mixed and used before being applied to a printed wiring board. That is, it is formulated with the above-mentioned (A), (A') or (B) component as the main component, in which a main agent solution such as an epoxy curing accelerator, and a hardening agent (E) as the main component It is a two-component type of agent solution. It is a method of mixing them when in use.

The photosensitive resin composition of the present invention can also be used as a dry film type solder mask including a structure in which the resin composition is sandwiched between a supported film and a protective film.

The dry film using the photosensitive resin composition of this invention can be obtained as follows, for example. That is, when a liquid resin composition is used, a film thickness of 5 μm to 160 μm is applied to the support film by screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc. The photosensitive resin composition of the present invention is applied, and the coating film is usually dried at a temperature of 50°C to 110°C, preferably 60°C to 100°C, thereby forming a coating film. After that, a protective film is attached to this coating film to obtain a dry film.

The photosensitive resin composition (liquid or film) of the present invention is useful in addition to resist materials such as insulating materials between layers of electronic parts, optical waveguides connecting optical parts, solder masks for printed boards, and covering layers. In addition, it can also be used as a color filter, printing ink, sealant, paint, coating agent, adhesive, etc.

The cured product of the present invention is formed by curing the resin composition of the present invention by irradiation with energy rays such as ultraviolet rays and electron beams. Curing can be performed by conventional methods by irradiation with energy rays such as ultraviolet rays. For example, in the case of irradiating ultraviolet rays, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, an ultraviolet light emitting laser (excimer laser, etc.) and other ultraviolet generating devices may be used.

The cured product of the present invention can be used, for example, as a resist film, an interlayer insulating material for a build-up method, or an optical waveguide in electrical/electronic/optical parts such as a printed board, an optoelectronic board, or an optical board. As specific examples of these, for example, computers, household appliances, portable devices, etc. can be cited. The thickness of the cured product layer is about 0.5 μm to 160 μm, preferably about 1 μm to 100 μm.

The printed wiring board using the photosensitive resin composition of this invention can be obtained from a dry film or a liquid resin composition, for example. In the case of using a dry film, the dry film using the photosensitive resin composition of the present invention is on a printed circuit board, using a heating roller at a temperature of 50°C to 100°C, and attaching the resin layer to the substrate while peeling off the protective film The whole face. Next, through the photomask screen with the circuit pattern formed, the coating film is irradiated directly or indirectly with high energy rays such as ultraviolet rays at an intensity of usually about 10 mJ/cm ² to 2000 mJ/cm ² , using the developer described later, for example The unexposed parts are developed by spraying, swinging dipping, brushing, scraping, etc. After washing and drying as needed, further irradiating with ultraviolet rays as needed, followed by heat treatment at a temperature of usually 100°C to 200°C, preferably 140°C to 180°C, to obtain the following excellent gold plating properties and satisfy heat resistance, Printed wiring boards with various characteristics such as solvent resistance, acid resistance, adhesion, and flexibility. When a liquid resin composition is used, a film thickness of 5 μm to 160 μm is applied to the printed wiring board by screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc. The photosensitive resin composition of the present invention is applied, and the coating film is usually dried at a temperature of 50°C to 110°C, preferably 60°C to 100°C, thereby forming a coating film. After that, through a mask screen with an exposure pattern such as a negative film, the coating film is directly or indirectly irradiated with high-energy rays such as ultraviolet rays at an intensity of about 10 mJ/cm ² to 2000 mJ/cm ² . The developer described later develops the unexposed part by, for example, spraying, swing immersion, brushing, scraping, or the like. After that, if necessary, further irradiate with ultraviolet rays, and then heat treatment at a temperature of usually 100°C to 200°C, preferably 140°C to 180°C, thereby obtaining excellent gold plating properties and meeting heat resistance, solvent resistance, and acid resistance. Permanent protective film printed wiring boards with various characteristics such as performance and adhesion.

As the alkaline aqueous solution used in the development, inorganic alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, etc., or tetramethylhydroxide can be used. Organic alkali aqueous solutions such as ammonium, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.

The base material having the layer of the cured product of the present invention includes, for example, a resist film, an interlayer insulating film or dry film for a build-up method, and a printed board, a flexible substrate, an optoelectronic substrate, or an optical substrate having an optical waveguide film.

Examples of articles having the substrate of the present invention include home appliances such as automobiles, computers, and liquid crystal displays, and portable devices such as mobile phones. [Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited to the following examples.

Synthesis example 1 In a 1 L flask equipped with a stirring device and a reflux tube, 298.8 g of carbitol acetate as a reaction solvent and NC-3500 (a) as an epoxy compound having two or more glycidyl groups in the molecule ( Nippon Kayaku Co., Ltd., softening point 71°C, epoxy equivalent 207 g/eq.) 513.1 g, acrylic acid as a monocarboxylic acid compound (b) having at least one ethylenic unsaturated group in the molecule (molecular weight: 72.06) 184.0 g, 2.1 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 2.1 g of triphenylphosphine as a reaction catalyst, the reaction was carried out at a temperature of 120°C until the reaction liquid was acidic The value becomes 3 mg･KOH/g or less, and a solution of the reactive epoxy carboxylate compound (R) is obtained. Let this resin solution be A-1. The reaction time at this time was 10 hours.

Synthesis Example 2 In a 1 L flask equipped with a stirring device and a reflux tube, 298.8 g of carbitol acetate as a reaction solvent and NC-6000 (a) as an epoxy compound having two or more glycidyl groups in the molecule ( Nippon Kayaku Co., Ltd., softening point 71°C, epoxy equivalent 208/eq.) 513.7 g, acrylic acid (molecular weight: 72.06) as a monocarboxylic acid compound (b) having one or more ethylenically unsaturated groups in the molecule ) 183.3 g, 2.1 g of 2,6-di-tert-butyl-p-cresol as a thermal polymerization inhibitor, and 2.1 g of triphenylphosphine as a reaction catalyst, the reaction was carried out at a temperature of 120°C until the acid value of the reaction liquid It becomes 3 mg･KOH/g or less, and a solution of the reactive epoxy carboxylate compound (R) is obtained. Let this resin solution be A-2. The reaction time at this time was 17 hours.

Synthesis Example 3 To 75.5 g of the reactive epoxy carboxylic acid ester compound (A-1) solution obtained in Synthesis Example 1, add 12.1 g of ASA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as the polybasic acid anhydride (c), carb 12.3 g of alcohol acetate was reacted at a temperature of 100° C. for 4 hours to obtain a resin solution containing 65% of the unsaturated group-containing polycarboxylic acid resin (A) of the present invention. The acid value of the resin solution is 50.1 mg･KOH/g (solid content acid value: 77.1 mg･KOH/g). Let this resin solution be A-3.

Synthesis Example 4 To 75.5 g of the reactive epoxy carboxylate compound (A-2) solution obtained in Synthesis Example 2, add 12.1 g of ASA (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a polybasic acid anhydride (c), carb 12.3 g of alcohol acetate was reacted at a temperature of 100° C. for 4 hours to obtain a resin solution containing 65% of the unsaturated group-containing polycarboxylic acid resin (A) of the present invention. The acid value of the resin solution is 49.2 mg･KOH/g (solid content acid value: 75.7 mg･KOH/g). Set this resin solution to A-4.

Synthesis Example 5 To 62.0 g of the reactive epoxy carboxylate compound (A-2) solution obtained in Synthesis Example 2, 14.0 g of ASA (manufactured by Fuji Photo Film Wako Pure Chemical Industries, Ltd.) as the polybasic acid anhydride (c), carb 12.3 g of alcohol acetate, reacted at 100°C for 4 hours. Next, 4.1 g of carbitol acetate and 7.6 g of glycidyl methacrylate as a compound (e) having an ethylenic unsaturated group and a glycidyl group in the molecule were added, and the reaction was carried out at a temperature of 120°C for 7 hours. A resin solution containing 65% of the unsaturated group-containing polycarboxylic acid resin (B) of the present invention was obtained. The acid value of the resin solution is 27.6 mg･KOH/g (solid content acid value: 42.4 mg･KOH/g). Set this resin solution to A-5.

Synthesis Example 6 To 82.8 g of the reactive epoxy carboxylate compound (A-1) solution obtained in Synthesis Example 1, THPA (1,2,3,6-tetrahydrophthalic anhydride) was added as the polybasic acid anhydride (c) , New Japan Physical Chemical Co., Ltd.) 7.0 g, carbitol acetate 10.3 g, reacted at 100° C. for 4 hours to obtain a resin solution containing 65% of polycarboxylic acid resin containing unsaturated groups. The acid value of the resin solution is 26.7 mg･KOH/g (solid content acid value: 41.1 mg･KOH/g). Set this resin solution to A-6.

Synthesis Example 7 To 65.1 g of the reactive epoxy carboxylate compound (A-2) solution obtained in Synthesis Example 2, THPA (1,2,3,6-tetrahydrophthalic anhydride) was added as the polybasic acid anhydride (c) , New Japan Physicochemical Co., Ltd.) 16.4 g, carbitol acetate 13.8 g, reacted at 100 ℃ for 4 hours. Next, 1.6 g of carbitol acetate and 3.0 g of glycidyl methacrylate as a compound (e) having an ethylenic unsaturated group and a glycidyl group in the molecule were added, and the reaction was carried out at a temperature of 120°C for 7 hours. A resin solution containing 65% of polycarboxylic acid resin containing unsaturated groups was obtained. The acid value of the resin solution is 50.3 mg･KOH/g (solid content acid value: 77.4 mg･KOH/g). Set this resin solution to A-7.

Synthesis Example 8 To 67.8 g of the reactive epoxy carboxylate compound (A-1) solution obtained in Synthesis Example 1, HTMA (1,2,4-cyclohexanetricarboxylic acid-1, 2-Anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 9.9 g, carbitol acetate 10.53 g, reacted at 100°C for 4 hours. Next, 4.1 g of carbitol acetate and 7.6 g of glycidyl methacrylate as the compound (e) having an ethylenic unsaturated group and a glycidyl group in the molecule were added, and the reaction was carried out at a temperature of 120°C for 10 hours. A resin solution containing 65% of polycarboxylic acid resin containing unsaturated groups was obtained. The acid value of the resin solution is 29.0 mg･KOH/g (solid content acid value: 44.6 mg･KOH/g). Set this resin solution to A-8.

Synthesis Example 9 To 80.6 g of the reactive epoxy carboxylate compound (A-2) solution obtained in Synthesis Example 2, HTMA (1,2,4-cyclohexanetricarboxylic acid-1, 2-Anhydride, manufactured by Mitsubishi Gas Chemical Co., Ltd.) 8.6 g, carbitol acetate 10.8 g, reacted at 100°C for 4 hours to obtain a resin containing 65% of polycarboxylic acid resin containing unsaturated groups Solution. The acid value of the resin solution is 67 mg･KOH/g (solid content acid value: 103 mg･KOH/g). Set this resin solution to A-9.

Example 1, Comparative Example 1 Add 6.0 g of the resin solution containing the unsaturated group-containing polycarboxylic acid resin (A) or (B) of the present invention obtained in Synthesis Example 3 to Synthesis Example 8 as a photopolymerization initiator (C) Irgacure 907 (manufactured by Ciba Specialty Chemicals) 0.27 g and Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) 0.01 g, as a crosslinking agent (D) DPCA-20 (trade name: manufactured by Nippon Kayaku Co., Ltd.) 1.2 g, TPP 0.01 g as a thermosetting catalyst, and diethylene glycol monomethyl ether monoacetate as a concentration adjustment solvent, adjust the solid content concentration to 60%. Thereafter, bisphenol A epoxy resin (trade name: YD-134, manufactured by Nippon Steel & Sumikin Co., Ltd.) was added as a hardener (E) so as to become 120% relative to the carboxyl group and dispersed uniformly. A resist resin composition is obtained.

Each item of the evaluation item is described in detail.

Evaluation of light sensitivity (abbreviated in the table: light sensitivity) The resist resin composition was applied to the rolled copper foil BHY-82F-HA-Ⅴ2 (made by JX Metal) with an applicator to a thickness of 20 μm. A hot air dryer at 80°C dries the coating film for 30 minutes. A step tablet (manufactured by Stouffer: Class 21) is placed on the dried coating film, and a UV irradiator (manufactured by USHIO (ultra-high pressure mercury lamp)) is used to distribute the irradiation amount for curing. After that, spray development was performed using a 1% sodium carbonate aqueous solution as a developer. The irradiation amount when the stepped plate was cured to level 7 was used as the evaluation of light sensitivity. ○ ･･150 mJ/cm ² or less × ･･150 mJ/cm ² or more

Development evaluation (abbreviation in the table: development) The developability refers to spray development using a 1% sodium carbonate aqueous solution as a developer on the coating film before ultraviolet irradiation. The time until the coating film is completely dissolved, the so-called break time is used as the evaluation of developability (unit: second). × ･･Swelling peeling

Evaluation of thermal decomposition resistance (abbreviated in the table: thermal decomposition resistance) The resist resin composition was applied to a rolled copper foil BHY-82F-HA-Ⅴ2 (made by JX Metal) with an applicator to a thickness of 20 μm After drying the coating film with a hot air dryer at 80°C for 30 minutes, an ultraviolet irradiator (manufactured by GS YUASA: CS 30L-1) is used to irradiate ultraviolet rays with an energy of 500 mJ/cm ² . Then, it was cured at 150°C for 30 minutes in an oven to obtain a cured product. Use ferric chloride (Ⅲ) 45° Baume (manufactured by Pure Chemical) to remove copper foil. A sample of 3 mg of the prepared hardened product was prepared, and the temperature at which the weight was reduced by 5% was measured using a TGA/DSC1 manufactured by METTLER in an air flow of 100 ml per minute.

Evaluation of heat-resistant adhesion (abbreviation in the table: heat-resistant adhesion) Apply the resist resin composition to the copper-clad laminate ELC-4762 (manufactured by SUMITOMO BAKELITE) with an applicator to a thickness of 20 μm, and apply a film with a hot air dryer at 80°C After drying for 30 minutes, an ultraviolet irradiator (manufactured by USHIO (ultra-high-pressure mercury lamp)) was used to irradiate ultraviolet rays with 7-level energy using a stepped plate (manufactured by Stouffer: 21 levels). Then, it was cured at 150°C for 30 minutes in an oven to obtain a cured product. After heating the produced hardened product at 165°C for 500 hours, the peeling condition was evaluated using a cross-cut peel test. Evaluation criteria: The previous number of grids (100) is used as the denominator, and the remaining number of grids is used as the numerator.

[Table 1] Example Polycarboxylic acid resin containing unsaturated groups Light sensitivity Developability Thermal decomposition resistance Heat-resistant adhesion Example 1-1 A-3 ○ 16 342 100/100 Example 1-2 A-4 ○ 14 340 100/100 Example 1-3 A-5 ○ 16 333 100/100 Comparative example 1-1 A-6 ○ × 336 3/100 Comparative example 1-2 A-7 × 16 337 10/100 Comparative example 1-3 A-8 ○ 20 333 0/100 Comparative example 1-4 A-9 × 16 341 0/100

From the above results, it can be seen that the photosensitive resin composition of the present invention has high sensitivity and excellent developability, and its cured film is also excellent in adhesion and thermal decomposition resistance after being left at high temperature, so it is particularly suitable for photosensitive resin for printed circuit boards. Resin composition. [Industrial availability]

The photosensitive resin composition of the present invention has excellent developability and light sensitivity in the formation of a coating film by exposure and curing with ultraviolet rays, and the obtained cured product also fully satisfies the adhesion, thermal decomposition resistance, etc. after being left at high temperature , Can be preferably used for light-curing paints, light-curing adhesives, etc., and is particularly suitable for photosensitive resin compositions for printed circuit boards.

no

Claims (11)

An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a reactive epoxy carboxylate compound (R) with a polybasic acid anhydride (c) represented by the following formula (1), the reaction The epoxy carboxylate compound (R) is made by reacting an epoxy compound (a) having two or more glycidyl groups in the molecule with a monocarboxylic acid compound (b) having one or more ethylenically unsaturated groups in the molecule. obtain,

In the formula, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. An unsaturated group-containing polycarboxylic acid resin (A'), which is obtained by reacting a reactive epoxy carboxylate compound (R') with a polybasic acid anhydride (c) represented by the following formula (1), The reactive epoxy carboxylate compound (R') is an epoxy compound having two or more glycidyl groups in the molecule (a), and a monocarboxylic acid compound having one or more ethylenically unsaturated groups in the molecule (b) ) And a monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule,

In the formula, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. An unsaturated group-containing polycarboxylic acid resin (B), which is obtained by combining the unsaturated group-containing polycarboxylic acid resin (A) as described in claim 1 with an ethylenic unsaturated group and a glycidyl group in the molecule Compound (e) is obtained by reaction. An unsaturated group-containing polycarboxylic acid resin (B'), which is obtained by combining the unsaturated group-containing polycarboxylic acid resin (A') as described in claim 2 with an ethylenically unsaturated group and glycidol in the molecule The compound (e) is obtained by reaction. The unsaturated group-containing polycarboxylic acid resin according to any one of claims 1 to 4, wherein the epoxy compound (a) having two or more glycidyl groups in the molecule is the following formula (2 ) The epoxy resin (f);

In the formula, n represents an average value and represents a value of 0-20. The unsaturated group-containing polycarboxylic acid resin according to any one of claims 1 to 4, wherein the epoxy compound (a) having two or more glycidyl groups in the molecule is the following formula (3 ) The epoxy resin (g);

In the formula, Ar is independently one of (I) or (II), the molar ratio of (I) and (II) is (I)/(II) = 1 to 3; G represents glycidyl ; M is the average of the number of repetitions, which is a positive number with 0>m≦5. The unsaturated group-containing polycarboxylic acid resin according to any one of claims 1 to 4, wherein the solid content acid value is 40 mg･KOH/g to 160 mg･KOH/g. A photosensitive resin composition characterized by containing: the unsaturated group-containing polycarboxylic acid resin (A), (A'), (B), or (as described in any one of claims 1 to 7) B'); photopolymerization initiator (C); crosslinking agent (D); and hardener (E). A cured product which is a cured product of the photosensitive resin composition according to claim 8. A base material having a layer of a cured product as described in claim 9. An article having the substrate according to claim 10.