阅读说明：本技术 含有不饱和基的聚羧酸树脂、感光性树脂组合物、硬化物、基材及物品 (Polycarboxylic acid resin containing unsaturated group, photosensitive resin composition, cured product, substrate, and article ) 是由 加贺大树 山本和义 内藤伸彦 锷本麻衣 于 2020-03-11 设计创作，主要内容包括：本发明提供一种对活性能量线的灵敏度、显影性、耐热性、高温放置后的密合性优异的含有不饱和基的聚羧酸树脂、感光性树脂组合物、硬化物、基材及物品。一种含有不饱和基的聚羧酸树脂(A),其为使分子中具有2个以上缩水甘油基的环氧化合物(a)与分子中具有1个以上乙烯性不饱和基的单羧酸化合物(b)的反应产物(R)跟下述式(1)所表示的多元酸酐(d)反应而获得。(式中,R表示氢原子或碳数1～3的烷基)[化1]<Image he="236" wi="390" file="1.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention provides an unsaturated group-containing polycarboxylic acid resin, a photosensitive resin composition, a cured product, a substrate and an article, which are excellent in sensitivity to active energy rays, developability, heat resistance and adhesion after high-temperature standing. An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a reaction product (R) of an epoxy compound (a) having 2 or more glycidyl groups in the molecule and a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule with a polybasic acid anhydride (d) represented by the following formula (1). (formula (II)Wherein R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms) [ formula 1])

1. An unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting a reactive epoxy carboxylate compound (R) obtained by reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule with a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, with a polybasic acid anhydride (c) represented by the following formula (1),

wherein X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

2. An unsaturated group-containing polycarboxylic acid resin (A') obtained by reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule, a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and a monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule with a polybasic acid anhydride (c) represented by the following formula (1),

wherein X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

3. An unsaturated group-containing polycarboxylic acid resin (B) obtained by reacting the unsaturated group-containing polycarboxylic acid resin (A) according to claim 1 with a compound (e) having an ethylenically unsaturated group and a glycidyl group in the molecule.

4. An unsaturated group-containing polycarboxylic acid resin (B ') obtained by reacting the unsaturated group-containing polycarboxylic acid resin (A') according to claim 2 with a compound (e) having an ethylenically unsaturated group and a glycidyl group in the molecule.

5. The polycarboxylic acid resin (B') containing an unsaturated group according to any one of claims 1 to 4, wherein the epoxy compound (a) having 2 or more glycidyl groups in the molecule is an epoxy resin (f) represented by the following formula (2);

wherein n represents an average value and represents a value of 0 to 20.

6. The polycarboxylic acid resin (B') containing an unsaturated group according to any one of claims 1 to 4, wherein the epoxy compound (a) having 2 or more glycidyl groups in the molecule is an epoxy resin (g) represented by the following formula (3);

wherein Ar is independently any one of (I) or (II), and the molar ratio of (I) to (II) is 1-3; g represents a glycidyl group; m is an average of the number of repetitions and is a positive number of 0< m ≦ 5.

7. The polycarboxylic acid resin (B') containing an unsaturated group according to any one of claims 1 to 4, wherein the solid content acid value is from 40 mg-KOH/g to 160 mg-KOH/g.

8. A photosensitive resin composition, comprising: the unsaturated group-containing polycarboxylic acid resin (A), (A '), (B) or (B') according to any one of claims 1 to 7; a photopolymerization initiator (C); a crosslinking agent (D); and a curing agent (E).

9. A cured product of the photosensitive resin composition according to claim 8.

10. A substrate having a layer of a hardened substance according to claim 9.

11. An article having the substrate of claim 10.

Technical Field

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

Background

Printed wiring boards are required to have high precision and high density for the purpose of downsizing and weight reduction of portable devices and improvement of communication speed, and along with this, there is an increasing demand for solder resists for covering the circuits themselves, and as compared with conventional demands, there is a demand for a film-forming material having more tough hardening properties, such as resistance to substrate adhesion, high insulation properties, and electroless gold plating while maintaining heat resistance and thermal stability.

As these materials, a carboxylate compound obtained by reacting a carboxylic acid, a compound having a hydroxyl group, and acrylic acid with a general epoxy resin is known as a material having a low acid value and excellent developability, and as an example thereof, a composition using a resin obtained by reacting a reaction product of a phenol novolac 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, it has been studied to improve heat resistance and developability after curing by changing the kind of acid anhydride which reacts with a reaction product of an epoxy compound and an unsaturated monobasic acid (patent document 4).

When the printed wiring board is provided in the vicinity of an internal combustion engine, a battery, or the like mounted in a vehicle or the like, the cured coating film may be required to have properties of not causing cracks and adhering to the printed wiring circuit board even after being left at a high temperature, and the solder mask (solder mask) under study at present cannot sufficiently cope with these requirements.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent application laid-open No. 7-67008

[ patent document 2] Japanese patent publication No. Hei 7-17737

[ patent document 3] Japanese patent No. 2598346

[ patent document 4] Japanese patent laid-open publication No. 2018-188623

Disclosure of Invention

[ problems to be solved by the invention ]

The purpose of the present invention is to provide a resin composition which has excellent photosensitivity to active energy rays, can form a fine image that can cope with the high functionality of current printed wiring boards, can form a pattern by development with an alkaline aqueous solution, and can obtain a cured film that satisfies the heat resistance required for solder masks and the adhesion after high-temperature exposure, and a cured product thereof.

[ means for solving problems ]

The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found that a resin composition containing a specific unsaturated group-containing polycarboxylic acid resin provides a cured product excellent in adhesion after being left at high temperatures and thermal decomposition resistance, and have completed the present invention. Namely, the present invention provides:

(1) an unsaturated group-containing polycarboxylic acid resin (A) which is a reactive epoxycarboxylate compound (R) obtained by reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule with a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and which is represented by the following formula (1)

[ solution 1]

(wherein X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

A polybasic acid anhydride (c) represented by (a);

(2) an unsaturated group-containing polycarboxylic acid resin (A ') which is a reactive epoxy carboxylate compound (R') obtained by reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule, a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and a monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule, with the following formula (1)

[ solution 2]

(wherein X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

A polybasic acid anhydride (c) represented by (a);

(3) an unsaturated group-containing polycarboxylic acid resin (B) obtained by reacting the unsaturated group-containing polycarboxylic acid resin (A) with a compound (e) having an ethylenically unsaturated group and a glycidyl group in the molecule;

(4) an unsaturated group-containing polycarboxylic acid resin (B ') obtained by reacting the unsaturated group-containing polycarboxylic acid resin (A') with a compound (e) having an ethylenically unsaturated group and a glycidyl group in the molecule;

(5) the unsaturated group-containing polycarboxylic acid resin according to any one of the (1) to (4), wherein the epoxy compound (a) having 2 or more glycidyl groups in the molecule is an epoxy resin (f) represented by the following formula (2);

[ solution 3]

(wherein n represents an average value and represents a value of 0 to 20);

(6) the unsaturated group-containing polycarboxylic acid resin according to any one of the (1) to (4), wherein the epoxy compound is an epoxy resin (g) represented by the following formula (3);

[ solution 4]

(wherein Ar is independently either one of (I) or (II) at a molar ratio of (I) to (II) of 1 to 3; G represents a glycidyl group; m is an average value of the number of repetitions and is a positive number of 0< m ≦ 5);

(7) the polycarboxylic acid resin having an unsaturated group according to any one of the (1) to (6), wherein the solid acid value is from 40 mg. KOH/g to 160 mg. KOH/g).

(8) A photosensitive resin composition comprising the unsaturated group-containing polycarboxylic acid resin (A), (A '), (B) or (B') according to any one of the above (1) to (7), a photopolymerization initiator (C), a crosslinking agent (D) and a curing agent (E).

(9) A cured product of the photosensitive resin composition according to the item (8).

(10) A substrate having a layer of the hardened substance according to the item (9).

(11) An article having the substrate according to (10).

[ Effect of the invention ]

The photosensitive resin composition characterized by containing the unsaturated group-containing polycarboxylic acid resin (a), (a '), (B) or (B') of the present invention, the photopolymerization initiator (C), the crosslinking agent (D) and the curing agent (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 temperatures.

Detailed Description

The epoxy compound (a) having 2 or more glycidyl groups in the molecule used for producing the unsaturated group-containing polycarboxylic acid resin (A), (A '), (B) or (B') of the present invention is particularly preferably an epoxy compound (a) having an epoxy equivalent of 100 to 900 g/equivalent. When the epoxy equivalent is less than 100, the molecular weight of the obtained unsaturated group-containing polycarboxylic acid resin ((a), (a '), (B) or (B')) may be small and film formation may be difficult or sufficient flexibility may not be obtained, and when the epoxy equivalent exceeds 900, the introduction rate of the monocarboxylic acid compound (B) having an ethylenically unsaturated group may be low and the photosensitivity may be lowered.

Specific examples of the epoxy compound (a) having 2 or more glycidyl groups in the molecule include: phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-a type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-a novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, glyoxal (glyoxal) type epoxy resins, heterocyclic epoxy resins, and the like.

Examples of the phenol novolac epoxy resin include: epilon (EPICLON) N-770 (manufactured by DIC (R)), D.E.N438 (manufactured by Dow chemical Co., Ltd.), Epicotte (Epikote)154 (manufactured by Mitsubishi chemical Co., Ltd.), EPPN-201, RE-306 (manufactured by Nippon chemical Co., Ltd.), and the like. Examples of the cresol novolak type epoxy resin include: epilon (EPICLON) N-695 (manufactured by DIC (manufactured by NIPPON CORPORATION)), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Chemicals (manufactured by NIPPON CORPORATION), UVR-6650 (manufactured by Union Carbide Corporation), ESCN-195 (manufactured by Sumitomo chemical industry (manufactured by NIPPON CORPORATION)), and the like.

Examples of the trishydroxyphenylmethane-type epoxy resin include EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon Kagaku K.K.), TACTIX-742 (manufactured by Dow chemical Co., Ltd.), Epicotte (Epikote) E1032H60 (manufactured by Mitsubishi chemical Co., Ltd.), and the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epilon (EPICLON) EXA-7200 (manufactured by DIC corporation) and TACTIX-556 (manufactured by Dow chemical Co., Ltd.).

Examples of the bisphenol epoxy resin include: epicott (Epikote)828, Epikote (Epikote)1001 (manufactured by Mitsubishi chemical Corporation), UVR-6410 (manufactured by Union Carbide Corporation), D.E.R-331 (manufactured by Dow chemical Corporation), YD-8125 (manufactured by Nippon epoxy Corporation), NER-1202, NER-1302 (manufactured by Nippon Chemicals), and other bisphenol-A type epoxy resins, UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Nippon epoxy Corporation), NER-7403, NER-7604 (manufactured by Nippon Chemicals), and the like.

Examples of the diphenol-type epoxy resin include diphenol-type epoxy resins such as NC-3000, NC-3000-H, and NC-3500 (manufactured by Nippon Kasei corporation), dixylenol-type epoxy resins such as YX-4000 (manufactured by Mitsubishi chemical corporation), and YL-6121 (manufactured by Mitsubishi chemical corporation). Examples of the bisphenol A novolak type epoxy resin include Epsilon N-880 (manufactured by DIC corporation), Epicote E157S75 (manufactured by Mitsubishi chemical corporation), and the like.

Examples of the epoxy resin having a naphthalene skeleton include NC-7000 (manufactured by Nippon Chemicals) and EXA-4750 (manufactured by DIC (Co., Ltd.)). Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon chemical Co., Ltd.). Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel (Daicel) stock), and the like. Examples of the heterocyclic epoxy resin include TEPIC (manufactured by nippon chemical industries, japan).

Among these, epoxy resins represented by the following formula (2) or (3) are preferable because epoxy compounds (a) having 2 or more glycidyl groups in the molecule have good heat resistance.

[ solution 5]

(wherein n represents an average value and represents a value of 0 to 20.)

[ solution 6]

(wherein Ar is independently either one of (I) or (II) in a molar ratio of (I) to (II) of 1 to 3; G represents a glycidyl group; m is an average value of the number of repetitions and is a positive number of 0< m ≦ 5.)

The monocarboxylic acid compound (B) having 1 or more ethylenically unsaturated groups in the molecule used for producing the unsaturated group-containing polycarboxylic acid resin (a), (a '), (B) or (B') of the present invention 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. Examples of the acrylic acid compound include: in terms of sensitivity when producing a photosensitive resin composition, half esters of (meth) acrylic acid, a reaction product of (meth) acrylic acid and caprolactone, or cinnamic acid are particularly preferable, for example, (meth) acrylic acid, β -styrylacrylic acid, β -furfurylacrylic acid, and half esters which are equimolar reaction products of a saturated or unsaturated dibasic acid anhydride and a (meth) acrylate derivative having 1 hydroxyl group in 1 molecule, and half esters which are equimolar reaction products of a saturated or unsaturated dibasic acid and a (meth) acrylic acid monoglycidyl derivative.

Specific examples of the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule used for producing the unsaturated group-containing polycarboxylic acid resin (A ') or (B') of the present invention include polyhydroxycarboxylic acids such as dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid and dimethylolhexanoic acid. Particularly preferred examples thereof include dimethylolpropionic acid and dimethylolbutyric acid.

Specific examples of the compound (e) having an ethylenically unsaturated group and a glycidyl group, which is used for producing the unsaturated group-containing polycarboxylic acid resin (B) or (B') of the present invention, include: glycidyl (meth) acrylate, glycidyl etherate of 3-hydroxypropyl (meth) acrylate, glycidyl etherate of 4-hydroxybutyl (meth) acrylate, glycidyl etherate of pentaerythritol triacrylate, glycidyl esterate of maleimidocaproic acid, glycidyl esterate of cinnamic acid, etc., and particularly preferred examples thereof include glycidyl (meth) acrylate and glycidyl etherate of 4-hydroxybutyl (meth) acrylate, and commercially available examples thereof include glycidyl methacrylate (manufactured by Wako pure chemical industries, Ltd.) and 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon chemical Co., Ltd.).

The reaction of the epoxy compound (a) having 2 or more glycidyl groups in the molecule with the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and the reaction of the epoxy compound (a) having 2 or more glycidyl groups in the molecule, the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule with the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule can be carried out in the absence of a solvent or an organic solvent, specifically, ketones such as acetone, ethyl methyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene; esters such as glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, and dialkyl adipate; cyclic esters such as γ -butyrolactone; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; and the crosslinking agent (D) or the like, either alone or in a mixture of organic solvents.

In the reaction of reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule with a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule to obtain a reactive epoxycarboxylate compound (R), the proportion of the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule is preferably 0.8 to 1.2 equivalents based on 1 equivalent of the epoxy compound (a) having 2 or more glycidyl groups in the molecule. When the amount is outside the above range, gelation may occur during the reaction, or the thermal stability of the finally obtained unsaturated group-containing polycarboxylic acid resin (a) may be lowered.

In the reaction of reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule, a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and a monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule to obtain a reactive epoxycarboxylate compound (R'), the addition ratio of the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule to the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule is preferably: the total of the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule and the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule is 80 to 120 equivalent% to 1 equivalent of the epoxy compound (a) having 2 or more glycidyl groups in the molecule. The ratio of the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule to the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule is preferably in the range of 5:95 to 95: 5. When the amount is outside the above range, gelation may occur during the reaction, or the thermal stability of the finally obtained unsaturated group-containing polycarboxylic acid resin (a) may be lowered.

In order to suppress the thermal polymerization reaction, it is preferable to add a thermal polymerization inhibitor in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the reaction product of the epoxy compound (a) having 2 or more glycidyl groups in the molecule, the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and optionally the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule, and the solvent. Examples of the thermal polymerization inhibitor include hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, and 2, 6-di-t-butyl-p-cresol.

In addition, in order to accelerate the reaction, it is preferable to use a catalyst in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the total amount of the reaction product of the epoxy compound (a) having 2 or more glycidyl groups in the molecule, the monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and the monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule, which is added as the case may be, and the solvent, in order to accelerate the reaction. The reaction temperature in this case is 60 ℃ to 150 ℃, and the reaction time is preferably 3 hours to 60 hours. Examples of the catalyst used in this reaction include: dimethylaminopyridine, triethylamine, benzyldimethylamine, triethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, triphenylstibine, methyltriphenylstibine, chromium 2-ethylhexanoate, chromium octoate, zinc 2-ethylhexanoate, zinc octoate, zirconium octoate, dimethyl sulfide, diphenyl sulfide, and the like.

The reaction is preferably carried out until the acid value (solid acid value) becomes 3mg KOH/g or less. The solid acid value is the amount (mg) of potassium hydroxide required to neutralize the acidity of carboxylic acid in 1g of the resin, and the acid value is the amount (mg) of potassium hydroxide required to neutralize 1g of the resin-containing solution, and is measured by a usual neutralization titration method according to Japanese Industrial Standards (JIS) K0070. Further, if the concentration of the resin in the solution is known, the solid acid value can be calculated from the acid value of the solution.

As a preferable molecular weight range of the reactive epoxycarboxylate compound (R) obtained by reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule with a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, or the reactive epoxycarboxylate compound (R') obtained by reacting an epoxy compound (a) having 2 or more glycidyl groups in the molecule, a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and a monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule, the polystyrene equivalent weight average molecular weight in Gel Permeation Chromatography (GPC) is in the range of 500 to 50,000, more preferably 1,000 to 30,000, particularly preferably 1000 to 10,000.

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

[ solution 7]

(wherein X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms)

Among these, preferred is a compound represented by the following formula (4), which is commercially available, and examples thereof include Fuji film and Allyl succinic acid anhydride (ASA) manufactured by Wako pure chemical industries, Ltd.

[ solution 8]

The polybasic acid anhydride (c) may be used alone, but may be used in combination with other polybasic acid anhydrides for the purpose of adjusting the developability, blocking occurrence, etc. of the photosensitive resin composition of the present invention. The combination with other polybasic acid anhydride may be any compound having an acid anhydride structure in its molecule, but succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, itaconic anhydride, 3-methyl-tetrahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, trimellitic anhydride, or maleic anhydride, which is excellent in alkali aqueous solution developability, heat resistance, hydrolysis resistance, and the like, is particularly preferable.

The reaction of adding the polybasic acid anhydride (c) can be carried out by adding the polybasic acid anhydride (c) to a reaction solution which gives a reaction product of an epoxy compound (a) having 2 or more glycidyl groups in the molecule, a monocarboxylic acid compound (b) having 1 or more ethylenically unsaturated groups in the molecule, and, if necessary, a monocarboxylic acid compound (d) having at least 2 hydroxyl groups in the molecule. The amount of addition is preferably calculated so that the solid acid value of the finally obtained unsaturated group-containing polycarboxylic acid resin (A) is 40mg KOH/g to 160mg KOH/g. When the solid acid value is less than 40 mg. KOH/g, the alkali aqueous developability of the photosensitive resin composition of the present invention is significantly reduced, and in the worst case, the development may be impossible, and when the solid acid value exceeds 160 mg. KOH/g, the developability may become too high, and the patterning may be impossible. The reaction temperature is, for example, 60 ℃ to 150 ℃, 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. Specific examples of the photopolymerization initiator (C) include: benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenones such as acetophenone, 2-diethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [ 4- (methylthio) phenyl ] -2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2, 4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone, 4-benzoyl-4 '-methyldiphenyl sulfide, and 4,4' -bismethylaminobenzophenone; and phosphine oxides such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4, 6-trimethylbenzoyl) -phenylphosphine oxide.

These may be used alone or in the form of a mixture of 2 or more, and may be used in combination with a tertiary amine such as triethanolamine or methyldiethanolamine, or an accelerator such as ethyl N, N-dimethylaminobenzoate or a benzoic acid derivative such as isoamyl N, N-dimethylaminobenzoate.

In the photosensitive resin composition of the present invention, a crosslinking agent (D) may be used as necessary. Specific examples of the crosslinking agent (D) include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, carbitol (meth) acrylate, acryloylmorpholine, half esters which are reaction products of hydroxyl group-containing (meth) acrylates (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1, 4-butanediol mono (meth) acrylate, etc.) and anhydrides of polycarboxylic acid compounds (e.g., succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.), polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxy tri (meth) acrylate, trimethylolpropane mono (meth) acrylate, propylene glycol mono (, Glycerol polypropoxy tri (meth) acrylate, di (meth) acrylate of caprolactone adduct of neopentyl glycol hydroxytrimethylacetate (e.g., Kayarad HX-220, HX-620, etc., manufactured by Kayaku chemical Co., Ltd.), pentaerythritol tetra (meth) acrylate, poly (meth) acrylate of a reaction product of dipentaerythritol and caprolactone, dipentaerythritol poly (meth) acrylate, monoglycidyl compounds or polyglycidyl compounds (e.g., butyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, glycerol polyglycidyl ether, glycerol polyethoxy glycidyl ether, trimethylolpropane polyglycidyl ether, Trimethylolpropane polyethoxy polyglycidyl ether, etc.) and (meth) acrylic acid, and the like.

In the photosensitive resin composition of the present invention, a curing agent (E) may be used as needed. Examples of the curing agent (E) include epoxy compounds and oxazine compounds. The curing agent (E) is particularly preferably used in the case where a cured coating film having a stronger chemical resistance is to be obtained by reacting with a carboxyl group or a hydroxyl group remaining in the resin coating film after photo-curing by heating.

Specific examples of the epoxy compound of the curing agent (E) include: phenol novolac type epoxy resins, cresol novolac type epoxy resins, trishydroxyphenylmethane type epoxy resins, dicyclopentadiene phenol type epoxy resins, bisphenol-a type epoxy resins, bisphenol-F type epoxy resins, biphenol type epoxy resins, bisphenol-a novolac type epoxy resins, glyoxal type epoxy resins, naphthalene skeleton-containing epoxy resins, heterocyclic epoxy resins, and the like.

Examples of the phenol novolac epoxy resin include: epilon (EPICLON) N-770 (manufactured by DIC (R)), D.E.N438 (manufactured by Dow chemical Co., Ltd.), Epicotte (Epikote)154 (manufactured by Mitsubishi chemical Co., Ltd.), RE-306 (manufactured by Nippon chemical Co., Ltd.), and the like. Examples of the cresol novolak type epoxy resin include: epilon (EPICLON) N-695 (manufactured by DIC (manufactured by NIPPON CORPORATION)), EOCN-102S, EOCN-103S, EOCN-104S (manufactured by Nippon Chemicals (manufactured by NIPPON CORPORATION), UVR-6650 (manufactured by Union Carbide Corporation), ESCN-195 (manufactured by Sumitomo chemical industry (manufactured by NIPPON CORPORATION)), and the like.

Examples of the trishydroxyphenylmethane-type epoxy resin include: EPPN-503, EPPN-502H, EPPN-501H (manufactured by Nippon chemical Co., Ltd.), TACTIX-742 (manufactured by Dow chemical Co., Ltd.), Epicotte (Epikote) E1032H60 (manufactured by Mitsubishi chemical Co., Ltd.), and the like. Examples of the dicyclopentadiene phenol type epoxy resin include Epilon (EPICLON) EXA-7200 (manufactured by DIC corporation) and TACTIX-556 (manufactured by Dow chemical Co., Ltd.).

Examples of the bisphenol epoxy resin include: epicott (Epikote)828, Epikote (Epikote)1001 (manufactured by Mitsubishi chemical Corporation), UVR-6410 (manufactured by Union Carbide Corporation), D.E.R-331 (manufactured by Dow chemical Corporation), YD-8125 (manufactured by Nippon epoxy Corporation), NER-1202, NER-1302 (manufactured by Nippon chemical Corporation), and other bisphenol-A type epoxy resins, UVR-6490 (manufactured by Union Carbide Corporation), YDF-8170 (manufactured by Nippon epoxy Corporation), NER-7403, NER-7604 (manufactured by Nippon chemical Corporation), and other bisphenol-F type epoxy resins.

Examples of the diphenol type epoxy resin include: bisphenol type epoxy resins such as NC-3000 and NC-3000H (manufactured by Nippon chemical Co., Ltd.), bixylenol type epoxy resin such as YX-4000 (manufactured by Mitsubishi chemical Co., Ltd.), YL-6121 (manufactured by Mitsubishi chemical Co., Ltd.), and the like. Examples of the bisphenol a novolac-type epoxy resin include: epilon (EPICLON) N-880 (manufactured by DIC (R)), Epicott (Epikote) E157S75 (manufactured by Mitsubishi chemical (R)), and the like.

Examples of the epoxy resin having a naphthalene skeleton include: NC-7000 and NC-7300 (both manufactured by Nippon Chemicals, Ltd.), EXA-4750 (manufactured by DIC, Ltd.), and the like. Examples of the glyoxal type epoxy resin include GTR-1800 (manufactured by Nippon chemical Co., Ltd.). Examples of the alicyclic epoxy resin include: EHPE-3150 (manufactured by Daicel stock), and the like. Examples of heterocyclic epoxy resins include: TEPIC-L, TEPIC-H, TEPIC-S (all manufactured by Nissan chemical Co., Ltd.), and the like.

Specific examples of the oxazine compound of the curing agent (E) include: b-m type benzoxazine, P-a type benzoxazine and B-a type benzoxazine (all manufactured by four chemical industries).

The amounts of the components (a), (a ') or (B), (C), (D) and (E) contained in the photosensitive resin composition of the present invention are preferably 10 to 80% by weight of the component (a), (a') or (B), 0 to 40% by weight of the component (C), 0 to 70% by weight of the component (D), 0 to 40% by weight of the component (E), and further 0.5 to 30% by weight of the component (C), 5 to 60% by weight of the component (D), and 5 to 30% by weight of the component (E), based on 100% by weight of nonvolatile components of the photosensitive resin composition.

Further, various additives such as fillers such as talc, barium sulfate, calcium carbonate, magnesium carbonate, barium titanate, aluminum hydroxide, alumina, silica, clay, etc. may be added as necessary for the purpose of improving various properties of the composition; thixotropy imparting agents such As Erythemos (AEROSIL); colorants such as phthalocyanine blue, phthalocyanine green and titanium oxide; silicone, fluorine-based leveling agents or defoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether.

The curing agent (E) may be mixed in advance with the photosensitive resin composition of the present invention, or may be mixed before application to a printed wiring board. That is, a two-pack type is prepared by mixing the above-mentioned components (A), (A') or (B) as a main component, and a base solution such as an epoxy curing accelerator and a curing agent solution mainly containing the curing agent (E) in use.

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

A dry film using the photosensitive resin composition of the present invention can be obtained, for example, as follows. That is, when a liquid resin composition is used, the photosensitive resin composition of the present invention is applied to a support film by a method such as screen printing, spraying, roll coating, electrostatic coating, or curtain coating in a film thickness of 5 to 160 μm, and the coating film is dried at a temperature of usually 50 to 110 ℃, preferably 60 to 100 ℃, to form a coating film. Thereafter, a protective film is attached to the coating film to obtain a dry film.

The photosensitive resin composition (liquid or film) of the present invention is useful as an insulating material between layers of electronic components, a resist material such as a solder mask or a cover layer for connecting an optical waveguide between optical components or a printed circuit board, and can be used as a color filter, a printing ink, a sealant, a coating material, a coating agent, an adhesive, or the like.

The cured product of the present invention is obtained 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 a conventional method by irradiation with energy rays such as ultraviolet rays. For example, when ultraviolet rays are irradiated, an ultraviolet ray generating device such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, or an ultraviolet ray emitting laser (excimer laser, etc.) may be used.

The cured product of the present invention can be used for an electric/electronic/optical component such as a printed circuit board, an optoelectronic circuit board, or an optical circuit board as a resist film, an interlayer insulating material for a build-up (build up) method, or an optical waveguide. Specific examples thereof include computers, home electric appliances, and portable devices. The thickness of the hardened layer is about 0.5 to 160 μm, preferably about 1 to 100 μm.

The printed wiring board using the photosensitive resin composition of the present 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 formed by attaching a resin layer to the entire surface of a printed circuit board using a heating roller having a temperature of 50 to 100 ℃ while peeling off the protective film. Next, the pattern is formed directly or indirectly at a rate of usually 10mJ/cm through a photomask having a circuit pattern formed thereon²～2000mJ/cm²The coating film is irradiated with high-energy rays such as ultraviolet rays at right and left intensities, and the unexposed portions are developed by spraying, dipping with a wave, brushing, scraping, or the like with a developer described later. After washing with water and drying as necessary, ultraviolet rays are further irradiated as necessary, and then heat treatment is performed at a temperature of usually 100 to 200 ℃, preferably 140 to 180 ℃, whereby a printed wiring board which is excellent in gold plating property and satisfies various properties such as heat resistance, solvent resistance, acid resistance, adhesiveness, and flexibility as described later can be obtained. When a liquid resin composition is used, the composition is applied to a substrate for printed wiring by a method such as screen printing, spraying, roll coating, electrostatic coating, or curtain coatingThe photosensitive resin composition of the present invention is applied in a film thickness of 5 to 160 μm, and the coating film is dried at a temperature of usually 50 to 110 ℃ and preferably 60 to 100 ℃ to form a coating film. Then, the resultant is directly or indirectly exposed to light at a concentration of usually 10mJ/cm through a photomask having an exposure pattern such as negative film (negative film) formed thereon²～2000mJ/cm²The coating film is irradiated with high-energy rays such as ultraviolet rays at right and left intensities, and the unexposed portions are developed by spraying, dipping with a wave, brushing, scraping, or the like with a developer described later. Thereafter, if necessary, ultraviolet rays are further irradiated, and then heat treatment is performed at a temperature of usually 100 to 200 ℃, preferably 140 to 180 ℃, whereby a printed wiring board having a permanent protective film which is excellent in gold plating property and satisfies various properties such as heat resistance, solvent resistance, acid resistance, and adhesiveness can be obtained.

As the aqueous alkaline solution used for the development, an aqueous inorganic alkaline solution such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, or potassium phosphate, or an aqueous organic alkaline solution such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, or triethanolamine may be used.

Examples of the substrate having a layer of the cured product of the present invention include a printed circuit board, a flexible circuit board, an optoelectronic circuit board, and an optical circuit board, each of which has a resist film, an interlayer insulating film or a dry film for a lamination process, and an optical waveguide film.

Examples of the article 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.