JP2010066444A - Alkali-developable curable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an alkali-developable photo- and/or heat-curable composition having excellent storage stability and giving an excellent cured film which satisfies such properties as hardness, heat resistance, chemical resistance, electroless gold plating resistance and electric insulation; and to provide a cured product thereof. <P>SOLUTION: The alkali-developable curable composition contains: (A) a carboxyl group-containing epoxy resin having an acid number of 20-150 mgKOH/g and an epoxy equivalent of ≤3,000 g/eq.; (B) a photosensitive (meth)acrylate compound; and (C) a photopolymerization initiator. The epoxy resin (A) is obtained by: reacting epoxy groups in a resin (a) having two or more epoxy groups per molecule with a monocarboxylic acid (b) in a ratio of 0.3-0.9 mol to 1 equiv. epoxy group; reacting epoxy groups in the resultant reaction product (c) with a polybasic acid (d) in a ratio of 0.2-5 mols to 1 equiv. epoxy group; and further reacting epoxy groups in the resultant reaction product (e) with a monocarboxylic acid (f) in a ratio of 0.0-5.0 mols to 1 equiv. epoxy group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a curable composition used for forming a solder resist or the like of a printed wiring board, and more particularly to a curable composition containing a carboxyl group-containing epoxy resin capable of alkali development and a cured product thereof.

At present, unsaturated group and carboxyl group-containing compounds that can be developed with a dilute aqueous alkali solution are mainly used as curable compounds used for forming a solder resist of a printed wiring board in consideration of environmental problems. As such a compound, a curable compound obtained by adding an acid anhydride to a reaction product of an epoxy resin and an unsaturated group-containing monocarboxylic acid is generally used.
For example, Patent Document 1 discloses a curable compound obtained by adding an acid anhydride to a reaction product of a novolak type epoxy resin and an unsaturated group-containing monocarboxylic acid. Patent Document 2 discloses an alcoholic resin obtained by reacting an aromatic epoxy resin having two glycidyl groups in one molecule with an aromatic alcohol resin having two phenolic hydroxyl groups in one molecule. A curable compound in which an epihalohydrin is reacted with a secondary hydroxyl group and an unsaturated group-containing monocarboxylic acid and then an acid anhydride is added to the resulting reaction product is disclosed.
In addition to these, several curable compounds have been proposed and are currently widely used in the production of actual printed wiring boards.

  The carboxyl group-containing compound is difficult to thermally cure at 150 ° C., which is a temperature for forming a solder resist. Such a compound is generally thermally cured at 150 ° C. by blending a polyfunctional epoxy resin. However, since polyfunctional epoxy resins have high reactivity, mixtures with carboxyl group-containing compounds have a short shelf life (storage life) and tend to thicken before application to circuit board blanks. Difficult to compose. Therefore, in general, the main agent solution mainly composed of carboxyl group-containing compound and the curing agent solution mainly composed of polyfunctional epoxy resin are stored separately, and these are mixed and used at the time of use. was there.

As a method for solving such a problem, Patent Document 3 discloses a carboxyl group-containing compound, a polyfunctional epoxy resin having a 1,3-dioxolane ring obtained by partially adding a ketone to a polyfunctional epoxy resin, and In addition, Patent Document 4 discloses a mixture of a carboxyl group-containing compound, a polyfunctional epoxy resin, an acid, and a ketone. However, these mixtures have a drawback that the shelf life is shortened by the reaction of the carboxyl group-containing compound with the polyfunctional epoxy resin having a 1,3-dioxolane ring as the ketone evaporates.
JP-A 61-243869 JP-A-5-32746 JP 2007-176987 A JP 2007-256742 A

  The present invention has been made in view of the problems as described above, and is excellent in storage stability and excellent in sufficiently satisfying characteristics such as hardness, heat resistance, chemical resistance, electroless gold plating resistance, and electrical insulation. It is an object to provide a light and / or thermosetting composition and a cured product thereof from which a cured film can be obtained.

The curable composition capable of being developed with an alkali according to the present invention, which has been made to solve the above-mentioned problems, is (A) an epoxy group in an epoxy group of a resin (a) having two or more epoxy groups in one molecule. The monocarboxylic acid (b) is reacted at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent, and the epoxy group of the obtained reaction product (c) is added to the epoxy group with 1 equivalent. The basic acid (d) is reacted at a ratio of 0.2 to 5 mol, and the monocarboxylic acid (f) is added to the epoxy group of the obtained reaction product (e) with respect to 1 equivalent of the epoxy group. An acid value of 20 to 150 mg KOH / g, epoxy equivalent of 3000 g / eq., Obtained by reacting at a ratio of 0 to 5.0 mol. The following carboxyl group-containing epoxy resins,
It contains (B) a photosensitive (meth) acrylate compound, and (C) a photopolymerization initiator.

  According to a specific and preferred embodiment of the present invention, the carboxyl group-containing epoxy resin which is one component of the curable composition is composed of the monocarboxylic acid (b) and the monocarboxylic acid (f) having an unsaturated group. Or the monocarboxylic acid (b) is an unsaturated group-containing monocarboxylic acid, the monocarboxylic acid (f) is a monocarboxylic acid not containing an unsaturated group, or the monocarboxylic acid (b) is unsaturated. Monocarboxylic acid containing no group, monocarboxylic acid (f) is an unsaturated group-containing monocarboxylic acid, or monocarboxylic acid (b) and monocarboxylic acid (f) are monocarboxylic acids containing no unsaturated group Is an acid, or the monocarboxylic acid (b) and / or (f) is a mixture of an unsaturated group-containing monocarboxylic acid and a monocarboxylic acid not containing an unsaturated group, in particular, two or more epoxies per molecule. Resins having a group (a) is a novolak epoxy resin.

  According to the present invention, it is possible to obtain a cured film that is excellent in storage stability as a one-pack type, can be developed with an alkali, and has excellent hardness, heat resistance, chemical resistance, electroless gold plating resistance, electrical insulation, and the like. Can do.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have made a partial addition reaction of a monocarboxylic acid to an epoxy group of a resin having two or more epoxy groups in one molecule, and then the rest A composition containing a carboxyl group-containing epoxy resin obtained by partially adding a polybasic acid to an epoxy group of the product and further partially adding a monocarboxylic acid to the remaining epoxy group is excellent in storage stability. In addition, the inventors have found that a cured product having excellent developability, hardness, heat resistance, chemical resistance, electroless gold plating resistance, and electrical insulation properties can be obtained, and have completed the present invention.

  That is, the carboxyl group-containing epoxy resin which is one component of the curable composition of the present invention partially adds the monocarboxylic acid (b) to the resin (a) having two or more epoxy groups in one molecule. Thus, the polybasic acid (d) can be partially added to the epoxy group of the reaction product (c) without gelation, and the monocarboxylic acid (f) can be partially added to the remaining epoxy group. As a result, an epoxy group and a carboxyl group coexist in one molecule, but they are in a position where they are difficult to react with each other, so that they are excellent in storage stability, and also have unsaturated groups and carboxyls. Group and epoxy group are located at the end of the side chain, so they are highly reactive, and such carboxyl group-containing epoxy resins are photosensitive (meth) acrylate compounds Fine photopolymerization initiator composition was added, the high crosslinking density, a cured product having excellent properties.

  In the production of the carboxyl group-containing compound (A), a carboxyl group is obtained by partial addition of the polybasic acid (d) to the epoxy group of the reaction product (c), but the reaction product (c) has a polybasic acid. Not all (d) reacts. In that case, a mixture of the reaction product (e) and the polybasic acid (d) is obtained in the presence of an unreacted epoxy group. Thereafter, the monocarboxylic acid (f) can be reacted with the epoxy group of the reaction product (e). Thus, the carboxyl group-containing epoxy resin of the present invention may be obtained in a state of being mixed with an unreacted polybasic acid (d) and an unreacted monocarboxylic acid (f). ) And unreacted monocarboxylic acid (f), and is excellent in storage stability without gelation regardless of the presence or absence.

Hereinafter, the light and / or thermosetting composition according to the present invention will be described in detail.
First, as described above, the carboxyl group-containing epoxy resin (A) which is one component of the present invention has 1 equivalent of epoxy group to the epoxy group of resin (a) having two or more epoxy groups in one molecule. The monocarboxylic acid (b) is reacted at a ratio of 0.3 to 0.9 mol, and the polybasic acid is added to the epoxy group of the obtained reaction product (c) with respect to 1 equivalent of the epoxy group. (D) is reacted at a ratio of 0.2 to 5 mol, and the monocarboxylic acid (f) is added to the epoxy group of the obtained reaction product (e) in an amount of 0.0 to 1 equivalent to 1 equivalent of the epoxy group. Although it is obtained by reacting at a ratio of 5.0 mol, each reaction is easily carried out in a solvent or without solvent using a catalyst as described later.

  Examples of the resin (a) having two or more epoxy groups in one molecule include, for example, Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, and Dainippon Ink and Chemicals, manufactured by Japan Epoxy Resin Co., Ltd. Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., D. Chemicals manufactured by Dow Chemical Co., Ltd. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Chemical Co., Ltd. bisphenol A type epoxy resins such as Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128 (all trade names); manufactured by Japan Epoxy Resin Co., Ltd. Epicort YL903, Daikoku Ink Chemical Co., Ltd. Epicron 152, Epicron 165, Toto Kasei Co., Ltd. Epototo YDB-400, YDB-500, Dow Chemical Co., Ltd. E. R. 542, brominated epoxy resins such as Sumi-epoxy ESB-400 and ESB-700 (both trade names) manufactured by Sumitomo Chemical Co., Ltd .; Epicoat 152, Epicoat 154, Dow Chemical (manufactured by Japan Epoxy Resin Co., Ltd.) D. manufactured by Co., Ltd. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865, manufactured by Dainippon Ink & Chemicals, Inc. Epototo YDCN-701, YDCN-704, manufactured by Tohto Kasei Co., Ltd., manufactured by Nippon Kayaku Co., Ltd. Novolak type epoxy such as EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220 (all trade names) manufactured by Sumitomo Chemical Co., Ltd. Resins; Bisphenols such as Epiklon 830 manufactured by Dainippon Ink & Chemicals, Ltd., Epicoat 807 manufactured by Japan Epoxy Resin, Epototo YDF-170, YDF-175, YDF-2004 manufactured by Toto Kasei Co., Ltd. (all trade names) F-type epoxy resin; Epototo ST-2004, ST-2 manufactured by Tohto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as 07 and ST-3000 (all are trade names); Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YH-434 manufactured by Toto Kasei Co., Ltd., Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as Sumi-Epoxy ELM-120 (both trade names) manufactured by Daicel Chemical Industries Ltd. Alicyclic epoxy resin such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; Japan Epoxy Resin Co., Ltd. YL-933 manufactured by Nippon Kayaku Co., Ltd., EPPN-501 manufactured by Nippon Kayaku Co., Ltd., trihydroxyphenylmethane type epoxy resin such as EPPN-502 (both trade names); YL-6056 manufactured by Japan Epoxy Resin Co., Ltd., YX -4000, YL-6121 (both trade names) and other bixylenol type or biphenol type epoxy resins or EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by Dainippon Ink & Chemicals Co., Ltd. (all trade names), etc. Bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan Epoxy Resin Co., Ltd .; Tetraphenylol such as Epicoat YL-931 (trade name) manufactured by Japan Epoxy Resin Co., Ltd. Ethane type epoxy resin; heterocyclic epoxy resin such as TEPIC (trade name) manufactured by Nissan Chemical Co., Ltd .; diglycidyl phthalate resin such as Blemmer DGT (trade name) manufactured by Nippon Oil &Fats; Toto Kasei Co., Ltd. Tetraglycidylxylenoylethane resin such as ZX-1063 (trade name) manufactured by Nippon Steel Chemical Co., Ltd .; ESN-190, ESN- manufactured by Nippon Steel Chemical Co., Ltd. 360, Naphthalene group-containing epoxy resins such as HP-4032, EXA-4750, EXA-4700 (all trade names) manufactured by Dainippon Ink & Chemicals, Inc .; HP-7200 manufactured by Dainippon Ink & Chemicals, Inc. Epoxy resin having a dicyclopentadiene skeleton such as HP-7200H (all trade names); Glycidyl methacrylate copolymer epoxy such as CP-50S and CP-50M (all trade names) manufactured by NOF Corporation Resin; Copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epihalohydrin is reacted with an alcoholic secondary hydroxyl group obtained by reacting 1,5-dihydroxynaphthalene and bisphenol A type epoxy resin. Polyfunctional epoxy resin obtained (International Publication WO 01/024774); Examples thereof include, but are not limited to, epoxy resins having a 1,3-dioxolane ring obtained by addition reaction of a ketone with a part of a poxy group (Japanese Patent Laid-Open No. 2007-176987). These epoxy resins can be used individually or in mixture of 2 or more types.

  Among these epoxy resins, a resin having 3 or more epoxy groups in one molecule is preferable, and a novolac type epoxy resin is more preferable.

  The epoxy resin (a) is partially reacted with the monocarboxylic acid (b). In this case, the reaction is preferably performed in a solvent using a polymerization inhibitor and a catalyst, and the reaction temperature is preferably 50. It is -150 degreeC, More preferably, it is 70-120 degreeC. The monocarboxylic acid (b) is reacted with the epoxy group of the epoxy resin (a) at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent of the epoxy group. 8 moles. When the monocarboxylic acid (b) is less than 0.3 mol, gelation occurs in the subsequent reaction.

  Representative examples of the monocarboxylic acid (b) include unsaturated groups such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, and β-furfurylacrylic acid. Containing monocarboxylic acid, formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, valeric acid, trimethylacetic acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecyl Acids, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid and other saturated aliphatic monocarboxylic acids, benzoic acid, alkylbenzoic acid, alkylaminobenzoic acid, halogenated benzoic acid, phenylacetic acid, anisic acid Aromatic monocarboxylic acids such as benzoylbenzoic acid and naphthoic acid The present invention is not limited to these. These monocarboxylic acids can be used alone or in admixture of two or more. Particularly preferred here are acrylic acid, methacrylic acid, benzoic acid and acetic acid.

  Examples of the reaction solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate , Ethylene glycol monobutyl ether Acetates such as cetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane, decane, etc. Aliphatic hydrocarbons: Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha are exemplified, but not limited thereto. These organic solvents can be used alone or in admixture of two or more.

  Examples of the reaction catalyst include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, phosphorus compounds such as triphenylphosphine, naphthenic acid, and laurin. Examples include, but are not limited to, metal salts of organic acids such as lithium, chromium, zirconium, potassium, and sodium of acid, stearic acid, oleic acid, and octoenoic acid. These reaction catalysts can be used alone or in admixture of two or more.

  Examples of the polymerization inhibitor include, but are not limited to, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, phenothiazine, and the like. These polymerization inhibitors can be used alone or in admixture of two or more.

  Further, the polybasic acid (d) is added to the epoxy group of the reaction product (c), and the reaction temperature is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The polybasic acid (d) is reacted with the epoxy group of the reaction product (c) at a ratio of 0.2 to 5.0 mol with respect to 1 equivalent of the epoxy group, preferably 0.2 to 2 0.0 mole. When the polybasic acid (d) exceeds 5.0 mol, a large amount of unreacted polybasic acid (d) remains, which adversely affects the cured film of the curable composition of the present invention.

  Representative examples of the polybasic acid (d) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, Examples include, but are not limited to, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, methanetricarboxylic acid, tricarballylic acid, benzenetricarboxylic acid, and benzenetetracarboxylic acid. These polybasic acids can be used alone or in admixture of two or more. Among these, dibasic acids are preferable, and malonic acid, glutaric acid, adipic acid, tetrahydrophthalic acid and phthalic acid are particularly preferable.

  After the monocarboxylic acid (b) and then the polybasic acid (d) are added to the epoxy resin (a), the monocarboxylic acid (f) is added to the remaining epoxy group. The role of the addition is to suppress the polymerization of the reaction product (e). However, depending on the reaction conditions and / or the type of polybasic acid (d), the monocarboxylic acid (f) is not necessary. The temperature at which the reaction product (e) and the monocarboxylic acid (f) are reacted is preferably 50 to 150 ° C, more preferably 70 to 120 ° C. The epoxy group of the reaction product (e) is reacted with the monocarboxylic acid (f) at a ratio of 0.0 to 5.0 mol with respect to 1 equivalent of the epoxy group, preferably 0.0 to 2 0.0 mole. When the monocarboxylic acid (f) exceeds 5.0 mol, a large amount of unreacted monocarboxylic acid (f) remains, which adversely affects the cured film of the curable composition of the present invention.

  As monocarboxylic acid (f), the same thing as monocarboxylic acid (b) is mentioned. These monocarboxylic acids can be used alone or in admixture of two or more. Particularly preferred here are acrylic acid, methacrylic acid, benzoic acid and acetic acid.

  The acid value of the carboxyl group-containing epoxy resin (A) is 20 to 150 mgKOH / g, preferably 30 to 100 mgKOH / g. However, when unreacted polybasic acid (d) and monocarboxylic acid (f) are present, if the acid value of the carboxyl group-containing epoxy resin is 150 mgKOH / g, the solid content acid value as a whole Over 150 mg KOH / g. However, unless the unreacted carboxylic acid is contained in a large amount, the cured film of the curable composition of the present invention will not be adversely affected.

  The epoxy equivalent of the reaction product was 3000 g / eq. Or less, preferably 2800 g / eq. It is as follows. Epoxy equivalent is 3000 g / eq. If it exceeds 1, thermosetting property cannot be obtained sufficiently. Accordingly, the acid value is 20 to 150 mgKOH / g, and the epoxy equivalent is 3000 g / eq. In the following cases, the curable composition of the present invention containing the carboxyl group-containing epoxy resin (A) or a mixture of the resin and unreacted carboxylic acid is excellent in storage stability, and the cured product has excellent characteristics. Indicates.

  Examples of the photosensitive (meth) acrylate compound (B) include hydroxyl group-containing acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate. Water-soluble acrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane tri (meth) acrylate, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate; Multifunctional alcohols such as trimethylolpropane and hydrogenated bisphenol A or polyhydric phenols such as bisphenol A and biphenol Acrylates of ethylene oxide adduct and / or propylene oxide adduct; polyfunctional or monofunctional polyurethane acrylate which is an isocyanate modification of the above hydroxyl group-containing acrylate; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol Epoxy acrylates that are (meth) acrylic acid adducts of novolak epoxy resins; caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolaclone-modified dipentaerythritol acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol ester diacrylate, etc. Acrylates, and methacrylates corresponding to the above acrylates. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable. These photosensitive (meth) acrylate compounds can be used alone or in admixture of two or more. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the carboxyl group-containing epoxy resin (A). The photosensitive (meth) acrylate compound which is liquid at room temperature plays a role of adjusting the composition to a viscosity suitable for various coating methods and assisting in solubility in an alkaline aqueous solution, in addition to the purpose of increasing photoreactivity. However, if a large amount of liquid photosensitive (meth) acrylate compound is used at room temperature, the dryness of the coating film cannot be obtained, and the characteristics of the coating film tend to deteriorate. It is not preferable. The blending amount of the photosensitive (meth) acrylate compound (B) is preferably 100 parts by mass or less with respect to 100 parts by mass of the carboxyl group-containing epoxy resin (A). In this specification, “(meth) acrylate” is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

  Examples of the photopolymerization initiator (C) include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, Acetophenones such as 2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Aminoacetophenones such as dimethylamino-1- (4-morpholinophenyl) -butan-1-one, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1- Chloro Anthraquinones such as nthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzoylper Organic peroxides such as oxide and cumene peroxide; 2,4,5-triarylimidazole dimer; Riboflavin tetrabutyrate; Thiols such as 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Compound; Organic halogen compounds such as 2,4,6-tris-s-triazine, 2,2,2-tribromoethanol, tribromomethylphenylsulfone; benzophenone, 4,4'-bisdie Benzophenones or xanthones such as Le aminobenzophenone; and 2,4,6-trimethylbenzoyl diphenylphosphine oxide. These known and commonly used photopolymerization initiators can be used alone or in admixture of two or more. Further, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl Photoinitiator aids such as tertiary amines such as -4-dimethylaminobenzoate, triethylamine, triethanolamine can be added. A titanocene compound such as CGI-784 (manufactured by Ciba Specialty Chemicals Co., Ltd.) having absorption in the visible light region can also be added to promote the photoreaction. Particularly preferred photopolymerization initiators are 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpholinophenyl) -butan-1-one and the like, but is not particularly limited thereto, and absorbs light in the ultraviolet light or visible light region, such as (meth) acryloyl group As long as the unsaturated group is radically polymerized, it is not limited to a photopolymerization initiator and a photoinitiator aid, and can be used alone or in admixture of two or more. And the usage-amount has the preferable ratio of 0.5-25 mass parts with respect to 100 mass parts of said carboxyl group-containing epoxy resins (A).

Moreover, the curable composition of this invention can mix | blend a thermosetting component to such an extent that storage stability is not impaired. For example, oxetane resin, the above-mentioned epoxy resin, etc. are mentioned.
Examples of the oxetane resin include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) propanediylbis (oxymethylene)) bis- ( 3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3- Bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol Bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3 Oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3) -Oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ) Ether. These thermosetting components can be used alone or in admixture of two or more.

  Moreover, since the curable composition of this invention is excellent in storage stability, the said thermosetting component can be mix | blended and it can also be made into a 2 liquid type. The blending amount is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the carboxyl group-containing epoxy resin (A).

Moreover, the curable composition of this invention can mix | blend an organic solvent in order to dissolve a carboxyl group-containing epoxy resin (A), and to adjust a composition to the viscosity suitable for the coating method.
Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether , Glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Monoethyl ether Acetates such as cetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; aliphatic hydrocarbons such as octane and decane; petroleum Examples include petroleum solvents such as ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These organic solvents can be used alone or in admixture of two or more. The compounding quantity of the organic solvent can be made into arbitrary quantity according to a use etc.

  Furthermore, the curable composition of this invention can mix | blend a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzyl Amine compounds such as amine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine can be used. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Co., Ltd., U-CAT3503N manufactured by San Apro Co., Ltd. U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, as long as it is for improving thermosetting properties, it is not limited to these, as long as it is a curing catalyst for a compound having a cyclic ether, or a compound that promotes the reaction between a compound having a cyclic ether and a carboxylic acid, It can use individually or in mixture of 2 or more types. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-4,6-diamino-S-triazine, 2 S-triazine derivatives such as -vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, These compounds are preferably used in combination with the curing catalyst. The amount of the curing catalyst is sufficient in a normal quantitative ratio, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the carboxyl group-containing epoxy resin (A). The ratio of parts.

  In addition, the curable composition of the present invention is blended with acid and ketone to the extent that characteristics and storage stability are not impaired, and the epoxy group of the carboxyl group-containing epoxy resin (A) is converted into a 1,3-dioxolane ring. be able to.

  The curable composition of the present invention further contains, as necessary, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, Known or commonly used inorganic fillers such as aluminum hydroxide and mica can be used alone or in combination of two or more. These are used for the purpose of suppressing curing shrinkage of the coating film and improving properties such as adhesion and hardness. The blending amount of the inorganic filler is 10 to 300 parts by mass, preferably 30 to 200 parts by mass with respect to 100 parts by mass of the carboxyl group-containing epoxy resin (A).

  Further, the curable composition of the present invention may further include a known and commonly used colorant such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, if necessary. Known and commonly used thermal polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol and phenothiazine, known and commonly used thickeners such as fine silica, organic bentonite and montmorillonite, silicones, fluorines, polymers, etc. Known and conventional additives such as a defoaming agent and / or a leveling agent, an imidazole series, a thiazole series, a triazole series silane coupling agent, and the like can be blended.

  Furthermore, the curable composition of this invention can mix | blend flame retardants, such as a halogenated flame retardant, a phosphorus flame retardant, and an antimony flame retardant, for the purpose of obtaining a flame retardance. The compounding quantity of a flame retardant is 1-200 mass parts normally with respect to 100 mass parts of said carboxyl group-containing epoxy resins (A), Preferably it is 5-50 mass parts. When the blending amount of the flame retardant is in the above range, the flame retardancy, solder heat resistance, and electrical insulation of the composition are highly balanced and suitable.

  Moreover, water can also be added to the curable composition of this invention for the fall of flammability. When water is added, the carboxyl group of the carboxyl group-containing compound (A) is converted to amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meta It is preferable to make the curable composition of the present invention compatible with water by salt formation with a (meth) acrylate resin having a tertiary amino group such as acrylamide or acryloylmorpholine.

  The curable composition of this invention can also be made into the form of the dry film provided with the support body and the layer which consists of the said curable composition formed on this support body. Preferably, a peelable cover film is further laminated on the curable composition layer of the film.

  A plastic film is used as the support, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Here, the thickness of the support is appropriately selected within a range of 10 to 150 μm.

  The curable composition layer on the support is coated with a uniform thickness on the support with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater or the like. It is obtained by evaporating the solvent by heating and drying. The thickness of the curable composition layer is not particularly limited and is appropriately selected within a range of 10 to 150 μm.

  Generally, a polyethylene film, a polypropylene film, a Teflon (registered trademark) film, a surface-treated paper, or the like is used as the cover film. The cover film is not limited to a specific one as long as the adhesive strength with the curable composition layer is smaller than the adhesive strength between the curable composition layer and the support.

The curable composition of the present invention is prepared to have a viscosity suitable for the coating method by dilution as necessary. The curable composition having a adjusted viscosity is applied to a printed wiring board formed with a circuit by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method, for example, at about 60 to 100 ° C. A tack-free coating film can be formed by evaporating and drying the organic solvent contained in the composition.
In the case of a dry film comprising a support and a layer made of the curable composition formed on the support, the dry film is pasted on a printed wiring board formed with a circuit using a hot roll laminator or the like. Match. At this time, a dry film is bonded to the printed wiring board so that the curable composition layer contacts the printed wiring board on which the circuit is formed. Thereby, the coating film of the said curable composition can be formed on the said printed wiring board. In the case of a dry film provided with a peelable cover film on the curable composition layer, after the cover film is peeled off, the curable composition layer and the printed wiring board formed with a circuit are in contact with each other. A dry film and a printed wiring board are bonded together using a hot roll laminator or the like. Thereby, the coating film of the said curable composition can be formed on the printed wiring board by which the circuit was formed.

After the coating film is formed on the printed circuit board on which the circuit is formed, the active energy rays such as laser light are directly irradiated according to the pattern, or the active energy rays are selectively irradiated through the photomask on which the pattern is formed. By exposing, an unexposed part can be developed with dilute alkaline aqueous solution to form a resist pattern. In the case of using the dry film, after selectively exposing without peeling off the support, the support is peeled off and developed.
After the resist pattern is formed, it is further cured by heating, or by heat curing after irradiation with active energy rays, or after heat curing, it is irradiated with active energy rays and finally cured (main curing). By doing so, a cured film (cured product) excellent in hardness, solder heat resistance, chemical resistance, electroless gold plating resistance, electrical insulation and the like can be formed.

As the alkaline aqueous solution, alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia and amines can be used.
As an irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. A laser beam or the like can also be used as an active energy ray.

EXAMPLES Examples of the present invention will be specifically described below with reference to some synthesis examples, but the present invention is not limited to these synthesis examples. In the following description, “part” means part by mass unless otherwise specified.
Synthesis example 1
Cresol novolac type epoxy resin (product name “YDCN-700-5”, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) 203 parts of reaction equipped with a thermometer, stirrer, reflux condenser and air blowing tube Into a container, 164 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 0.2 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95 to 105 ° C. for 8 hours while blowing air. Thereafter, 52 parts of malonic acid, 35 parts of diethylene glycol monoethyl ether acetate and 0.3 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 2 hours to obtain a solution having a nonvolatile content of 60%. The carboxyl group-containing epoxy resin thus obtained had an acid value of 142.9 mgKOH / g and an epoxy equivalent of 1189 g / eq. Hereinafter, this solution is referred to as A-1.

Synthesis example 2
Cresol novolac type epoxy resin (product name “YDCN-700-5”, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) 203 parts of reaction equipped with a thermometer, stirrer, reflux condenser and air blowing tube Into a container, 164 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 0.2 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95 to 105 ° C. for 8 hours while blowing air. Thereafter, 31.2 parts of malonic acid, 21 parts of diethylene glycol monoethyl ether acetate and 0.3 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 60%. The carboxyl group-containing epoxy resin thus obtained had an acid value of 72.4 mgKOH / g and an epoxy equivalent of 1105 g / eq. Hereinafter, this solution is referred to as A-2.

Synthesis example 3
Cresol novolac type epoxy resin (product name “YDCN-700-5”, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) 203 parts of reaction equipped with a thermometer, stirrer, reflux condenser and air blowing tube Into a container, 164 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 0.2 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95 to 105 ° C. for 8 hours while blowing air. Thereafter, 31.2 parts of malonic acid, 14.6 parts of adipic acid, 21 parts of diethylene glycol monoethyl ether acetate and 0.3 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 62%. It was. The carboxyl group-containing epoxy resin thus obtained had an acid value of 100.5 mgKOH / g and an epoxy equivalent of 1170 g / eq. Hereinafter, this solution is referred to as A-3.

Synthesis example 4
Cresol novolac type epoxy resin (product name “YDCN-700-5”, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) 203 parts of reaction equipped with a thermometer, stirrer, reflux condenser and air blowing tube Into a container, 164 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 6 parts of acetic acid, 0.2 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95-105 ° C. for 8 hours while blowing air. Thereafter, 31.2 parts of malonic acid, 21 parts of diethylene glycol monoethyl ether acetate and 0.3 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 4 hours to obtain a solution having a nonvolatile content of 61%. The carboxyl group-containing epoxy resin thus obtained had an acid value of 85.7 mgKOH / g and an epoxy equivalent of 1268 g / eq. Hereinafter, this solution is referred to as A-4.

Synthesis example 5
Cresol novolac type epoxy resin (product name “YDCN-700-5”, manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 203 g / eq.) 203 parts of reaction equipped with a thermometer, stirrer, reflux condenser and air blowing tube Into a container, 164 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 43.2 parts of acrylic acid, 0.2 part of methylhydroquinone and 1 part of triphenylphosphine were added and reacted at 95 to 105 ° C. for 8 hours while blowing air. Thereafter, 31.2 parts of malonic acid, 26 parts of diethylene glycol monoethyl ether acetate and 0.3 part of methylhydroquinone were added and reacted at 95 to 105 ° C. for 3 hours, and 7.2 parts of acrylic acid was further added at 95 to 105 ° C. for 4 hours. Reaction was performed to obtain a solution having a nonvolatile content of 60%. The carboxyl group-containing epoxy resin thus obtained had an acid value of 83.4 mgKOH / g and an epoxy equivalent of 1198 g / eq. Hereinafter, this solution is referred to as A-5.

Comparative Synthesis Example 1
A reaction vessel equipped with 220 parts of cresol novolac type epoxy resin Epicron N-695 (manufactured by Dainippon Ink and Chemicals, epoxy equivalent: 220 g / eq.) With a thermometer, stirrer, reflux condenser and air blowing tube Into this, 220 parts of diethylene glycol monoethyl ether acetate was added and dissolved by heating. Next, 0.46 parts of methylhydroquinone and 3.0 parts of triphenylphosphine were added. This mixture was heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and reacted for 4 hours while blowing air. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added and reacted for 5 hours to obtain a solution having a nonvolatile content of 65%. The carboxyl group-containing compound thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as B-1.

Comparative Synthesis Example 2
In a reaction vessel equipped with a gas introduction tube, a stirring device, a cooling tube, a thermometer, and a dropping funnel for continuous dropping of an alkali metal hydroxide aqueous solution, a phenolic hydroxyl group equivalent of 80 g / eq. 224 parts of 1,5-dihydroxynaphthalene and 1075 parts of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 828, epoxy equivalent 189 g / eq.) Were added at 110 ° C. with stirring in a nitrogen atmosphere. Dissolved. Thereafter, 0.65 part of triphenylphosphine was added, the temperature in the reaction vessel was raised to 150 ° C., the reaction was continued for about 90 minutes while maintaining the temperature at 150 ° C., and an epoxy resin having an epoxy equivalent of 452 g / equivalent ( a) was obtained. Next, the temperature in the flask was cooled to 40 ° C., 1920 parts of epichlorohydrin, 1690 parts of toluene, and 70 parts of tetramethylammonium bromide were added, and the temperature was raised to 45 ° C. and maintained with stirring. Thereafter, 364 parts of a 48 wt% aqueous sodium hydroxide solution were continuously added dropwise over 60 minutes, and then reacted for another 6 hours. After completion of the reaction, excess epichlorohydrin and most of toluene were recovered by distillation under reduced pressure, and the reaction product containing by-product salt and toluene was dissolved in methyl isobutyl ketone and washed with water. After the organic solvent layer and the aqueous layer were separated, methyl isobutyl ketone was distilled off from the organic solvent layer under reduced pressure to obtain an epoxy equivalent of 277 g / eq. The polynuclear epoxy resin (b) was obtained. When the obtained polynuclear epoxy resin (b) is calculated from the epoxy equivalent, about 1.59 of 1.98 alcoholic hydroxyl groups in the epoxy resin (a) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%. Next, 277 parts of the polynuclear epoxy resin (b) is placed in a flask equipped with a stirrer, a cooling tube and a thermometer, 290 parts of propylene glycol monomethyl ether acetate is added, and dissolved by heating, 0.46 part of methyl hydroquinone, 1.38 parts of phenylphosphine was added, heated to 95 to 105 ° C., 72 parts of acrylic acid was gradually added dropwise, and reacted for 4 hours while blowing air. The reaction product was cooled to 80 to 90 ° C., 129 parts of tetrahydrophthalic anhydride was added and reacted for 5 hours to obtain a solution having a nonvolatile content of 62%. The carboxyl group-containing compound thus obtained had an acid value of 100 mgKOH / g. Hereinafter, this solution is referred to as B-2.

Comparative Synthesis Example 3
To an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device, a novolac type cresol resin (trade name “Shonol CRG951” manufactured by Showa Polymer Co., Ltd., phenolic hydroxyl group equivalent: 119.4 g / eq) .) 119.4 parts, 1.19 parts of potassium hydroxide, and 119.4 parts of toluene were charged, and the system was purged with nitrogen while stirring and heated. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide, the nonvolatile content was 62.1%, and the alcoholic hydroxyl group equivalent was 182.2 g / eq. A novolak-type cresol resin propylene oxide reaction solution was obtained. This was an average of about 1.08 mole of alkylene oxide added per equivalent of phenolic hydroxyl group. 293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone, and 252.9 parts of toluene were mixed with a stirrer and a temperature. A reaction vessel equipped with a total and an air blowing tube was charged, air was blown at a rate of 10 ml / min, and the reaction was carried out at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 149 parts of propylene glycol monomethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution. Next, 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were charged into a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was supplied at a rate of 10 ml / min. While blowing and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added and reacted at 95 to 101 ° C. for 6 hours to obtain a solution having a nonvolatile content of 65%. The carboxyl group-containing compound thus obtained had an acid value of 84 mgKOH / g. Hereinafter, this solution is referred to as B-3.

Preparation of photo-curing / thermosetting resin composition and characteristic value of each composition Each solution of Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 is blended in the components and component ratios shown in Table 1, and 3 Each was kneaded with a roll mill to prepare a photocurable / thermosetting resin composition.

Table 2 shows the characteristic values of each composition.

Each characteristic value was evaluated by the following method.
(1) Storage stability Each of the curable resin compositions prepared in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 was allowed to stand for 3 days in a sealed state at 50 ° C. and evaluated according to the following criteria. .
○: not gelled ×: gelled

(2) Pencil hardness Each of the curable compositions prepared in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 to 3 (those that have not been left in a 50 ° C. heat-reserving bath for 3 days) are screen-printed by 100 mesh. A polyester screen is used to coat the entire surface of the patterned copper through-hole printed wiring board so as to have a thickness of 30 to 40 μm, and the coating film is dried for 15 minutes in an 80 ° C. hot-air circulating drying oven. A negative film having a pattern was brought into close contact with the coating film, and irradiated with ultraviolet rays (exposure amount: 400 mJ / cm ² ) using an ultraviolet exposure device (manufactured by Oak Manufacturing Co., Ltd., model HMW-680GW). Subsequently, development was performed with a 1% aqueous sodium carbonate solution for 60 seconds at a spray pressure of 2.0 kg / cm ² to dissolve and remove unexposed portions. Thereafter, heat curing was performed for 60 minutes in a hot air circulation drying oven at 150 ° C., and the pencil hardness test was performed on the evaluation substrate having the obtained cured film in accordance with JIS K 5400.

(3) Heat resistance According to the test method of JIS C 6481, the said evaluation board | substrate was immersed in 260 degreeC solder bath twice for 10 second, and the change of the external appearance was evaluated on the following references | standards. As the post flux (rosin type), a flux according to JIS C 6481 was used.
○: No change in appearance △: Discoloration of the cured film is observed ×: Hardened film is lifted, peeled off, or soldered

(4) Acid resistance The said evaluation board | substrate was taken out after 30-minute immersion at 10 degreeC sulfuric acid aqueous solution for 30 minutes, and the state and adhesiveness of the cured film were comprehensively evaluated. The judgment criteria are as follows.
○: No change is observed Δ: Only a slight change ×: The coating has blisters or swelling drops

(5) Alkali resistance A test similar to the acid resistance test was conducted on the evaluation substrate, except that the 10 volume% sulfuric acid aqueous solution was changed to a 10 volume% sodium hydroxide aqueous solution, and evaluation was performed.

(6) Resistance to electroless gold plating The evaluation substrate was subjected to electroless nickel plating and then electroless gold plating, and appearance change and a peeling test using a cellophane adhesive tape were performed to determine the peeled state of the cured film. Judgment criteria are as follows.
○: No change in appearance and no peeling of the cured film.
(Triangle | delta): Although there is no change of an external appearance, there exists slight peeling in a cured film.
X: Lifting of the cured film is observed, plating stagnation is observed, and peeling of the cured film is large in the peeling test.

(7) Electrical insulation In place of the copper through hole printed wiring board on which the pattern is formed, the B pattern of the printed circuit board (thickness 1.6 mm) defined by the IPC is used, and the curable composition is formed by the above method. The product was applied and cured, and the electrical insulation of the resulting cured film was evaluated under the following conditions and criteria.
Humidification conditions: temperature 121 ° C., humidity 85% RH, applied voltage 5 V, 50 hours.
Measurement conditions: measurement time 60 seconds, applied voltage 500V.
○: Insulation resistance value after humidification of 10 ⁹ Ω or more, no copper migration.
Δ: Insulation resistance value after humidification of 10 ⁹ Ω or more, copper migration.
X: Insulation resistance value after humidification of 10 ⁸ Ω or less, copper migration.

  The curable composition of the present invention is excellent in storage stability, and a cured product excellent in various properties as described above is obtained. Therefore, a solder resist, an etching resist, a plating resist, an interlayer insulating layer of a multilayer wiring board, It is also useful for applications such as permanent masks, flexible wiring board resists, color filter resists, dry film resists, and inkjet resists used in the manufacture of tape carrier packages.

Claims (8)

(A) The monocarboxylic acid (b) is added to the epoxy group of the resin (a) having two or more epoxy groups in one molecule at a ratio of 0.3 to 0.9 mol with respect to 1 equivalent of the epoxy group. The polybasic acid (d) is reacted with the epoxy group of the obtained reaction product (c) at a ratio of 0.2 to 5 mol with respect to 1 equivalent of the epoxy group, and further the reaction product obtained An acid value of 20 to 150 mgKOH / g obtained by reacting the epoxy group of the product (e) with a monocarboxylic acid (f) at a ratio of 0.0 to 5.0 mol with respect to 1 equivalent of the epoxy group, epoxy Equivalent 3000 g / eq. The following carboxyl group-containing epoxy resins,
A curable composition capable of alkali development, comprising (B) a photosensitive (meth) acrylate compound, and (C) a photopolymerization initiator.   The curable composition according to claim 1, wherein the monocarboxylic acids (b) and (f) are unsaturated group-containing monocarboxylic acids.   The curable composition according to claim 1, wherein the monocarboxylic acid (b) is an unsaturated group-containing monocarboxylic acid, and the monocarboxylic acid (f) is a monocarboxylic acid not containing an unsaturated group.   The curable composition according to claim 1, wherein the monocarboxylic acid (b) is a monocarboxylic acid not containing an unsaturated group, and the monocarboxylic acid (f) is an unsaturated group-containing monocarboxylic acid.   The curable composition according to claim 1, wherein the monocarboxylic acids (b) and (f) are monocarboxylic acids not containing an unsaturated group.   The curable composition according to claim 1, wherein the monocarboxylic acid (b) and / or (f) is a mixture of an unsaturated group-containing monocarboxylic acid and a monocarboxylic acid not containing an unsaturated group.   The curable composition according to any one of claims 1 to 6, wherein the resin (a) having two or more epoxy groups in one molecule is a novolac type epoxy resin.   Hardened | cured material of the curable composition in any one of Claims 1-7.