JP2007197530A - Curable composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition excellent in storage stability, capable of taking the form of a one-part composition, and capable of giving a cured film highly able to withstand a pressure cooker test and excellent in moisture absorption resistance, etc. <P>SOLUTION: The curable composition comprises (A) a mixture of a carboxyl-containing photosensitive compound (A-1) obtained by reacting a polybasic acid anhydride with the reaction product of a compound having at least two epoxy groups in the molecule with an unsaturation-containing monocarboxylic acid or a mixture thereof with an epoxy-reactive group and a carboxyl-containing photosensitive resin (A-2) obtained by reacting an unsaturation-containing monocarboxylic acid with the reaction product of a novolak phenolic resin with an alkylene oxide and/or a cyclic carbonate and reacting a polybasic acid anhydride with the obtained reaction product, (B) a 1,3-dioxolane-ring-containing epoxy resin obtained by effecting the partial addition reaction of an epoxy resin having at least two epoxy groups in the molecule with a ketone, and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a curable composition used in the production of printed wiring boards and the like, and in particular, adhesion to a base material required for an IC package resist, solder heat resistance, and PCT (pressure cooker test) resistance. The present invention relates to a photocurable and thermosetting composition that can be developed with a dilute alkaline aqueous solution suitable for obtaining a film excellent in crack resistance, electroless gold plating resistance, and electrical insulation, and a cured product thereof.

Conventionally, curing containing a curable resin obtained from a novolak type epoxy resin as a starting material, a photopolymerization initiator, a photopolymerizable monomer, and a polyfunctional epoxy resin having two or more epoxy groups in one molecule on the market. Composition (see Patent Document 1) has a cured film with excellent properties such as heat resistance, chemical resistance, and electrical insulation, and therefore, a solder resist used in the production of printed wiring boards and a tape carrier package Widely used in many fields of electronic materials such as permanent masks used in the manufacture of
However, in response to the recent development of the electrical industry, the semiconductor industry, and the increase in the density of printed wiring boards accompanying the reduction in the thickness and size of electronic equipment, further improvement in characteristics, for example, improvement in heat resistance and PCT resistance, is required. Various curable resins have been developed to satisfy these requirements.

  More recently, instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc. using a lead frame and sealing resin, a printed wiring board with a solder resist is sealed. An IC package using a stop resin has appeared. In these new packages, metal such as ball-shaped solder is arranged in one area on one side of the printed wiring board with solder resist, and the IC chip is directly connected to the other side with wire bonding or bumps, and sealed resin It has a sealed structure and is called by a name such as BGA (ball grid array), CSP (chip scale package) or the like. These packages have a larger number of pins and can be further reduced in size than packages of the same size such as QFP. Also in the mounting, a low defect rate is realized by the self-alignment effect of the ball-shaped solder, and its introduction is progressing rapidly.

  However, a printed wiring board obtained by using a commercially available resist ink composition is inferior in PCT resistance, which is a long-term reliability test of a package, and resist peeling occurs. Also, the so-called popcorn phenomenon, in which moisture absorbed inside the package boiled during reflow during package mounting due to moisture absorption of the resist film, causing cracks in the resist inside the package and its periphery, has been regarded as a problem. Such problems of moisture absorption resistance and long-term reliability are not limited only to the above mounting technology, and are not desirable in products for other applications such as an interlayer insulating layer of a multilayer wiring board such as a build-up board. .

  As a curable resin composition excellent in heat resistance and PCT resistance capable of coping with the above-mentioned problems, the present applicant has prepared an epoxy compound having two or more epoxy groups in one molecule and 2 in one molecule. A reaction product of a compound having one reactive group other than a hydroxyl group that reacts with one or more hydroxyl groups and an epoxy group (for example, dimethylolpropionic acid) and an unsaturated group-containing monocarboxylic acid (for example, acrylic acid) is polybasic. An unsaturated group-containing polycarboxylic acid resin obtained by reacting an acid anhydride (for example, tetrahydrophthalic anhydride), a photopolymerization initiator, a photopolymerizable monomer, and a polymer having two or more epoxy groups in one molecule A curable composition containing a functional epoxy resin (see Patent Document 2), an epoxy compound having two or more epoxy groups in one molecule, and a phenol having a hydroxyl group-containing substituent Photosensitivity obtained by reacting a polybasic acid anhydride (for example, tetrahydrophthalic anhydride) with a reaction product of a compound (for example, p-hydroxyphenethyl alcohol) and an unsaturated group-containing monocarboxylic acid (for example, acrylic acid). A photocurable / thermosetting composition (see Patent Document 3) containing a prepolymer, a photopolymerization initiator, a photosensitive (meth) acrylate compound, and a polyfunctional epoxy resin has been developed.

  Further, the present applicant made an unsaturated group-containing monocarboxylic acid react with a reaction product of an alkylene oxide and a compound having 3 or more phenolic hydroxyl groups in one molecule, and obtained reaction product and polybasic acid anhydride. Curable resin containing photopolymerization initiator, photopolymerization initiator, photosensitive (meth) acrylate compound, and polyfunctional epoxy compound having two or more epoxy groups in one molecule. An unsaturated group-containing monocarboxylic acid and / or its ester to a reactive resin composition (see Patent Document 4) or a reaction product of a compound having two or more phenolic hydroxyl groups in one molecule and a cyclic carbonate, Carboxy group-containing photosensitive resin, photopolymerization initiator, photosensitive (meth) acrylate compound, and polyfunctional epoxy obtained by reacting the obtained reaction product with a polybasic acid anhydride Curable composition containing a fat is also developed (see Patent Document 5), etc..

  With the curable composition as described above, a cured film that is almost satisfactory in terms of properties can be obtained. However, the conventional curable composition as described above includes a polyfunctional epoxy resin having two or more epoxy groups in one molecule as a thermosetting component in order to improve solder heat resistance and the like. Yes. However, since this polyfunctional epoxy resin has high reactivity, the curable composition containing it has a short shelf life (preservation life) and tends to thicken before application to a circuit board blank. Difficult to compose into mold. Therefore, in general, it is composed of a two-part composition consisting of a curing agent solution mainly composed of a polyfunctional epoxy resin and a main agent solution mainly composed of a photosensitive prepolymer, and these are mixed and used in use. There was a problem in terms.

Recently, from the viewpoint of processability and smoothness of the cured film surface, it has been required to form a solder resist in a dry film. However, when the curable composition containing a polyfunctional epoxy resin is in the form of a dry film, there is a problem in storage stability at room temperature, and shelf life (storage life) is shortened. Therefore, at present, most solder resist dry films need to be stored at 0 ° C. or less, and there is a problem that it takes time for transportation and storage.
JP 61-243869 (Claims, page 3, lower left column, line 10 to page 4, upper left column, line 5; page 4, lower left column, lines 12 to 19) JP-A-6-324490 (Claims, paragraph [0033]) JP 11-288091 A (claims, paragraph [0024]) International Publication WO 03 / 078494A1 (Claims, pages 22-23) JP 2004-359729 A (Claims, paragraph [0029])

  The present invention has been made in view of the problems of the prior art as described above, and its purpose is excellent in storage stability, can be composed in a one-pack type, and can be used as a resist for conventional printed wiring boards. Excellent adhesion, heat resistance, crack resistance, electroless plating resistance, electrical insulation, and other characteristics required for interlayer insulation layers of multilayer wiring boards, especially PCT resistance and moisture absorption resistance required for IC packages Another object of the present invention is to provide a curable composition capable of obtaining a cured film excellent in crack resistance, capable of dealing with higher density and surface mounting of a printed wiring board and capable of alkali development.

In order to achieve the above object, according to the present invention, (A) a compound (a) having two or more epoxy groups in one molecule, an unsaturated group-containing monocarboxylic acid (b), or an unsaturated group It is obtained by reacting polybasic acid anhydride (f) with a reaction product (e) of a mixture (d) of a compound (c) having a reactive group that reacts with an epoxy group and containing monocarboxylic acid (b). To the reaction product of the carboxyl group-containing photosensitive compound (A-1), the novolak-type phenol resin (g), the alkylene oxide (h) and / or the cyclic carbonate (i). ), A mixture with the carboxyl group-containing photosensitive resin (A-2) obtained by reacting the resulting reaction product with the polybasic acid anhydride (f), (B) 2 in one molecule An epoxy resin having an epoxy group and a ketone Partially by addition reaction obtained curable composition characterized by containing an epoxy resin, (C) a photopolymerization initiator having a 1,3-dioxolane ring is provided.
According to a preferred embodiment, in the epoxy resin (B), the reaction ratio of the ketone to the polyfunctional epoxy resin is 0.03 to 0.9 equivalent of the carbonyl group with respect to 1 equivalent of the epoxy group.

The curable composition may be in a liquid form or a so-called dry film.
According to still another aspect of the present invention, a cured product obtained by using the curable composition is provided.

Since the curable composition of the present invention uses an epoxy resin (B) having a 1,3-dioxolane ring instead of a polyfunctional epoxy resin generally used in the past, it has excellent storage stability and is a one-part solution. The epoxy resin (B) can be combined with two types of carboxyl group-containing photosensitive compounds (A-1) and carboxyl group-containing photosensitive resins (A-2) having different structures. Because it is used, it is photo-curing and thermosetting, as well as the adhesion, heat resistance, electroless plating resistance, electrical resistance required for conventional resists of printed wiring boards and interlayer insulation layers of multilayer wiring boards, etc. A cured film having excellent properties such as insulation properties and particularly excellent PCT resistance, moisture absorption resistance and crack resistance required for IC packages can be obtained, and can be applied to high density and surface mounting of printed wiring boards. By using such a curable composition of the present invention, even in an IC package such as BGA or CSP of a printed wiring board, the resist is not peeled or cracked, and highly reliable mounting is possible.
Moreover, since both the carboxyl group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2) have a carboxyl group, the coating film is made of an alkaline aqueous solution. It can be developed. Furthermore, since it is excellent in storage stability, can be composed in a one-pack type, and can produce a photosensitive dry film excellent in storage stability at room temperature, it is advantageous in terms of workability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors, as an essential component of the composition, together with an epoxy resin (B) having a 1,3-dioxolane ring, two kinds of carboxyls having different structures. It has been found that the object can be achieved by combining the group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2), and has completed the present invention. is there.
That is, an epoxy resin (B) obtained by partially adding a ketone to a polyfunctional epoxy resin and having a 1,3-dioxolane ring, in particular, the reaction ratio of the ketone to the polyfunctional epoxy resin is 1 equivalent of an epoxy group. An epoxy resin (B) having a 1,3-dioxolane ring having a carbonyl group of 0.03 to 0.9 equivalent, two kinds of carboxyl group-containing photosensitive compounds (A-1) and carboxyl having different structures. The combination with the group-containing photosensitive resin (A-2) is superior in storage stability to the combination of a polyfunctional epoxy resin and a carboxyl group-containing photosensitive compound that are generally used in the past, and further obtained curing The product is inferior in heat resistance compared to a cured product of a composition comprising a normal polyfunctional epoxy resin, a carboxyl group-containing photosensitive compound and a photopolymerization initiator. In addition, it forms a flexible coating film, and is excellent in adhesion to the substrate and moisture absorption resistance, and even in IC packages such as BGA and CSP of printed wiring boards, there is no peeling or cracking in the resist. The inventors have found that highly reliable mounting is possible, and have completed the present invention.

  An epoxy resin (B) having a 1,3-dioxolane ring obtained by partially adding a ketone to a polyfunctional epoxy resin contained in the curable composition of the present invention is, for example, a reaction of a ketone with an epoxy resin. When the ratio is 0.03 to 0.9 equivalent of carbonyl group to 1 equivalent of epoxy group, it has an unreacted epoxy group and a 1,3-dioxolane ring formed by the reaction of epoxy group and ketone. Has a structure. (However, the reaction with an acid catalyst used in the reaction, for example, the reaction of phosphoric acid with an epoxy group may produce a small amount of phosphate ester.) This 1,3-dioxolane ring is a normal curing agent. Under the conditions, the ring hardly opens and reacts with the carboxyl group. Therefore, the reactivity of the epoxy resin having a 1,3-dioxolane ring and the carboxyl group-containing photosensitive compound thus obtained is reduced by the presence of the 1,3-dioxolane ring. Compared with the case of using the (normal) polyfunctional epoxy resin, the storage stability is excellent. However, since there is a sufficient amount of epoxy groups, the cured coating film obtained by the reaction of the epoxy resin having a 1,3-dioxolane ring and the carboxyl group-containing photosensitive compound is the original (normal) polyfunctional epoxy. It is not inferior to the cured coating film obtained by the reaction between the resin and the carboxyl group-containing photosensitive compound, and is excellent in various properties as described above.

  Therefore, together with the epoxy resin (B) having a 1,3-dioxolane ring obtained by partial addition reaction of a polyfunctional epoxy resin and a ketone, two kinds of carboxyl group-containing photosensitive compounds (A -1) and the carboxyl group-containing photosensitive resin (A-2) and the photopolymerization initiator (C), the curable composition of the present invention is excellent in storage stability and can be composed in a one-pack type. In addition to exhibiting excellent alkali developability, photocurability and / or thermosetting properties, solder heat resistance, PCT resistance, adhesion to various substrates by selective exposure, development and finish curing of the coating film Cured products having excellent properties, chemical resistance, crack resistance, electroless gold plating resistance, electrical insulation, moisture absorption resistance and the like can be obtained.

Hereinafter, the curable composition of the present invention will be described in detail.
First, the carboxyl group-containing photosensitive compound (A-1) is obtained by adding an unsaturated group-containing monocarboxylic acid (b) or an unsaturated group-containing monovalent compound to a compound (a) having two or more epoxy groups in one molecule. The reaction product (e) obtained by reacting the mixture (d) of the carboxylic acid (b) with the compound (c) having a reactive group that reacts with the epoxy group is further reacted with the polybasic acid anhydride (f). Each reaction is easily performed in a solvent using a catalyst as described later.

  As a compound (a) having two or more epoxy groups in one molecule (hereinafter referred to as a polyfunctional epoxy compound), Epicoat 828, Epicoat 834, Epicoat 1001, Epicoat 1004, Dainippon Nippon, manufactured by Japan Epoxy Resin Co., Ltd. Epicron 840, Epicron 850, Epicron 1050, Epicron 2055, Etototo YD-011, YD-013, YD-127, YD-128, manufactured by Ink Chemical Industry Co., Ltd., 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; Epicoat YL903 manufactured by Japan Epoxy Resins Co., Ltd., Dainippon Ink & Chemicals, Inc. Epicron 152, Epicron 165, East Brominated epoxy resins such as EPOTOTO YDB-400 and YDB-500 manufactured by Kasei Co., Ltd., Sumi-epoxy ESB-400 and ESB-700 (both trade names) manufactured by Sumitomo Chemical Co., Ltd .; Japan Epoxy Resin ( Epicoat 152, Epicoat 154, manufactured by Dainippon Ink & Chemicals, Inc., Epicron N-730, Epicron N-770, Epicron N-865, Etototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Co., Ltd. Novolak type epoxy resin such as (trade name); Epicron 83 manufactured by Dainippon Ink & Chemicals, Inc. Bisphenol F type epoxy resin such as Epicote 807 manufactured by Japan Epoxy Resin Co., Ltd., Epototo YDF-170, YDF-175, YDF-2004 (all trade names) manufactured by Toto Kasei Co., Ltd .; manufactured by Toto Kasei Co., Ltd. Hydrogenated bisphenol A type epoxy resin such as Epototo ST-2004, ST-2007, ST-3000 (all trade names); Epicoat 604 manufactured by Japan Epoxy Resin Co., Ltd. Epototo YH-434 manufactured by Toto Kasei Co., Ltd. Glycidylamine type epoxy resins such as Sumi-epoxy ELM-120 (all trade names) manufactured by Sumitomo Chemical Co., Ltd .; Alicyclic epoxy resins such as Celoxide 2021 (trade names) manufactured by Daicel Chemical Industries, Ltd. ; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., EPPN-501 manufactured by Nippon Kayaku Co., Ltd., EP Trihydroxyphenylmethane type epoxy resin such as PN-502 (all are trade names); Bixylenol type such as YL-6056, YX-4000, YL-6121 (all are trade names) manufactured by Japan Epoxy Resin Co., Ltd. Biphenol type epoxy resin or a mixture thereof; 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. Bisphenol S type epoxy resin such as Japan Epoxy Resin Co., Ltd. Epicoat 157S (trade name) and other bisphenol A novolak type epoxy resins; Japan Epoxy Resin Co., Ltd. Epicoat YL-931 (trade name), etc. Tetraphenylolethane type epoxy resin; TEPIC (trade name) manufactured by Nissan Chemical Industries, Ltd. Heterocyclic epoxy resins such as diglycidyl phthalate resin such as Bremer DGT (trade name) manufactured by NOF Corporation; Tetraglycidyl xylenoyl ethane such as ZX-1063 (trade name) manufactured by Tohto Kasei Co., Ltd. Resins: Epoxy naphthalene group-containing epoxies such as ESN-190 and ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, and EXA-4700 manufactured by Dainippon Ink & Chemicals, Inc. (all trade names) Resins; Epoxy resins having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H (both trade names) manufactured by Dainippon Ink and Chemicals, Inc .; CP-50S and CP-50M manufactured by Nippon Oil & Fats Co., Ltd. (All are trade names) glycidyl methacrylate copolymer epoxy resin; cyclohexylmaleimide and glycidyl methacrylate Copolymerized epoxy resins such bets, and the like, but not limited thereto. These epoxy resins can be used alone or in combination of two or more.

  Representative examples of the unsaturated group-containing monocarboxylic acid (b) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, α-cyanocinnamic acid, β-styrylacrylic acid, β-furfurylacrylic acid and the like. Is mentioned. Among these, acrylic acid and / or methacrylic acid are preferable from the viewpoints of photoreactivity and physical properties of the cured product, particularly heat resistance, electrical characteristics, and moisture absorption resistance. These unsaturated group-containing monocarboxylic acids can be used alone or in admixture of two or more.

  In addition, representative examples of the compound (c) having a reactive group that reacts with the epoxy group include polyhydroxy-containing monocarboxylic acids such as dimethylolpropionic acid, dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid. Acids; dialkanolamines such as diethanolamine and diisopropanolamine; (bis) hydroxymethylphenol, (bis) hydroxymethylcresol, hydroxymethyl-di-t-butylphenol, p-hydroxyphenyl-2-methanol, p-hydroxyphenyl -3-propanol, p-hydroxyphenyl-4-butanol, hydroxyethylcresol, 2,6-dimethyl-4-hydroxymethylphenol, 2,4-dihydroxymethyl-2-cyclohexylphenol Hydroxyalkylphenol or hydroxyalkylcresol such as trimethylolphenol, 3,5-dimethyl-2,4,6-trihydroxymethylphenol; carboxyl-containing substituent such as hydroxybenzoic acid, hydroxyphenylbenzoic acid, or hydroxyphenoxybenzoic acid Esterified products of phenols having ethylene glycol, propylene glycol, glycerol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like; bisphenol monoethylene oxide adduct, bisphenol monopropylene oxide adduct, p- Examples thereof include hydroxyphenethyl alcohol.

  Mixture of the polyfunctional epoxy compound (a) and the unsaturated group-containing monocarboxylic acid (b) or the unsaturated group-containing monocarboxylic acid (b) and the compound (c) having a reactive group that reacts with the epoxy group ( The reaction with d) is usually carried out at about 50 to 150 ° C. in the presence of an organic solvent described later in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine are added as a catalyst. May be.

  The reactant (e) is further reacted with a polybasic acid anhydride (f) to obtain a carboxyl group-containing photosensitive compound (A-1) used in the composition of the present invention. In this reaction, The amount of polybasic acid anhydride (f) used is such that the acid value of the resulting carboxyl group-containing photosensitive compound is preferably 30 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g. . When the acid value of the carboxyl group-containing photosensitive compound is lower than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film becomes difficult. On the other hand, if it is higher than 200 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.

  The above reaction is usually carried out at about 50 to 150 ° C. in the presence of a polymerization inhibitor such as hydroquinone or oxygen in the presence of an organic solvent described later. At this time, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, and a phosphorus compound such as triphenylphosphine are added as a catalyst. May be.

  Examples of the polybasic acid anhydride (f) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Cycloaliphatic dibasic anhydrides such as methylendomethylenetetrahydrophthalic anhydride and tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, anhydrous Aliphatic or aromatic dibasic acid anhydrides such as trimellitic acid; or biphenyl tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, Pyromellitic anhydride, benzofu Non tetracarboxylic dianhydride aliphatic such as anhydrides or aromatic tetracarboxylic acid dianhydride and the like, can be used one or two or more of these. Among these, alicyclic dibasic acid anhydrides are particularly preferable.

  Next, the carboxyl group-containing photosensitive resin (A-2) having a structure different from that of the carboxyl group-containing photosensitive compound (A-1) is a novolak-type phenol resin (g), an alkylene oxide (h) and / or a cyclic carbonate. The reaction product with (i) is obtained by reacting the unsaturated group-containing monocarboxylic acid (b), and the reaction product obtained is reacted with the polybasic acid anhydride (f). It is easily carried out in a solvent using a catalyst as described later. Such a carboxyl group-containing photosensitive resin (A-2) desirably has an acid value in the range of 30 to 150 mgKOH / g, preferably 50 to 120 mgKOH / g.

  The novolac-type phenol resin (g) is obtained by a condensation reaction of phenols and formaldehyde, and these reactions are usually performed in the presence of an acidic catalyst.

  Examples of phenols include phenol, cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol, and the like.

  The addition ratio of alkylene oxide (h) and / or cyclic carbonate (i) to the novolac type phenol resin (g) is 0.3 to 5.0 mol per equivalent of the phenolic hydroxyl group of the novolac type phenol resin (g). Is preferred. When less than 0.3 mol and more than 5.0 mol, the photocurability and developability of the carboxyl group-containing photosensitive resin (A-2) may be poor.

The addition reaction of alkylene oxide (h) and / or cyclic carbonate (i) to the novolak-type phenol resin (g) includes, for example, alkali metal compounds such as sodium hydroxide; trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide, A quaternary basic salt compound such as tetraethylammonium hydroxide; or a mixture of an alkali metal compound and a quaternary basic salt compound; or a phosphorus compound such as triphenylphosphine as a catalyst, for example, ethylene glycol monoethyl ether acetate. , Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol Ether acetate, and acetic esters such as dipropylene glycol monomethyl ether acetate, using a solvent mixture such as toluene and methyl isobutyl ketone, or without a solvent, 80 to 250 ° C., under normal pressure to 10 kg / cm ² Conditions Is done.

  Examples of the alkylene oxide (h) include ethylene oxide, propylene oxide, butylene oxide, trimethylene oxide, tetrahydrofuran, and tetrahydropyran.

  Examples of the cyclic carbonate (i) include ethylene carbonate, propylene carbonate, butylene carbonate, 2,3-carbonate propyl methacrylate, and preferably 5-membered ethylene carbonate and propylene carbonate are preferable in terms of reactivity and supply system. . These cyclic carbonates can be used alone or in admixture of two or more.

  The reaction temperature in the esterification reaction of the novolac type phenol resin (g) with the alkylene oxide (h) and / or cyclic carbonate (i) and the unsaturated group-containing monocarboxylic acid (b) is about 50. The reaction can be carried out under reduced pressure, normal pressure, or increased pressure. As a reaction solvent, n-hexane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, trichloroethane, tetrachloroethylene, methyl chloroform, diisopropyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, Acetic esters such as diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and dipropylene glycol monomethyl ether acetate are preferably used. These solvents can be used alone or in admixture of two or more. As the esterification catalyst, sulfuric acid, hydrochloric acid, phosphoric acid, boron fluoride, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, cation exchange resin, and the like are used as appropriate. The esterification reaction is preferably performed in the presence of a polymerization inhibitor. As the polymerization inhibitor, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like are preferably used.

  The reaction product is reacted with a polybasic acid anhydride (f) to obtain a carboxyl group-containing photosensitive resin (A-2). In this reaction, the amount of the polybasic acid anhydride (f) used is The added amount is such that the acid value of the produced carboxyl group-containing photosensitive resin (A-2) is 30 to 150 mgKOH / g, preferably 50 to 120 mgKOH / g. When the acid value of the carboxyl group-containing photosensitive resin (A-2) is lower than 30 mgKOH / g, the solubility in an alkaline aqueous solution is deteriorated, and development of the formed coating film becomes difficult. On the other hand, if it is higher than 150 mgKOH / g, the surface of the exposed area is developed regardless of the exposure conditions, which is not preferable.

  The mixing ratio of the carboxyl group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2) may be arbitrary depending on the purpose, but the carboxyl group-containing photosensitive compound (A-1). It is preferable to mix | blend carboxyl group-containing photosensitive resin (A-2) with the ratio of 80: 20-20: 80 with respect to this.

  Next, the epoxy resin (B) having a 1,3-dioxolane ring can be easily obtained by partial addition reaction of a polyfunctional epoxy resin and a ketone using an acid as a catalyst. The reaction ratio of the ketone to the polyfunctional epoxy resin is 0.03 to 0.9 equivalent of the carbonyl group with respect to 1 equivalent of the epoxy group, preferably 0.05 to 0.8 equivalent, more preferably 0.8. 1 to 0.7 equivalent, particularly preferably 0.2 to 0.5 equivalent.

  Examples of the polyfunctional epoxy resin include epoxy resins exemplified as the polyfunctional epoxy compound (a) having two or more epoxy groups in one molecule. For an electronic material, a polyfunctional epoxy resin having three or more epoxy groups in one molecule is preferable, and among these, a novolak type epoxy resin is particularly preferable from the viewpoint of reactivity.

  As ketones, acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl isobutyl ketone, methyl n-butyl ketone, methyl n-amyl ketone, ethyl benzyl ketone, di-n-amyl ketone, n-hexyl benzyl ketone, cyclohexanone, acetophenone And benzoin.

  Examples of the acid used as a catalyst for the reaction include phosphoric acid, hydrochloric acid, sulfuric acid, phosphotungstic acid, boron trifluoride ether complex, silicotungstic acid, trifluoromethanesulfonic acid, and polyphosphoric acid. Among these, electrons From the viewpoint of materials, phosphoric acid is preferable. The amount of the acid used is preferably 0.001 to 20% or less with respect to the polyfunctional epoxy resin, more preferably 0.01 to 5%, and particularly preferably 0.01 to 3%. If the ratio of the acid is 20% or more, gelation may occur. On the other hand, if the ratio is 0.001% or less, the reaction between the polyfunctional epoxy resin and the ketone takes a long time, which is not preferable.

  The reaction between the polyfunctional epoxy resin and the ketone is preferably carried out in the ketone, but a ketone and another solvent, for example, a mixed solvent of ketone and toluene, or a mixed solvent of ketone and carbitol can be used. 0-100 degreeC of reaction temperature is preferable, More preferably, it is 10-80 degreeC. If the reaction temperature exceeds 100 ° C., gelation may occur, which is not preferable. On the other hand, when the reaction temperature is less than 0 ° C., the reactivity is lowered, which is not preferable.

  The blending ratio in the composition of the epoxy resin (B) having a 1,3-dioxolane ring obtained in this way is the carboxyl group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A- A ratio of 5 to 100 parts by mass (the same applies hereinafter as the solid content) is appropriate with respect to 100 parts by mass of the total amount of 2).

Examples of the photopolymerization initiator (C) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, acetophenone such as N, N-dimethylaminoacetophenone Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; Thioxanthones such as n-tone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone Benzophenones such as 4,4'-bisdiethylaminobenzophenone and 4-benzoyl-4'-methyldiphenyl sulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc., may be used alone or in combination of two or more Can be used. Further, the photopolymerization initiator (C) includes N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like. Photosensitizers such as secondary amines can be used alone or in combination of two or more. A preferred combination is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-benzoyl-4'-methyldiphenyl For example, a combination with sulfide.
Moreover, 0.5-20 mass% of the whole curable composition of this invention is preferable, and, as for the usage-amount of a photoinitiator (C), Most preferably, it is 1-10 mass%.

  The curable composition of the present invention may further contain a photosensitive (meth) acrylate compound (D). As the photosensitive (meth) acrylate compound (D), a liquid, solid or semisolid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule at room temperature can be used. The purpose of using these photosensitive (meth) acrylate compounds is to increase the photoreactivity of the composition. The photosensitive (meth) acrylate compound that is liquid at room temperature is used for the purpose of increasing the photoreactivity of the composition, as well as adjusting the composition to a viscosity suitable for various coating methods and assisting in solubility in an aqueous alkali solution. Also fulfills. 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 compounding quantity of a photosensitive (meth) acrylate compound (D) is 100 with respect to 100 mass parts of total amounts of the said carboxyl group-containing photosensitive compound (A-1) and carboxyl group-containing photosensitive resin (A-2). A proportion of not more than mass parts, preferably 10 to 50 mass parts is appropriate.

  Examples of the photosensitive (meth) acrylate compound (D) include hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate; polyethylene glycol diacrylate Water-soluble acrylates such as polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; trimethylolpropane, hydrogenated bisphenol A, etc. Of polyfunctional alcohols of polyphenols such as bisphenol A and biphenol, and ethylene oxide adducts Acrylates of propylene oxide adducts; polyfunctional or monofunctional polyurethane acrylates which are isocyanate modified products of the above hydroxyl group-containing acrylates; (meth) of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin Examples thereof include epoxy acrylates which are acrylic acid adducts and methacrylates corresponding to the above acrylates. These photosensitive (meth) acrylate compounds can be used alone or in combination of two or more. Among these, a polyfunctional (meth) acrylate compound having two or more (meth) acryloyl groups in one molecule is preferable. In this specification, “(meth) acrylate” is a term that collectively refers to acrylate and methacrylate, and the same applies to other similar expressions.

The curable composition of the present invention includes the carboxyl group-containing photosensitive compound (A-1), the carboxyl group-containing photosensitive resin (A-2), and an epoxy resin (B) having a 1,3-dioxolane ring. In addition, an organic solvent can be added to adjust the composition to a viscosity suitable for the coating method.
Examples of the organic 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. These organic solvents can be used alone or as a mixture of two or more. The usage-amount of an organic solvent is not limited to a specific ratio, It can set suitably according to the coating method to select.

  Furthermore, the curable composition of the present invention is a polyfunctional compound having two or more epoxy groups in one molecule so as not to impair the storage stability in order to improve properties such as heat resistance and PCT resistance of the cured film. An epoxy resin exemplified as the epoxy compound (a) can be blended.

  Moreover, the carboxyl group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2) used in the curable composition of the present invention, and an epoxy resin (B) having a 1,3-dioxolane ring, In order to accelerate the reaction, a curing catalyst can be used. Examples of the curing 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-dimethylbenzylamine Amine compounds such as 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid hydrazide and sebacic acid hydrazide; and phosphorus compounds such as triphenylphosphine. 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, These may be used alone or in admixture of two or more. 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, Preferably, a compound that also functions as an adhesion promoter is used in combination with the curing catalyst. The amount of these used is a normal quantitative ratio. In general, the total amount of the carboxyl group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2) is 100 parts by mass. A ratio of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass is appropriate.

  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. 0-60 mass% of the whole composition of this invention is preferable, and, as for the compounding quantity of an inorganic filler, Most preferably, it is 5-40 mass%.

  Further, the curable composition of the present invention may contain, as necessary, known and commonly used colorants such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and hydroquinone. , Hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, and other known and conventional thermal polymerization inhibitors, fine silica, asbestos, organic bentonite, montmorillonite and other known and conventional thickeners, silicones, fluorines, and polymers And other conventional additives such as an antifoaming agent and / or a leveling agent, an adhesion-imparting agent such as an imidazole-based, thiazole-based, triazole-based, and silane coupling agent.

  Also known binder resins such as copolymers of ethylenically unsaturated compounds such as acrylic esters, polyester resins synthesized from polyhydric alcohols and polybasic acid compounds, and polyester (meth) acrylates Photopolymerizable oligomers such as polyurethane (meth) acrylate and epoxy (meth) acrylate can also be used within a range that does not affect various properties as a solder resist.

  Furthermore, 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 photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2) is converted to an amine such as trimethylamine or triethylamine, or N, N-dimethylamino. Tertiary amino groups such as ethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, acryloylmorpholine, N-isopropyl (meth) acrylamide, N-methylolacrylamide, etc. By making a salt with the (meth) acrylate compound having, the carboxyl group-containing photosensitive compound (A-1) and the carboxyl group-containing photosensitive resin (A-2) used in the present invention are dissolved in water. preferable.

  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, about the thickness of a support body, it selects suitably in the range of 10-150 micrometers.

  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 volatilizing the solvent by heating and drying, but the thickness is not particularly limited and is appropriately selected within the range of 10 to 150 μm.

  As the cover film, a polyethylene film, a polypropylene film, a Teflon (registered trademark) film, a surface-treated paper or the like is generally used. The cover film is not particularly limited as long as the adhesive force between the curable composition layer and the cover film is smaller than the adhesive force between the curable composition layer and the support.

  Carboxyl group-containing photosensitive compound (A-1) as described above, carboxyl group-containing photosensitive resin (A-2), epoxy resin (B) having a 1,3-dioxolane ring, photopolymerization initiator (C), Alternatively, a curable composition in which a photosensitive (meth) acrylate compound, an epoxy resin, a curing catalyst or a curing accelerator, and further, if necessary, an inorganic and / or organic filler, other additives, and the like is conventionally known. A cured product can be easily obtained by photocuring and / or heat-curing in the same manner as the existing method.

  In addition, the curable composition is diluted as necessary to adjust the viscosity suitable for the coating method, and sufficiently mixed until uniform using a roll. It is applied to a printed wiring board on which a circuit has been formed by a screen printing method, a curtain coating method, a spray coating method, a roll coating method or the like. By doing so, a tack-free coating film can be formed. Moreover, in the case of 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, it bonds together using a hot roll laminator etc. to the printed wiring board by which the circuit was formed ( By bonding the curable composition layer and the printed wiring board on which the circuit is formed, the coating film can be formed on the printed wiring board on which the circuit is formed. In the case of a dry film provided with a peelable cover film on the curable composition layer of the film, after the cover film is peeled off, the curable composition layer and the printed wiring board on which the circuit is formed contact. Thus, it is possible to form a coating film on a printed wiring board on which a circuit is formed by laminating using a hot roll laminator or the like.

  After a coating film is formed on the printed wiring board having the circuit formed in this way (when the dry film is used, the support is not peeled off), and then exposed to active energy rays and photocured. For example, a photomask having a predetermined exposure pattern is brought into direct contact with the coating film (or placed on the coating film in a non-contact state), and selectively exposed with active energy rays such as ultraviolet rays, and unexposed portions are removed. Development (dissolution removal) is performed with a dilute alkaline aqueous solution (when the dry film is used, the support is peeled off and developed after exposure). Alternatively, exposure and drawing can be performed directly according to a pattern by a laser beam. Thereafter, it is further heat-resistant at a high level by being fully cured (main curing) by irradiation with active energy rays and / or heating (for example, at about 100 ° C. to 200 ° C. for 0.5 to 1 hour). A cured product having a good balance of PCT resistance, high hardness, excellent adhesion to a substrate, and excellent chemical resistance, moisture absorption resistance, and the like can be obtained.

As alkaline aqueous solution used for the said image development, alkaline aqueous solution, such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, can be used.
As the 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. In addition, laser beams and the like can also be used as active energy rays.

  EXAMPLES Hereinafter, although an Example etc. are shown and this invention is demonstrated more concretely, this invention is not limited to these Examples. In the following description, “part” means part by mass unless otherwise specified.

Synthesis example 1
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”, OH equivalent: 119.4) 119.4 manufactured by Showa Polymer Co., Ltd. Parts, 1.19 parts of potassium hydroxide and 119.4 parts of toluene were charged, and the system was replaced with nitrogen while stirring, and the temperature was raised. 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 hydroxyl value 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 an alkylene 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 reactor 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 118.1 parts of diethylene glycol monoethyl 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, reacted at 95 to 101 ° C. for 6 hours, cooled and taken out. The carboxyl group-containing photosensitive resin thus obtained had a nonvolatile content of 70.6% and a solid content acid value of 87.7 mgKOH / g.

Synthesis example 2
120 parts of poly-p-hydroxystyrene resin (trade name “Marcalinker M”, OH equivalent: 120) manufactured by Maruzen Petrochemical Co., Ltd. in an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device and a stirring device Then, 1.2 parts of potassium hydroxide and 120 parts of toluene were charged, the inside of the system was replaced with nitrogen while stirring, and the temperature was increased. 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 1.57 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide. The nonvolatile content was 62.0%, and the hydroxyl value was 182 g / eq. Thus, a propylene oxide reaction solution of poly-p-hydroxystyrene resin was obtained. This was an average of 1.07 moles of alkylene oxide added per equivalent of phenolic hydroxyl group.

  293.0 parts of an alkylene oxide reaction solution of the obtained poly-p-hydroxystyrene resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methyl hydroquinone, and 252.9 parts of toluene were stirred. A reactor equipped with a machine, a thermometer, 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 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a poly-p-hydroxystyrene resin solution.

  Next, 332.5 parts of the obtained poly-p-hydroxystyrene 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 added at 10 ml / min. While stirring and stirring, 60.8 parts of tetrahydrophthalic anhydride was gradually added, reacted at 95 to 101 ° C. for 6 hours, cooled, and taken out. The carboxyl group-containing photosensitive resin thus obtained had a non-volatile content of 71.8% and a solid content acid value of 85.3 mgKOH / g.

Synthesis example 3
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 aqueous alkali metal hydroxide solution, a hydroxyl group equivalent of 80 g / eq. Of 1,5-dihydroxynaphthalene and 1075 parts of bisphenol A type epoxy resin Epicoat 828 (manufactured by Japan Epoxy Resin Co., Ltd., epoxy equivalent of 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., and the mixture was allowed to react for about 90 minutes while maintaining the temperature at 150 ° C. to obtain an epoxy equivalent of 452 g / eq. The epoxy compound (1-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. with stirring and held. Thereafter, 364 parts of a 48% aqueous sodium hydroxide solution was 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 (1-b) was obtained. When the obtained polynuclear epoxy resin (1-b) is calculated from the epoxy equivalent, about 1.59 of 1.98 alcoholic hydroxyl groups in the epoxy compound (1-a) are epoxidized. Therefore, the epoxidation rate of the alcoholic hydroxyl group is about 80%.
Next, 277 parts of the polynuclear epoxy resin (1-b) is placed in a flask equipped with a stirrer, a condenser tube and a thermometer, 290 parts of carbitol acetate is added, and heated to dissolve, 0.46 parts of methyl hydroquinone, 1.38 parts of phenylphosphine was added and heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 129 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. In the reaction, oxidation of the reaction solution by potentiometric titration and total oxidation measurement are performed, followed by the obtained addition rate, and the end point is 95% or more of the reaction rate. The carboxyl group-containing photosensitive compound thus obtained had a nonvolatile content of 62% and a solid content acid value of 100 mgKOH / g.

Synthesis example 4
Add 330 parts of cresol novolac type epoxy resin (Epiclon N-695, manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent 220) to a flask equipped with a gas introduction tube, a stirrer, a cooling tube and a thermometer, and add carbitol. 400 parts of acetate was added and dissolved by heating, and 0.46 part of hydroquinone and 1.38 parts of triphenylphosphine were added. This mixture was heated to 95 to 105 ° C., 108 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 163 parts of tetrahydrophthalic anhydride was added, and the reaction was allowed to proceed for 8 hours. In the reaction, oxidation of the reaction solution by potentiometric titration and total oxidation measurement are performed, followed by the obtained addition rate, and the end point is 95% or more of the reaction rate. The carboxyl group-containing photosensitive compound thus obtained had a nonvolatile content of 58% and a solid content acid value of 102 mgKOH / g.

Synthesis example 5
Cresol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220) 2200 parts (10 equivalents), dimethylolpropionic acid 134 parts (1 mole), acrylic acid 648. 5 parts (9 mol), 4.6 parts of methylhydroquinone, 1131 parts of carbitol acetate and 484.9 parts of solvent naphtha were charged, heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 13.8 parts of triphenylphosphine, heated to 100 ° C., reacted for about 32 hours, and a reaction product having an acid value of 0.5 mg KOH / g (hydroxyl group: 12 equivalents) Got. Next, 364.7 parts (2.4 moles) of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate and 58.8 parts of solvent naphtha were added to this, heated to 95 ° C., and reacted for about 6 hours. Then, a carboxyl group-containing photosensitive compound having a solid content acid value of 40 mgKOH / g and a solid content concentration of 65% was obtained.

Synthesis Example 6
In a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel for continuous dripping, 70 parts of a novolak type epoxy resin (Epototo YDCN-704 manufactured by Toto Kasei Co., Ltd.), a novolak type epoxy resin (Nipponization) 30 parts of RE-306 (manufactured by Yakuhin Co., Ltd.) and 100 parts of acetone were added and stirred at 20 to 25 ° C. to dissolve the epoxy resin in acetone. Next, a mixture of 1 part of 85% phosphoric acid and 50 parts of acetone was gradually added dropwise and reacted at 20 to 25 ° C. for 24 hours. Next, 70 parts of dipropylene glycol monomethyl ether was added, and the mixture was stirred at 60 to 65 ° C. for 6 hours. Acetone was recovered with an evaporator, and the epoxy equivalent of 274 g / eq. A reaction solution was obtained.

Synthesis example 7
In a reaction vessel equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel for continuous dripping, 70 parts of a novolac type epoxy resin (Epototo YDCN-704 manufactured by Toto Kasei Co., Ltd.), a bisphenol type epoxy resin (Japan epoxy) 30 parts of Epicoat 1004) manufactured by Resin Co., Ltd. and 100 parts of acetone were charged and stirred at 20 to 25 ° C. to dissolve the epoxy resin in acetone. Next, a mixture of 1 part of 85% phosphoric acid and 50 parts of acetone was gradually added dropwise and reacted at 20 to 25 ° C. for 16 hours. Subsequently, 70 parts of dipropylene glycol monomethyl ether was added, and the mixture was stirred at 60 to 65 ° C. for 4 hours. Acetone was recovered with an evaporator, and the epoxy equivalent of 357 g / eq. A reaction solution was obtained.

Examples 1 to 4 and Comparative Examples 1 and 2
The carboxyl group-containing photosensitive resin solution obtained in Synthesis Examples 1 and 2, the carboxyl group-containing photosensitive compound solution obtained in Synthesis Examples 3 to 5, and the reaction product of the epoxy resin obtained in Synthesis Examples 6 and 7 Using the solution, each component was blended according to the blending composition shown in Table 1 (the numerical value is part by weight), kneaded separately with a three-roll mill, each curable composition was prepared, and the storage stability was evaluated. . Next, this is applied to the entire surface of the copper through-hole printed wiring board that has been patterned so as to have a thickness of 20 to 30 μm using a 100-mesh polyester screen by a screen printing method. The film is dried for 60 minutes using a hot air drier, and then a negative film having a resist pattern is brought into close contact with the coating film, and irradiated with ultraviolet rays using an ultraviolet exposure device (Model HMW-680GW, manufactured by Oak Manufacturing Co., Ltd.). The exposure amount was 600 mJ / cm ² ). Subsequently, development was performed with a 1 wt% 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 dryer at 150 ° C. to prepare a test substrate.
About each test board | substrate which has the obtained cured film, each test of solder heat resistance, PCT tolerance, adhesiveness, acid resistance, alkali resistance, and electroless gold-plating tolerance was done with the below-mentioned test method and evaluation method.
In addition, using a B pattern of a printed circuit board (thickness 1.6 mm) defined by IPC instead of a copper through-hole printed wiring board, a test board was produced under the same conditions as described above, and an electrical insulation resistance test was performed. .
Further, a glass plate was used in place of the copper through-hole printed wiring board, and processing was performed under the same conditions as described above to determine the water absorption rate.

(1) Storage stability:
The compositions in Table 1 were placed in a 50 ° C. heat insulation bath and evaluated according to the following criteria.
○: not gelled Δ: slightly gelled ×: gelled Test results are shown in Table 2.

(2) Solder heat resistance:
According to the test method of JIS C 6481, the test substrate was immersed in a solder bath at 260 ° C. for 10 seconds three times, and the change in appearance was evaluated according to the following criteria. However, only the sample which did not gel was tested.
○: No change in appearance Δ: Discoloration of the cured film is observed ×: The cured film is floated, peeled off, and solder is submerged. Table 3 shows the test results.

(3) PCT resistance:
The test substrate was further allowed to stand in a hot air dryer at 170 ° C. for 5 hours, and the PCT resistance after the standing was evaluated according to the following criteria under the conditions of 121 ° C. and 50 hours in saturated steam. However, only the sample which did not gel was tested.
○: The cured film has no blistering, peeling, or discoloration Δ: The cured film has slight blistering, peeling, or discoloration ×: The cured film has blistering, peeling, or discoloration Table 4 shows the test results.

(4) Adhesion:
According to the test method of JIS D 0202, the cured film of the test substrate was cross-cut in a grid pattern, and then the peelability after the peeling test using the cellophane adhesive tape was evaluated according to the following criteria. However, only the sample which did not gel was tested.
○: 100/100 with no peeling Δ: 50/100 to 90/100
X: 0/100 to 50/100
The test results are shown in Table 5.

(5) Acid resistance:
The test substrate was taken out after being immersed in a 10 vol% sulfuric acid aqueous solution at 20 ° C. for 30 minutes, and the state of the cured film was evaluated according to the following criteria. However, only the sample which did not gel was tested.
○: No change is observed Δ: Only a slight change ×: The cured film has blisters or swelling drops Test results are shown in Table 6.

(6) Alkali resistance:
The test substrate was evaluated in the same manner as in the acid resistance test except that the 10 vol% sulfuric acid aqueous solution was replaced with a 10 wt% sodium hydroxide aqueous solution. However, only the sample which did not gel was tested.
The test results are shown in Table 7.

(7) Electroless gold plating resistance:
The test substrate was subjected to electroless gold plating according to the steps described below, and the test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape, and the peeled state of the cured film was determined according to the following criteria. However, only the sample which did not gel was tested.
○: 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 lag is observed, and peeling of the cured film is large in the peeling test.
The test results are shown in Table 8.

Electroless gold plating process:
1. Degreasing: The test substrate was dipped in an acidic degreasing solution at 30 ° C. (manufactured by Nippon McDermid Co., Ltd., 20 vol% aqueous solution of Metex L-5B) for 3 minutes.
2. Rinsing: The test substrate was immersed in running water for 3 minutes.
3. Soft etch: The test substrate was immersed in a 14.3 wt% ammonium persulfate aqueous solution at room temperature for 3 minutes.
4). Rinsing: The test substrate was immersed in running water for 3 minutes.
5). Acid immersion: The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute.
6). Washing with water: The test substrate was immersed in running water for 30 seconds to 1 minute.
7). Catalyst application: The test substrate was immersed for 7 minutes in a 30 ° C. catalyst solution (manufactured by Meltex, 10 vol% aqueous solution of metal plate activator 350).
8). Rinsing: The test substrate was immersed in running water for 3 minutes.
9. Electroless nickel plating: The test substrate was immersed in a nickel plating solution (manufactured by Meltex Co., Ltd., Melplate Ni-865M, 20 vol% aqueous solution) at 85 ° C. and pH = 4.6 for 20 minutes.
10. Acid immersion: The test substrate was immersed in a 10 vol% sulfuric acid aqueous solution at room temperature for 1 minute.
11. Washing with water: The test substrate was immersed in running water for 30 seconds to 1 minute.
12 Electroless gold plating: The test substrate was immersed for 10 minutes in a gold plating solution of 95 ° C. and pH = 6 (manufactured by Meltex Co., Ltd., an aqueous solution of Ourolectroles UP 15 vol%, potassium gold cyanide 3 wt%).
13. Water washing: The test substrate was immersed in running water for 3 minutes.
14 Hot water washing: The test substrate was immersed in warm water at 60 ° C., thoroughly washed with water for 3 minutes, thoroughly drained and dried.
Through such a process, a test substrate plated with electroless gold was obtained.

(8) Electrical insulation:
The electrical insulation of the cured film was evaluated according to the following criteria. However, only the sample which did not gel was tested.
Humidification conditions: temperature 85 ° C., humidity 85% RH, applied voltage 100 V, 500 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 ×: Insulation resistance value after humidification of 10 ⁸ Ω or less, copper migration Yes Test results are shown in Table 9.

(9) Water absorption rate:
Using a PCT apparatus (TABAI ESPEC HASTSYSTEM TPC-412MD), the test substrate was 121 ° C., 100% R.D. H. The water absorption rate of the cured film was determined by the following formula.
Water absorption (%) = [(W ₂ −W ₁ ) / (W ₁ −W _g )] × 100
Here, W ₁ is the mass of the test substrate, W ₂ is the mass of the test substrate after the PCT treatment, and W _g is the mass of the glass plate. However, only the sample which did not gel was tested.
The results of the above test are shown in Table 10.

  Since the curable composition of the present invention as described above is excellent in storage stability, can be composed in a one-pack type, and a cured product having excellent properties as described above can be obtained, a solder resist for a printed wiring board can be obtained. In addition, not only can it be advantageously used as a dry film thereof, but also IC packages such as BGA and CSP of printed wiring boards can be mounted with high reliability without peeling or cracking in the resist. Further, the curable composition of the present invention includes an etching resist, a plating resist, an interlayer insulating layer of a multilayer wiring board, a permanent mask used for manufacturing a tape carrier package, a resist for a flexible wiring board, a resist for a color filter, and a resist for an ink jet. It is also useful for such applications.

Claims (3)

  (A) A reaction in which a compound (a) having two or more epoxy groups in one molecule reacts with an unsaturated group-containing monocarboxylic acid (b) or an unsaturated group-containing monocarboxylic acid (b) and an epoxy group. A carboxyl group-containing photosensitive compound (A-1) obtained by reacting a polybasic acid anhydride (f) with a reaction product (e) with a mixture (d) with a compound (c) having a group; The reaction product of the novolak type phenol resin (g), the alkylene oxide (h) and / or the cyclic carbonate (i) is reacted with the unsaturated group-containing monocarboxylic acid (b), and the resulting reaction product is polybasic. A mixture with a carboxyl group-containing photosensitive resin (A-2) obtained by reacting an acid anhydride (f), (B) a ketone partially on an epoxy resin having two or more epoxy groups in one molecule 1,3-obtained by addition reaction Epoxy resins having an oxolane ring, and (C) curable composition characterized by containing a photopolymerization initiator.   In the said epoxy resin (A), the reaction ratio of the ketone with respect to an epoxy resin is 0.03-0.9 equivalent for a carbonyl group with respect to 1 equivalent of epoxy groups, The hardening of Claim 1 characterized by the above-mentioned. Sex composition.   A cured product of the curable composition according to claim 1 or 2.