JP2003280191A - Photosetting and thermosetting resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting and thermosetting resin composition giving a cured film excellent in adhesion, heat resistance, electroless plating resistance, moisture absorption resistance, PCT resistance and electric properties. <P>SOLUTION: The composition comprises (A) a carboxylic photosensitive resin obtained by reacting an epoxy compound (a) having two or more epoxy groups in one molecule with a compound (b) having two or more hydroxyl groups and one reactive group other than a hydroxyl group and reacting with an epoxy group in one molecule and an unsaturated group-containing monocarboxylic acid (c) and reacting the resulting reaction product with a polybasic acid anhydride (d), (B) a carboxylic photosensitive resin obtained by reacting the reaction product of a novolak type phenolic resin (e) and an alkylene oxide (f) with the unsaturated group-containing monocarboxylic acid (c) and reacting the resulting reaction product with the polybasic acid anhydride (d), (C) a photopolymerization initiator, (D) a photosensitive (meth)acrylate compound, (E) an epoxy compound and (F) a diluting solvent. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable / thermosetting resin composition used as a solder resist or the like for printed wiring boards, and in particular, adhesion to a base material required for a resist for an IC package. , Dilute alkali development type photocurable / thermosetting resin composition suitable for obtaining a cured film excellent in electroless gold plating resistance, solder heat resistance, moisture absorption resistance, PCT (pressure cooker) resistance, electric insulation, etc. Regarding things.

[0002]

2. Description of the Related Art At present, solder resists for some consumer printed wiring boards and most industrial printed wiring boards are exposed to ultraviolet rays and developed to form an image from the viewpoint of high accuracy and high density. Liquid development type solder resist that is hardened (mainly cured) by heat and / or light irradiation is used, and from the viewpoint of environmental issues, alkali development type photo solder resist using a dilute alkaline aqueous solution as a developing solution has become the mainstream. There is. As an alkaline development type solder resist using such a dilute alkaline aqueous solution,
For example, JP-A-61-243869 discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a photopolymerizable monomer and an epoxy compound. A solder resist composition comprising the following is disclosed. Also, Japanese Patent Laid-Open No. 3-2530
No. 93 discloses a photosensitive resin obtained by adding an acid anhydride to a reaction product of a novolac type epoxy compound and an unsaturated monobasic acid, a photopolymerization initiator, a diluent, vinyltriazine or a mixture of vinyltriazine and dicyandiamide, and melamine. A solder resist composition comprising a resin is disclosed in JP-A-3-7.
In Japanese Patent No. 1137 and Japanese Patent Laid-Open No. 3-250012,
A solder resist composition comprising salicylaldehyde, an epoxy resin which is a reaction product of monohydric phenol and epichlorohydrin, a photopolymerization initiator, an organic solvent and the like is disclosed.

[0003]

As described above, several composition systems have been conventionally proposed as the solder resist, and they are currently used in large quantities in the actual production of printed wiring boards. However, workability and high performance have been required for solder resists in response to the higher density of printed wiring boards accompanying the recent trend of lighter, thinner, shorter, and smaller electronic devices. More recently, in place of IC packages called QFP (Quad Flat Pack Package) and SOP (Small Outline Package) that use lead frames and sealing resin, printed wiring boards with solder resist and sealed I using antistatic resin
C package has appeared. These new packages are
A ball-shaped metal such as solder is arranged in an area on one side of a printed wiring board with a solder resist, and I
The C chip has a structure in which it is directly connected by wire bonding or bumps and sealed with a sealing resin.
(Ball grid array), CSP (chip scale package), etc. These packages have more pins and are easier to miniaturize than packages of the same size such as QFP. Also in mounting, a low defect rate is realized by the self-alignment effect of the ball-shaped solder, and its introduction is being promoted rapidly.

However, in the conventional printed wiring board on which a commercially available alkali-development type solder resist is applied, the PCT resistance which is a long-term reliability test of the package is inferior, and the solder resist film peels off. Further, due to the moisture absorption of the solder resist, the moisture absorbed inside the package is boiled during the reflow at the time of mounting the package, and a so-called popcorn phenomenon is caused, which causes cracks in the solder resist film inside the package and the periphery thereof.
Such problems of moisture absorption resistance and long-term reliability are not limited to the case of the above-mentioned mounting technology, but include solder resists of general printed wiring boards and interlayer insulating layers of multilayer wiring boards such as build-up boards. , Is not desirable in products for other applications.

Therefore, an object of the present invention is to provide excellent properties such as adhesion, heat resistance, electroless plating resistance, and electrical characteristics required for a solder resist of a printed wiring board or an interlayer insulating layer of a multilayer wiring board. In addition, a cured film with excellent PCT resistance and moisture absorption resistance, which is especially required for IC packages, can be obtained, and it can be used for high density and surface mounting of printed wiring boards. To provide a sex composition.

[0006]

In order to achieve the above-mentioned object, according to the present invention, (A) an epoxy compound (a) having two or more epoxy groups in one molecule and two in one molecule.
1 other than hydroxyl groups that react with one or more hydroxyl groups and epoxy groups
Containing a carboxyl group obtained by reacting a compound (b) having one reactive group with an unsaturated group-containing monocarboxylic acid (c) and reacting the obtained reaction product with a polybasic acid anhydride (d) A reaction product of a photosensitive resin (B) a novolac type phenol resin (e) and an alkylene oxide (f) is reacted with an unsaturated group-containing monocarboxylic acid (c), and the obtained reaction product is a polybasic acid. Carboxyl group-containing photosensitive resin obtained by reacting anhydride (d), (C) photopolymerization initiator, (D) photosensitive (meth) acrylate compound, (E)
Provided is a photocurable / thermosetting resin composition comprising an epoxy compound and (F) a diluting solvent. In a preferred embodiment, the composition further comprises (G) curing catalyst.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that a photosensitive prepolymer starting from an epoxy compound and a novolac type phenol are essential components of the composition. The inventors have found that the above objects can be achieved by incorporating a photosensitive prepolymer having a resin as a starting material in combination, and have completed the present invention.

That is, the photocurable / thermosetting resin composition of the present invention is characterized by a combination of two kinds of carboxyl group-containing photosensitive resins contained therein. One of the carboxyl group-containing photosensitive resins (B) used in the present invention is excellent in flexibility and elongation due to chain extension by the addition reaction of alkylene oxide (f) of novolac type phenol resin (e), and is excellent in alkylene oxide content. Unsaturated group-containing monocarboxylic acid (c) and polybasic acid anhydride (d) were added to the terminal hydroxyl group generated by the addition reaction, and an unsaturated group and a carboxyl group were not present on the same side chain. Moreover, since they are respectively located at the ends of the side chains, they have excellent reactivity, and also have excellent alkali developability due to the presence of terminal carboxyl groups distant from the main chain. Moreover, since the resin does not have a hydrophilic alcoholic hydroxyl group having low reactivity such as the other carboxyl group-containing photosensitive resin (A), or has only a small amount, it has excellent moisture absorption resistance. ing. However, since such a carboxyl group-containing photosensitive resin (B) having no alcoholic hydroxyl group is inferior in dryness to the touch, it is necessary to use it in combination with another photosensitive resin from the viewpoint of workability. . In order to obtain dryness to the touch without deteriorating various properties, in the present invention, as one carboxyl group-containing photosensitive resin used in combination, while exhibiting excellent alkali developability, adhesion with various substrates, Solder heat resistance,
An epoxy compound (a) having two or more epoxy groups in one molecule, which gives a cured film excellent in chemical resistance, resistance to electroless gold plating, and electrical insulation, and two or more hydroxyl groups in one molecule. And a compound (b) having one reactive group other than a hydroxyl group that reacts with an epoxy group and an unsaturated group-containing monocarboxylic acid (c) are reacted, and the resulting reaction product is a polybasic acid anhydride ( d) The photosensitive resin (A) containing a carboxyl group obtained by the reaction is used in combination.

Therefore, these two kinds of carboxyl group-containing photosensitive resins (A) and (B) are added to the photopolymerization initiator (C),
The photocurable / thermosetting resin composition of the present invention containing the photosensitive (meth) acrylate compound (D), the epoxy compound (E), the diluting solvent (F) and the like has excellent dryability to touch and alkali development. It exhibits excellent properties and excellent workability, and by selective exposure, development and finish curing of the coating film, adhesion, solder heat resistance, chemical resistance, electroless gold plating resistance, moisture absorption resistance, PCT resistance, electrical insulation It gives a cured film having excellent properties.

The photocurable / thermosetting resin composition of the present invention will be described in detail below. First, the compounding ratio of the carboxyl group-containing photosensitive resins (A) and (B) constituting the photocurable / thermosetting resin composition of the present invention is arbitrary depending on the purpose, but the carboxyl group-containing photosensitive resin Carboxyl group-containing photosensitive resin (B) is added to resin (A) at 70:30
To 30:70, and the total acid value of both resins is 30 to 150 mgKOH / g, preferably 40.
It is desirable to be in the range of 110 mgKOH / g. When the acid value after compounding the carboxyl group-containing photosensitive resins (A) and (B) is lower than 30 mgKOH / g,
Solubility in an alkaline aqueous solution becomes poor, and development of the formed coating film becomes difficult. On the other hand, when it is higher than 150 mgKOH / g, the surface of the exposed portion is developed regardless of the exposure conditions, which is not preferable.

Next, as described above, the carboxyl group-containing photosensitive resin (A) contains the epoxy compound (a) having two or more epoxy groups in one molecule and the epoxy compound (a) having two or more epoxy groups in one molecule.
1 other than hydroxyl groups that react with one or more hydroxyl groups and epoxy groups
Containing a carboxyl group obtained by reacting a compound (b) having one reactive group with an unsaturated group-containing monocarboxylic acid (c) and reacting the obtained reaction product with a polybasic acid anhydride (d) It is a photosensitive resin. Such a carboxyl group-containing photosensitive resin (A) contains 30 to 150 mgKOH / g,
It is desirable to have an acid value preferably within the range of 50 to 120 mg KOH / g. When the acid value of the carboxyl group-containing photosensitive resin (A) is lower than 30 mgKOH / g, the solubility in an alkaline aqueous solution becomes poor and the formed coating film becomes difficult to develop. Meanwhile, 150 mg KO
When it is higher than H / g, the surface of the exposed portion is developed regardless of the exposure conditions, which is not preferable.

As the epoxy compound (a) having two or more epoxy groups in one molecule, Epicoat 828 and Epicoat 83 manufactured by Japan Epoxy Resin Co., Ltd.
4, Epicoat 1001, Epicoat 1004, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by Dainippon Ink and Chemicals, Inc.
Toto Kasei Co., Ltd. Epotote YD-011, YD-0
13, YD-127, YD-128, Sumi-epoxy ESA-011, ESA-0 manufactured by Sumitomo Chemical Co., Ltd.
Bisphenol A type epoxy resins such as 14, ELA-115 and ELA-128 (all are trade names); Epicoat YL903 manufactured by Japan Epoxy Resin Co., Ltd., Epicron 152, Epicron 165 manufactured by Dainippon Ink and Chemicals, Inc. Toto Kasei Co., Ltd. Epotote YDB-40
0, YDB-500, 2 sumi made by Sumitomo Chemical Co., Ltd.
Brominated epoxy resins such as epoxy ESB-400 and ESB-700 (both are trade names); Epicoat 152, Epicoat 154 manufactured by Japan Epoxy Resin Co., Ltd., Epicron N-730 manufactured by Dainippon Ink and Chemicals, Inc.,
Epicron N-770, Epicron N-865, Epotote YDCN-701, YDCN- manufactured by Tohto Kasei Co., Ltd.
704, EPKA-201, EOC manufactured by Nippon Kayaku Co., Ltd.
N-1025, EOCN-1020, EOCN-104
S, RE-306, Sumitomo Chemical Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220 (all are trade names) and other novolac type epoxy resins; Dainippon Ink and Chemicals Co., Ltd. Epicron 830, Epikote 807 manufactured by Japan Epoxy Resins, Epotote YDF-170, YDF-175, YDF-2 manufactured by Tohto Kasei Co., Ltd.
Bisphenol F type epoxy resin such as 004 (all are trade names); Epotote ST-200 manufactured by Tohto Kasei Co., Ltd.
4, ST-2007, ST-3000 (all are trade names)
Hydrogenated bisphenol A type epoxy resin such as Epikote 604 manufactured by Japan Epoxy Resins Co., Ltd., Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., and Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. Glycidylamine type epoxy resin such as trade name; alicyclic epoxy resin such as Celoxide 2021 (trade name) manufactured by Daicel Chemical Industries, Ltd .; YL-933 manufactured by Japan Epoxy Resin Co., Ltd., Nippon Kayaku Co., Ltd. ) Made EPPN-50
1, trihydroxyphenylmethane type epoxy resin such as EPPN-502 (all are trade names); YL-6056, YX-4000, Y manufactured by Japan Epoxy Resin Co., Ltd.
Bixylenol type or biphenol type epoxy resins such as L-6121 (all are trade names) or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Co., Ltd., Dainippon Ink Chemical Industry Co., Ltd.
Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Japan; Japan Epoxy Resin Co., Ltd.
Bisphenol A novolac type epoxy resin such as Epicoat 157S (trade name) manufactured by Japan; Tetraphenylolethane type epoxy resin such as Epicoat YL-931 (trade name) manufactured by Japan Epoxy Resins Co., Ltd .; Nissan Kagaku Co., Ltd.
Heterocyclic epoxy resin such as TEPIC (trade name) manufactured by;
Diglycidyl phthalate resin such as Bremmer DGT (trade name) manufactured by NOF CORPORATION; ZX- manufactured by Toto Kasei Co., Ltd.
Tetraglycidyl xylenoylethane resins such as 1063 (trade name); ESN-190, E manufactured by Nippon Steel Chemical Co., Ltd.
SN-360, HP-manufactured by Dainippon Ink and Chemicals, Inc.
Naphthalene group-containing epoxy resins such as 4032, EXA-4750, and EXA-4700 (all are trade names); HP-7200, HP-72 manufactured by Dainippon Ink and Chemicals, Inc.
Epoxy resin having a dicyclopentadiene skeleton such as 00H (all are trade names); CP-50 manufactured by NOF CORPORATION
S, CP-50M (both are trade names) glycidyl methacrylate copolymer epoxy resins; cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resins, and the like, and further biphenol diglycidyl ether, bixylenol di An aromatic epoxy compound having two glycidyl groups in one molecule of at least one selected from the group consisting of glycidyl ether, bisphenol diglycidyl ether and naphthalene diglycidyl ether, dihydroxynaphthalene and its derivatives, biphenol and Its derivatives, bixylenol and its derivatives, bisphenol and its derivatives,
And a line obtained by reacting epihalohydrin with an alcoholic hydroxyl group in a reaction product of an aromatic alcohol having at least one phenolic hydroxyl group in one molecule selected from the group consisting of hydroquinone derivatives However, the present invention is not limited to these. These epoxy compounds can be used alone or in combination of two or more kinds.

Specific examples of the compound (b) having two or more hydroxyl groups in one molecule and one reactive group other than the hydroxyl group which reacts with the epoxy group (for example, a carboxylic acid group, a secondary amino group, etc.) Is, for example, dimethylolpropionic acid,
Examples thereof include polyhydroxy-containing monocarboxylic acids such as dimethylolacetic acid, dimethylolbutyric acid, dimethylolvaleric acid, and dimethylolcaproic acid; dialkanolamines such as diethanolamine and diisopropanolamine. Particularly preferred is, for example, dimethylolpropionic acid.

Typical examples of the unsaturated group-containing monocarboxylic acid (c) include acrylic acid, methacrylic acid,
Alternatively or additionally, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, Phenylglycidyl (meta)
Examples thereof include acrylates and unsaturated dibasic acid anhydride adducts of hydroxyl group-containing acrylates such as (meth) acrylic acid caprolactone adducts. Particularly preferred here are acrylic acid and / or methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more kinds.

The reaction between the epoxy compound (a), the compound (b) and the unsaturated group-containing monocarboxylic acid (c) is carried out by the epoxy compound (a) and the compound (b) (or unsaturated group-containing monocarboxylic acid). Acid (c)), and then the unsaturated group-containing monocarboxylic acid (c) (or compound (b)) is reacted, the epoxy compound (a), compound (b) and unsaturated There is a second method in which the group-containing monocarboxylic acid (c) is simultaneously reacted. Either method is acceptable, but the second method is preferred. Such a reaction is carried out in the presence or absence of an organic solvent described later in the presence or absence of a polymerization inhibitor such as hydroquinone and oxygen, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, and 2-ethyl. Usually, it can be easily carried out at 60 to 130 ° C. in the presence of a reaction catalyst such as an imidazole compound such as -4-methylimidazole or a phosphorus compound such as triphenylphosphine.

In the reaction of the epoxy compound (a) with the compound (b) and the unsaturated group-containing monocarboxylic acid (c), the compound (b) is added to 1 equivalent of the epoxy group of the epoxy compound (a). And the unsaturated group-containing monocarboxylic acid (c) are preferably reacted in a ratio of about 0.8 to 1.3 mol, particularly preferably about 0.9 to 1.
The reaction is carried out at a ratio of 1 mol. The ratio of the compound (b) and the unsaturated group-containing monocarboxylic acid (c) used is the same as that of the compound (b).
And the total amount of unsaturated group-containing monocarboxylic acid (c), and the amount of the compound (b) used is preferably 0.05 to 0.5 mol, particularly preferably 0.1 to 0. 3 mol.

The alcoholic hydroxyl group of the reaction product produced by the above reaction is reacted with a polybasic acid anhydride (d) to obtain a carboxyl group-containing photosensitive resin (A). In this reaction, the polybasic acid anhydride is used. The amount of the product (d) used is appropriately a ratio of 0.3 to 0.8 equivalent of the anhydride group of the polybasic acid anhydride (d) to 1 equivalent of the alcoholic hydroxyl group in the reaction product, The acid value of the carboxyl group-containing photosensitive resin (A) produced is preferably 50 to 120 mgKOH / g.
The added amount is such that The reaction is usually carried out at 50 to 130 ° C. in the presence or absence of an organic solvent and in the presence of a polymerization inhibitor such as hydroquinone or oxygen. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, an imidazole compound such as 2-ethyl-4-methylimidazole, or a phosphorus compound such as triphenylphosphine is added as a catalyst. You may.

Examples of the polybasic acid anhydride (d) include methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, and 3,6-endomethylenetetrahydroanhydride. Alicyclic dibasic acid anhydrides such as phthalic acid, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride; succinic anhydride, maleic anhydride, itaconic anhydride, octenylsuccinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride Acid, aliphatic or aromatic dibasic acid anhydride such as trimellitic anhydride, or biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride Anhydrous, anhydrous pyromellitic , Aliphatic or aromatic tetracarboxylic acid dianhydride such as benzophenone tetracarboxylic acid dianhydride and the like, can be used one or two or more of these.

Next, the carboxyl group-containing photosensitive resin (B) is obtained by reacting the novolac type phenol resin (e) and the alkylene oxide (f) with the unsaturated group-containing monocarboxylic acid (c) as described above. ) Is reacted and the obtained reaction product is reacted with the polybasic acid anhydride (d). Such a carboxyl group-containing photosensitive resin (B) has a content of 30 to 150 mgKOH / g, preferably 5
It is desirable to have an acid number within the range of 0 to 120 mg KOH / g.

The above novolac type phenolic resin (e)
Is obtained by a condensation reaction of phenols and formaldehyde, and these reactions are usually carried out in the presence of an acidic catalyst. As phenols, phenol,
Cresol, ethylphenol, propylphenol,
Butylphenol, hexylphenol, octylphenol, nonylphenol, phenylphenol, cumylphenol and the like can be mentioned.

The addition ratio of the alkylene oxide (f) to the novolac type phenol resin (e) is preferably 0.3 to 5.0 mol per equivalent of the phenolic hydroxyl group of the novolac type phenol resin (e). If it is less than 0.3 mol and more than 5.0 mol, the photocurability of the photocurable / thermosetting resin composition containing the carboxyl group-containing photosensitive resin (B) may be poor.

The addition reaction of the alkylene oxide (f) to the novolac type phenol resin (e) is carried out, for example, by an alkali metal compound such as sodium hydroxide, trimethylbenzylammonium hydroxide, tetramethylammonium hydroxide or tetraethylammonium hydrode. In the presence of a quaternary basic salt compound such as oxide, or a mixture of an alkali metal compound and a quaternary basic salt compound, for example, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomer Using acetic acid esters such as ether ether acetate, aromatic hydrocarbons such as toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone, and a mixed solvent such as toluene and methyl isobutyl ketone at 80 to 180 ° C. under normal pressure. -10kg / cm ²
Done in.

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

The reaction temperature in the esterification reaction of the reaction product of the novolac type phenol resin (e) with the alkylene oxide (f) and the unsaturated group-containing monocarboxylic acid (c) is preferably about 50 to 150 ° C. The reaction can be performed under reduced pressure, normal pressure, or increased pressure. In this esterification reaction, the unsaturated group-containing monocarboxylic acid (c) is preferably added in such an amount that the double bond equivalent of the carboxyl group-containing photosensitive resin (B) of the present invention is 300 to 700. . As the reaction solvent, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl isobutyl ketone and methyl ethyl ketone;
Hydrocarbons such as n-hexane, cyclohexane and methylcyclohexane; halogenated hydrocarbons such as trichloroethane, tetrachloroethylene and methylchloroform;
Ethers such as diisopropyl ether; acetic acid esters such as ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate It is preferably used. These solvents may 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 or the like is appropriately used. The esterification reaction is preferably carried out in the presence of a polymerization inhibitor, and as the polymerization inhibitor, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol or the like is preferably used.

The reaction product contains a polybasic acid anhydride (d)
To obtain a carboxyl group-containing photosensitive resin (B). The reaction is usually carried out in the presence or absence of an organic solvent in the presence of a polymerization inhibitor such as hydroquinone or oxygen at 50%.
Perform at ~ 130 ° C. At this time, if necessary, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, 2-ethyl-
An imidazole compound such as 4-methylimidazole or a phosphorus compound such as triphenylphosphine may be added as a catalyst. In this reaction, polybasic acid anhydride (d)
The amount used is such that the acid value of the resulting carboxyl group-containing photosensitive resin (B) is 30 to 150 mgKOH / g, preferably 50 to 120 mgKOH / g. The acid value of the carboxyl group-containing photosensitive resin (B) is 3
When it is lower than 0 mgKOH / g, the solubility in an alkaline aqueous solution becomes poor and the formed coating film becomes difficult to develop. On the other hand, when it is higher than 150 mgKOH / g, the surface of the exposed portion is developed regardless of the exposure conditions, which is not preferable.

Next, as the photopolymerization initiator (C) constituting the photocurable / thermosetting resin composition of the present invention, for example,
Benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-
2-phenylacetophenone, 2,2-diethoxy-2
-Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylpheniketone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone-
Aminoacetophenones such as 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2 Anthraquinones such as -tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone Thioxanthones such as; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenone, methylbenzophenone,
4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4-benzoyl-4'-
Benzophenones such as methyldiphenyl sulfide;
2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like can be mentioned. These photopolymerization initiators can be used alone or in combination of two or more kinds. Further, the photopolymerization initiator (C) is N, N-
Dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4
-It can be used in combination with one or more photosensitizers or photoinitiator aids such as tertiary amines such as dimethylaminobenzoate, triethylamine and triethanolamine. Also, C which has absorption in the visible light region
A titanocene compound such as GI-784 (manufactured by Ciba Specialty Chemicals) can also be added to accelerate the photoreaction. It is not particularly limited to these, as long as it absorbs light in the ultraviolet light or visible light region and radically polymerizes an unsaturated group such as a (meth) acryloyl group, a photopolymerization initiator, a photosensitizer ( Photo initiation aid)
Not limited to these, they can be used alone or in combination.

The preferred combination is 2-methyl-1- [4
-(Methylthio) phenyl] -2-morpholino-aminopropanone-1 and 2,4-diethylthioxanthone or 2
-Isopropylthioxanthone, 4-benzoyl-4 '
-Combination with methyldiphenyl sulfide and the like.

The blending amount of the photopolymerization initiator (C) (when the photosensitizer or photoinitiating auxiliary agent is used, the total amount thereof) is the same as that of the carboxyl group-containing photosensitive resins (A) and (B). 0.1 to 30 parts by mass, preferably 0.5 to 100 parts by mass based on the total amount (as solid content, the same applies below).
A ratio of 20 parts by mass is desirable. When the blending amount of the photopolymerization initiator (C) is less than the above range, it does not cure even when irradiated with active energy rays, or the irradiation time needs to be increased, and it becomes difficult to obtain appropriate film characteristics. On the other hand, even if the photopolymerization initiator is added in a larger amount than the above range,
There is no change in photocurability, which is economically unfavorable.

As the photosensitive (meth) acrylate compound (D), a photosensitive (meth) acrylate compound having at least one (meth) acryloyl group in one molecule which is liquid, solid or semi-solid at room temperature is used. it can. 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 has the role of increasing the photoreactivity of the composition, adjusting the composition to have a viscosity suitable for various coating methods, and helping the solubility in an alkaline aqueous solution. Also fulfills. However, if a large amount of a photosensitive (meth) acrylate compound that is liquid at room temperature is used, the dryness to the touch of the coating film cannot be obtained and the characteristics of the coating film tend to deteriorate. Not preferable. The blending amount of the photosensitive (meth) acrylate compound (D) is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resins (A) and (B).

Examples of the photosensitive (meth) acrylate compound (D) include hydroxyl group-containing acrylates such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate; polyethylene. Water-soluble acrylates such as glycol diacrylate and polypropylene glycol diacrylate; polyfunctional polyester acrylates of polyhydric alcohols such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; trimethylolpropane, hydrogenation Ethylene of polyfunctional alcohols such as bisphenol A or polyhydric phenols such as bisphenol A and biphenol Oxide adduct and / or acrylates of propylene oxide adducts; isocyanate modified product in which a polyfunctional or monofunctional polyurethane acrylates of the hydroxyl group-containing acrylate; bisphenol A diglycidyl ether, hydrogenated bisphenol A
Examples include epoxy acrylates, which are (meth) acrylic acid adducts of diglycidyl ether or phenol novolac epoxy resins, and methacrylates corresponding to the above acrylates, which may be used alone or in combination of two or more. You can Among these, polyfunctional (meth) acrylate compounds having two or more (meth) acryloyl groups in one molecule are preferable.

As the epoxy compound (E) used as the thermosetting component in the photocurable / thermosetting resin composition of the present invention, the epoxy compound previously used in the synthesis of the carboxyl group-containing photosensitive resin (A) is used. Those exemplified as (a) can be used alone or in combination of two or more kinds. The compounding amount of the epoxy compound (E) can be appropriately set according to the application, and is generally 5 to 100 parts by mass relative to 100 parts by mass of the total amount of the carboxyl group-containing photosensitive resins (A) and (B). Is appropriate.

The diluent solvent (F) is used to dissolve the carboxyl group-containing photosensitive resins (A) and (B) and to adjust the composition to have a viscosity suitable for the coating method. As the diluting solvent, for example, ethyl methyl ketone,
Ketones such as cyclohexanone; toluene, xylene,
Aromatic hydrocarbons such as tetramethylbenzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether,
Glycol ethers such as dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbyl acetate; alcohols such as ethanol, propanol, ethylene glycol, propylene glycol; octane And aliphatic hydrocarbons such as decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The amount of the diluent solvent (F) used is preferably 10 to 300 parts by mass based on 100 parts by mass of the total solid content of the carboxyl group-containing photosensitive resins (A) and (B).

The curing catalyst (G) further improves various properties as a solder resist, such as toughness, adhesion, heat resistance, resistance to electroless gold plating, and the like. Specific examples of the curing catalyst (G) include 2MZ, 2E4MZ, C11Z, C17Z and 2M manufactured by Shikoku Chemicals Co., Ltd.
PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN,
C11Z-CN, 2PZ-CN, 2PHZ-CN, 2M
Z-CNS, 2E4MZ-CNS, 2PZ-CNS, 2
MZ-AZINE, 2E4MZ-AZINE, C11Z
-AZINE, 2MA-OK, 2P4MHZ, 2PH
Imidazole derivatives such as Z, 2P4BHZ and 1B2PZ; guanamines such as acetoguanamine and benzoguanamine; Polyamines; Organic acid salts and / or epoxy adducts of these: amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-
Triazine derivatives such as diamino-S-triazine and 2,4-diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methyl Tertiary amines such as morpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol; polyvinylphenol, polyvinylphenol bromide, phenol novolac, alkylphenol Polyphenols such as novolac; tributylphosphine, triphenylphosphine, tris-2-
Organic phosphines such as cyanoethylphosphine; tri-
Phosphonium salts such as n-butyl (2,5-dihydroxyphenyl) phosphonium bromide and hexadecyltributylphosphonium chloride; quaternary ammonium salts such as benzyltrimethylammonium chloride and phenyltributylammonium chloride; the polybasic acid anhydride; diphenyliodonium tetra Fluoroborate, triphenylsulfonium hexafluoroantimonate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, Irgacure 261, manufactured by Ciba Specialty Chemicals, Optomer SP-170 manufactured by Asahi Denka Co., Ltd. Cationic polymerization catalyst of styrene-maleic anhydride resin; equimolar reaction product of phenylisocyanate and dimethylamine, tolylene diisocyanate, isophore Curing agents or curing accelerators such conventionally known, such as equimolar reaction product of an organic polyisocyanate and dimethyl amine such emissions diisocyanate and the like, can be used alone or in combination of two or more. The amount of the curing catalyst (G) used is preferably 0.01 to 25 parts by mass, and particularly preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the epoxy compound (E).

The photo-curable / thermo-curable resin composition of the present invention further contains barium sulfate, barium titanate, and, if necessary, for the purpose of improving properties such as adhesion and hardness.
Known and commonly used inorganic fillers such as silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide and mica powder can be used. The amount used is preferably 0 to 60 mass of the entire composition of the present invention, and particularly preferably 5
Is about 40% by mass.

If necessary, known phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, and other known coloring agents, hydroquinone, hydroquinone monomethyl ether, Known and commonly used polymerization inhibitors such as tert-butylcatechol, pyrogallol, phenothiazine,
Known and commonly used thickeners such as asbestos, orben, benton and montmorillonite, defoaming agents and / or leveling agents such as silicone type, fluorine type, polymer type, imidazole type, thiazole type, triazole type, silane coupling agent, etc. Well-known and commonly used additives such as the adhesion-imparting agent can be added.

Further, water can be added to the photocurable / thermosetting resin composition of the present invention in order to reduce the flammability. When water is added, the carboxyl groups of the carboxyl group-containing photosensitive resins (A) and (B) are converted to amines such as trimethylamine and triethylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N- Dimethylaminopropyl (meth) acrylamide, N, N
-Dimethyl (meth) acrylamide, acryloylmorpholine, N-isopropyl (meth) acrylamide, N
-By salt formation with a (meth) acrylate compound having a tertiary amino group such as methylol acrylamide,
It is preferable to dissolve the carboxyl group-containing photosensitive resin of the components (A) and (B) in water.

The photocurable / thermosetting resin composition of the present invention can be obtained by blending the above-mentioned blending components preferably in the above proportions and uniformly mixing them with a roll mill or the like. Further, the photocurable / thermosetting resin composition of the present invention can be cured, for example, as described below to obtain a cured product. That is, the photocurable / thermosetting resin composition of the present invention having a film thickness of 10 to 100 μm on a printed wiring board by a method such as a screen printing method, a spray method, a roll coating method, an electrostatic coating method and a curtain coating method. Is applied, and the coating film is dried at 60 to 110 ° C., and then the negative film is brought into direct contact with the coating film (or is placed on the coating film without contacting it), followed by irradiation with ultraviolet rays, and After the exposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution (for example, 0.5 to 2% sodium carbonate aqueous solution), further ultraviolet irradiation and / or heating (for example, 100
Sufficiently cure at ~ 200 ° C for 0.5 to 1 hour) to obtain a cured film.

[0038]

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

Synthesis Example 1 2200 parts of cresol / novolak type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220), dimethylolpropionic acid 134 parts, acrylic acid 648.5 parts , 4.6 parts of methylhydroquinone, 1131 parts of carbitol acetate and 484.9 parts of solvent naphtha were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Then, the reaction solution is 60
The mixture was cooled to ℃, charged with 13.8 parts of triphenylphosphine, heated to 100 ℃ and reacted for about 32 hours to obtain a reaction product having an acid value of 0.5 mgKOH / g. Next, 364.7 parts of tetrahydrophthalic anhydride, 137.5 parts of carbitol acetate and 58.8 of solvent naphtha were added thereto.
Parts, heated to 95 ° C., reacted for about 6 hours, cooled, solid acid value 40 mg KOH / g, nonvolatile content 65%
To obtain a carboxyl group-containing photosensitive resin.

Synthetic Example 2 2200 parts of cresol / novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., EOCN-104S, softening point 92 ° C., epoxy equivalent 220), dimethylolpropionic acid 402 parts, acrylic acid 504.4 parts , 4.8 parts of methylhydroquinone, 1178 parts of carbitol acetate and 505 parts of solvent naphtha were charged and heated to 90 ° C. and stirred to dissolve the reaction mixture. Next, the reaction solution is heated to 60 ° C.
After cooling to 14.3 parts of triphenylphosphine, the mixture was heated to 100 ° C. and reacted for about 32 hours to obtain a reaction product having an acid value of 0.8 mgKOH / g. Next, 276.5 parts of tetrahydrophthalic anhydride, 104 parts of carbitol acetate and 45 parts of solvent naphtha were charged, heated to 95 ° C., reacted for about 6 hours, cooled, and the solid acid value was 30 mgKOH / g. Thus, a carboxyl group-containing photosensitive resin having a nonvolatile content of 65% was obtained.

Synthesis Example 3 An autoclave equipped with a thermometer, a nitrogen introducing device and an alkylene oxide introducing device, and a stirrer was placed in a novolac-type cresol resin (Showa High Polymer Co., Ltd., trade name "Shonor CRG951", OH equivalent: 119.4) 119.
4 parts, potassium hydroxide 1.19 parts and toluene 119.
4 parts were charged, the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise to 1 at 125 to 132 ° C. and 0 to 4.8 kg / cm ² .
The reaction was carried out for 6 hours. Then, the mixture was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with this reaction solution to neutralize potassium hydroxide, and the nonvolatile content was 62.1% and the hydroxyl value was 18%.
2.2 g / eq. A propylene oxide reaction solution of the novolac type cresol resin was obtained. The average alkylene oxide is 1.0 per equivalent of phenolic hydroxyl group.
It was added with 8 mol.

293.0 parts of an alkylene oxide reaction solution of the obtained novolac type cresol resin, acrylic acid 4
3.2 parts, 11.53 parts of methanesulfonic acid, 0.18 parts of methylhydroquinone and 252.9 parts of toluene were charged into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at 10 ml / min. The mixture was blown at a speed and reacted at 110 ° C. for 12 hours while stirring. The water generated by the reaction was an azeotropic mixture with toluene, and 12.6 parts of water was distilled out. Then, the mixture was cooled to room temperature, the resulting reaction solution was neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, and then washed with water. Then, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the obtained novolak type 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 to the mixture at 95 to 101 ° C. for 6 hours.
React for hours, cool down, acid value of solids 87.7 mg KO
A carboxyl group-containing photosensitive resin having H / g and a nonvolatile content of 70.6% was obtained.

Examples 1 to 4 and Comparative Example 1 Each component was blended according to the blending composition shown in Table 1 (numerical values are parts by mass), and kneaded separately with a three-roll mill to obtain photocurable and thermosetting properties. A resin composition was prepared. This is screen-printed using a 100-mesh polyester screen to a thickness of 20 to 30 μm, and the whole surface is applied to a patterned copper through-hole printed wiring board. Was dried for a predetermined time (30 minutes, 40 minutes, 50 minutes or 60 minutes). Then, a negative film having a resist pattern was brought into close contact with the coating film, and ultraviolet rays were irradiated (exposure amount 600 mJ / cm ² ) using an ultraviolet exposure device (Oak Seisakusho Co., Ltd., model HMW-680GW) to give 1% carbonic acid. The unexposed portion was dissolved and removed by developing with an aqueous sodium solution for 60 seconds at a spray pressure of 2.0 kg / cm ² , and the developability was evaluated by the evaluation method described below. Then, using a hot air dryer at 150 ° C, 6
A heat curing was performed for 0 minutes to prepare a test substrate. The test substrate having a cured film obtained under the condition of a drying time of 30 minutes was tested for adhesion, solder heat resistance, PCT resistance, and electroless gold plating resistance by the test method and evaluation method described below. Further, instead of the copper through-hole printed wiring board, a printed circuit board (thickness 1.6
mm) B pattern was used to fabricate a test substrate under the same conditions as described above, and an electrical insulation resistance test was performed. The results of the above tests are shown in Tables 2 and 3.

[0044]

[Table 1]

[0045]

[Table 2] Developability: The developability of each coating film, which was dried for 30 minutes, 40 minutes, 50 minutes, and 60 minutes, was visually evaluated with a magnifying glass. ◯: During development, the coating film was completely removed and development was possible. X: At the time of development, even a little residue remains, and there is a portion that is not developed.

[0046]

[Table 3] The evaluation method of each performance test in Table 3 above is as follows.

Adhesion: According to the test method of JIS D 0202, a cross-cut was put on the cured film in a grid pattern, and then the peeling ability after a peeling test with a cellophane adhesive tape was visually judged. ⊚: 100/100 with no peeling ○: 100/100 with a slight peeling of the cross-cut portion Δ: 50/100 to 90/100 ×: 0/100 to 50/100

Solder heat resistance: 1 of the test substrate in a solder bath at 260 ° C. according to the test method of JIS C 6481
Immersion for 0 seconds was performed 3 times and the change in appearance was evaluated. In addition,
As post flux (rosin type), JIS C
A flux according to 6481 was used. ○: No change in appearance Δ: Discoloration of the cured film is recognized ×: Floating, peeling, and solder dip in the cured film

PCT resistance: The PCT resistance of the cured film is 12
The following criteria were evaluated under the conditions of 1 ° C. and saturated steam for 50 hours. ◯: The cured film has no blistering, peeling or discoloration. Δ: The cured film has some swelling, peeling and discoloration. X: The cured film has blisters, peeling, and discoloration.

Electroless gold plating resistance: The copper surface of the copper through-hole printed wiring board on which the pattern is formed is surface-treated (Ishii Inscription Co., Ltd., after No. 1200 roll buff polishing, and then Ishii Inscription Co., Ltd.). No. 270 abrasive grain, jet scrub polished, washed with water, and dried.)
Then, in the same manner as described above, coating → drying → exposure → developing → heating were performed to obtain a test substrate having a resist film formed thereon. Using this test substrate, electroless gold plating was performed as in the step described below, and the test substrate was subjected to a change in appearance and a peeling test using a cellophane adhesive tape to determine the peeled state of the resist film. ◯: No change in appearance and no peeling of the resist film. Δ: There is no change in appearance, but the resist film is slightly peeled off. X: Lifting of the resist film was observed, plating subsidence was recognized, and peeling of the resist film was large in the peeling test.

Electroless gold plating process: 1. Degreasing: Test substrate was an acidic degreasing solution at 30 ° C. (Metex L-5B, 20 Vol, manufactured by Nippon MacDermid Co., Ltd.)
% Aqueous solution) for 3 minutes. 2. Washing with water: 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 for 3 minutes at room temperature. 4. Washing with water: 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 dipped in a catalyst solution at 30 ° C. (10 vol% aqueous solution of METAL PLATE ACTIVATOR 350, manufactured by Meltex Co., Ltd.) for 7 minutes. 8. Washing with water: The test substrate was immersed in running water for 3 minutes. 9. Electroless nickel plating: Test substrate at 85 ° C, pH
= 4.6 nickel plating solution (manufactured by Meltex Co., Ltd.,
It was soaked in Melplate Ni-865M, 20 Vol% aqueous solution) 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: Test substrate at 95 ° C, pH = 6
Gold plating solution (Meltex Co., Ltd., Ourollectrores UP 15 Vol%, potassium gold cyanide 3 Vo)
1% aqueous solution) for 10 minutes. 13. Washing with water: The test substrate was immersed in running water for 3 minutes. 14. Washing with hot water: The test substrate was immersed in warm water at 60 ° C., thoroughly washed with water for 3 minutes, thoroughly washed with water, and dried. Through these steps, a test substrate plated with electroless gold was obtained.

Electric insulation: The electric insulation of the cured film was evaluated according to the following criteria. Humidification conditions: temperature 85 ° C, humidity 85% RH, applied voltage 10
0V, 500 hours. Measurement conditions: measurement time 60 seconds, applied voltage 500V. ◯: Insulation resistance value after humidification is 10 ⁹ Ω or more, copper migration is not found Δ: Insulation resistance value after humidification is 10 ⁹ Ω or more, copper migration is present ×: Insulation resistance value after humidification is 10 ⁸ Ω or less, copper migration Yes

[0053]

As described above, according to the present invention, the adhesiveness, heat resistance and electroless plating resistance required for the solder resist of a printed wiring board and the interlayer insulating layer of a multilayer wiring board,
A cured film with excellent characteristics such as electrical characteristics, and especially excellent PCT resistance and moisture absorption resistance required for IC packages can be obtained, and it can be used for high density and surface mounting of printed wiring boards and can be alkali developed. A liquid photocurable / thermosetting composition is provided. By using such a photo-curable / thermo-curable composition of the present invention, a BG of a printed wiring board can be obtained.
Also in IC packages such as A and CSP, peeling and cracks do not occur in the solder resist film, and highly reliable mounting is possible. In addition, even when exposed to high temperature or high humidity conditions, it does not cause cracks in the cured film or peels from the base material, and since it has excellent properties as described above, it is suitable for dry films. It can be advantageously used for various resists such as resists and interlayer insulating layers of multilayer wiring boards.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/28 H05K 3/28 D (72) Inventor Shigeru Ushiki 388, Okura, Okura, Arakiyama, Hiki-gun, Saitama Prefecture Yo Ink Manufacturing Co., Ltd. Arashiyama Plant (72) Inventor Noboru Hinoyama No. 388, Okura, Arashiyama-cho, Hiki-gun, Saitama Taiyo Ink Manufacturing Co., Ltd. Arashiyama Plant F-term (reference) 2H025 AA04 AA10 AA14 AB15 AC01 AD01 BC13 BC42 BC43 BC65 BC74 BC81 BC85 CA00 CC03 CC17 CC20 FA17 4J027 AC03 AC06 AE01 AH03 BA08 BA23 BA24 CD10 4J036 AA01 CA20 CA21 CA25 DA02 EA04 FA10 FB08 HA02 5E314 AA25 AA27 AA32 BB06 DD07 FF01 GG01 GG05 GG10 GG11GG

Claims (3)

[Claims] 1. (A) An epoxy compound (a) having two or more epoxy groups in one molecule and one or more reactive groups other than hydroxyl groups which react with two or more hydroxyl groups and epoxy groups in one molecule. A carboxyl group-containing photosensitive resin obtained by reacting a compound (b) having ## STR1 ## with an unsaturated group-containing monocarboxylic acid (c), and reacting the resulting reaction product with a polybasic acid anhydride (d) , (B) the reaction product of the novolac type phenolic resin (e) and the alkylene oxide (f) is reacted with the unsaturated group-containing monocarboxylic acid (c), and the resulting reaction product is polybasic acid anhydride ( Carboxyl group-containing photosensitive resin obtained by reacting d), (C) photopolymerization initiator, (D) photosensitive (meth) acrylate compound, (E)
A photocurable / thermosetting resin composition comprising an epoxy compound and (F) a diluting solvent. 2. The carboxyl group-containing photosensitive resin (A) contains the compound (b) and the unsaturated group-containing monocarboxylic acid (c) per 1 equivalent of the epoxy group of the epoxy compound (a). The total amount is 0.8 to 1.3 mol, and the amount of the compound (b) used is 1 mol based on 1 mol of the total amount of the compound (b) and the unsaturated group-containing monocarboxylic acid (c). It is obtained by reacting at a reaction ratio of 0.05 to 0.5 mol and has an acid value of 30.
It is-150 mgKOH / g, The photocurable and thermosetting resin composition of Claim 1 characterized by the above-mentioned. 3. The photocurable / thermosetting resin composition according to claim 1, further comprising (G) a curing catalyst.