JPH11140145A - Resin composition, permanent resist resin composition, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin compsn. and a cured product thereof which can be easily developed, possess excellent solvent resistance and plating solution resistance, possess heat resistance high enough to withstand soldering temps., and are particularly suitable for permanent resists of printed wiring boards. SOLUTION: This resin compsn. and a cured product thereof comprise: an epoxy (meth)acrylate resin obtd. by reacting an epoxy resin represented by the formula (wherein (n) is an average value and is an no. of 0 or more) with a monocarboxylic acid contg. an unsatd. group; and a diluent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, particularly a resin composition useful as a permanent resist for a printed wiring board, and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, printed wiring boards have been manufactured by using a copper-clad laminate and by a subtractive method of removing unnecessary copper foil portions by etching by a circuit. This subtractive method uses fine patterns and high-density wiring. Difficult to form plate, small diameter through hole,
At present, via holes have drawbacks such as the fact that they cannot be uniformly formed by electroplating, and are not able to cope with higher densities of electronic devices.

[0003] On the other hand, recently, a full additive method of forming an adhesive layer on a laminate made of an insulating base material and forming a circuit and a through hole by electroless plating has attracted attention. In this method, the conductor pattern accuracy is determined only by the transfer accuracy of the plating resist, and since the conductor portion is formed only by electroless plating, even with a substrate having a high aspect ratio through hole, uniform through hole plating with high throwing power can be achieved. It is possible to do. Until now, the additive method, which has been considered suitable for general consumer use, has begun to be put into practical use as an industrial, high-density, high-multilayer substrate manufacturing process.

In general, in an additive method for producing a base plate for consumer use, a plating resist pattern is transferred by a screen printing method. However, in order to produce a printed wiring board having high-density wiring, the plating resist pattern must be transferred. It is necessary to form by photolithography, that is, to adopt a photo-additive method using a photoresist. A photoresist suitable for the photo-additive method is required to have the following characteristics in addition to the inherent characteristics of the photoresist such as sensitivity, degree of development and developability. Since the chemicals used in the development process are limited to 1,1,1-trichloroethane-based organic solvents or alkaline aqueous solutions, they can be developed with either, and electroless treatment performed for a long time under high temperature and high alkaline conditions Withstands plating, has excellent solder resist properties as a permanent resist after plating, and has 26
Having heat resistance to withstand temperatures around 0 ° C., having solvent resistance to organic solvents for cleaning flux used at the time of soldering, and furthermore, does not lower the thermal reliability of the entire substrate even when laminated. And so on. At present, photoresists that can be used in the additive method are commercially available, but their performance is not yet satisfactory.

[0005]

Accordingly, it is an object of the present invention to form a resist having high pattern accuracy by a photographic method using an organic solvent (for example, γ-butyrolactone, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, etc.). ), A mixture of these organic solvents and water or an aqueous alkaline solution (eg, N 2
a ₂ CO ₃ aqueous solution, KOH aqueous solution, diethanolamine aqueous solution, etc.), and sufficiently withstands the electroless copper plating solution of the full-additive method, or withstands the temperature of about 260 ° C. in the soldering process. To provide a resin composition suitable for a permanent resist used without removing even a final product, and a cured product thereof, having heat resistance, and solvent resistance to an organic solvent for cleaning flux used at the time of soldering. is there.

[0006]

Means for Solving the Problems In order to achieve the above object, as a result of intensive studies, it has been found that a resin composition having a specific composition solves those problems, and the present invention has been completed. Reached. That is, the present invention provides the following equation (1):

[0007]

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(Wherein n is an average value and represents 0 or a number greater than or equal to 0). Epoxy which is a reaction product of an epoxy resin (a) and an unsaturated group-containing monocarboxylic acid (b) (2) The epoxy resin (a) described in (1) and an unsaturated group-containing monocarboxylic acid (b), comprising a acrylate resin (A) and a diluent (B).
A resin composition comprising a carboxyl group-containing epoxy (meth) acrylate resin (A ′) which is a reaction product of a polybasic acid anhydride (c) and a diluent (B),

(3) The carboxyl group-containing epoxy (meth) acrylate resin (A ') is a reaction product of the epoxy (meth) acrylate resin (A) described in (1) and a polybasic anhydride (c) ( 2) The resin composition according to the above,
(4) The resin composition according to any one of (1) to (3), which is used for a permanent resist, and (5) (1) to (4).
A cured product of the resin composition according to any one of the above, (6) a cured product according to (5), which is a permanent resist, (7) a printed wiring board having a cured product layer according to (5) or (6), About.

The resin composition of the present invention comprises an epoxy (meth) acrylate resin (A) or a carboxyl group-containing epoxy (meth) acrylate resin (A ') and a diluent (B).
It is characterized by containing. The use ratio of each component (A) or (A ′) and (B) of the resin composition of the present invention is as follows:
The component (A) or (A ') is used in the composition of the present invention.
It is preferably from 80 to 80% by weight, particularly preferably from 30 to 70% by weight. The component (B) is contained in the composition of the present invention in an amount of from 20 to 8;
0% by weight is preferable, and particularly preferably 25 to 70% by weight.
It is.

The epoxy (meth) acrylate resin (A) used in the present invention is obtained by reacting the epoxy resin (a) represented by the above formula (1) with the unsaturated group-containing monocarboxylic acid (b). be able to. The epoxy resin (a) can be easily obtained from the market, for example, XD-1000 (Nippon Kayaku Co., Ltd.)
-260, softening point 50-80 ° C), Dainippon Ink Co., Ltd.
EXA-7200 (epoxy equivalent 257, softening point 6)
3 ° C.). Note that n in the above formula (1) is back calculated from the epoxy equivalent of the epoxy resin (a), and is an average value of 0 or a number of 0 or more, preferably 0.5 to 0.
It is a number of ten.

Examples of the unsaturated group-containing monocarboxylic acid (b) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-styrylacrylic acid, β-furfurylacrylic acid, and a saturated or unsaturated dicarboxylic acid. Half-esters, which are equimolar reactants of a basic acid anhydride and a (meth) acrylate derivative having one hydroxyl group in one molecule, or a saturated or unsaturated dibasic acid and an unsaturated group-containing monoglycidyl compound Half esters which are equimolar reactants are mentioned. These monocarboxylic acids (b) can be used alone or as a mixture. A particularly preferred monocarboxylic acid is acrylic acid.

The saturated or unsaturated dibasic anhydride which is a raw material for obtaining the half esters includes, for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrate. Hydrophthalic anhydride, methyltetrahydrophthalic anhydride,
Examples include itaconic anhydride, methylendomethylenetetrahydrophthalic anhydride and the like. Examples of (meth) acrylate derivatives having one hydroxyl group in one molecule include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, and the like. Glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate,
Examples thereof include pentaerythritol tri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and (meth) acrylate of phenylglycidyl ether.

Examples of the saturated or unsaturated dibasic acid as a raw material for obtaining another half ester include succinic acid,
Maleic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, itaconic acid, fumaric acid and the like can be mentioned. Further, examples of the unsaturated group-containing monoglycidyl compound include glycidyl (meth) acrylate and the following monoglycidyl compounds.

[0015]

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Epoxy (meth) acrylate resin (A)
The reaction for obtaining the unsaturated group-containing monocarboxylic acid (b) is about 0.3 to 1.3 with respect to one equivalent of the epoxy group of the epoxy resin (a) represented by the formula (1). It is preferably carried out in a molar ratio, particularly preferably about 0.5-1.
The ratio is 1 mol. The reaction temperature is preferably from 60 to
150 ° C. The reaction time is preferably 5 to 60 hours. During the reaction, it is preferable to use, for example, the diluent (B) described below. Further, it is preferable to use a catalyst to promote the reaction, and the amount of the catalyst to be used is preferably 0.1 to 10% by weight based on the reaction raw material mixture. Examples of the catalyst include triethylamine, benzyldimethylamine, methyltriethylammonium chloride, benzyltrimethylammonium bromide, triphenylphosphine, triphenylstibine and the like. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor, and the amount of the polymerization inhibitor is preferably 0.01 to 1% by weight based on the reaction raw material mixture. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and the like.

The carboxyl group-containing epoxy (meth) acrylate resin (A ') comprises the epoxy resin (a) represented by the formula (1), the unsaturated group-containing monocarboxylic acid (b) and the polybasic acid anhydride. It is a reaction product with the product (c) and can be obtained, for example, by reacting the epoxy (meth) acrylate resin (A) with the polybasic acid anhydride (c). Examples of the polybasic acid anhydride (c) include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, 3-methyl-tetrahydrophthalic anhydride,
Examples thereof include hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, endomethylene-tetrahydrophthalic anhydride, methyl-endomethyl-tetrahydrophthalic anhydride, and trimellitic acid.

Epoxy (meth) acrylate resin (A)
The reaction of the polybasic anhydride (c) with the polybasic anhydride (c) is preferably performed by reacting 0.1 to 0.9 equivalent of the polybasic anhydride (c) per equivalent of the hydroxyl group in the epoxy (meth) acrylate resin (A). The reaction temperature is preferably from 60 to 150C. The reaction time is preferably 1 to 10 hours. The carboxyl group-containing epoxy (meth) acrylate resin (A ') thus obtained has an acid value (mg KOH / g) of preferably from 40 to 110, particularly preferably from 50 to 100.

Specific examples of the diluent (B) include, for example, organic solvents (B-1) and reactive monomers (B-2). Examples of the organic solvent (B-1) include ketones such as ethyl methyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; and glycols such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether. Ethers, ethyl acetate, butyl acetate,
Esters such as butyl cellosolve acetate, carbitol acetate and propylene glycol monomethyl ether acetate; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha and the like. Examples of the reactive monomers (B-2) include carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and tris (hydroxyethyl). ) Isocyanurate tri (meth) acrylate, dipentaerythritol hexa and penta (meth) acrylate. These diluents (B) can be used alone or
Used as a mixture of more than one species. Further, the diluent (B) may be added during the synthesis of the epoxy (meth) acrylate resin (A).

In the resin composition of the present invention, it is preferable to use a photopolymerization initiator (C) and a curing component (D) in addition to the components (A) and (B). The use ratio of the photopolymerization initiator (C) in the composition of the present invention is preferably from 0 to 20% by weight, particularly preferably from 1 to 10% by weight. The above-mentioned curing component (D) is used alone or as a mixture of two or more, and is contained in the composition of the present invention.
Is preferably from 0 to 50% by weight, particularly preferably from 3 to 40% by weight, in the composition. The purpose of using the curing component (D) is to improve various properties as a resist such as adhesion, heat resistance, and plating resistance.

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-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-propan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone,
Anthraquinones such as -ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2-isopropylthioxanthone; benzyldimethylketal; Ketals such as acetophenone dimethyl ketal, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone,
There are benzophenones such as 4-benzoyl-4'-methyldiphenylsulfide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and these can be used alone or in combination of two or more. further,
Photopolymerization initiators (C) include tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine. Can be used alone or in combination of two or more.

As the hardening component (D), for example, one having no unsaturated double bond and itself hardening by heat or ultraviolet rays, or (A) or (A) which is the main component in the composition of the present invention. A component which reacts with a hydroxyl group, a carboxyl group or the like of the component (A ') by heat, ultraviolet light or the like may be used. Specifically, for example, epoxy compounds having one or more epoxy groups in one molecule, melamine derivatives such as hexamethoxymelamine, hexabutoxylated melamine, condensed hexamethoxymelamine, urea compounds such as dimethylolurea, tetramethylol Bisphenol A-based compounds such as bisphenol A, oxazoline compounds and the like can be mentioned.

Examples of the epoxy compound having one or more epoxy groups in one molecule include bisphenol type epoxy resins, EPPN-201, EOCN-103, EO
CN-1020, BREN (both Nippon Kayaku Co., Ltd.)
Novolak type epoxy resin, Epicron N-8
YL-931, a novolak type epoxy resin of bisphenol A such as 80 (manufactured by Dainippon Ink and Chemicals, Inc.)
YL-933 (both manufactured by Yuka Shell Epoxy Co., Ltd.)
Such as amino group-containing epoxy resin, Epicron TSR-6
01 (manufactured by Dainippon Ink and Chemicals, Inc.), R-1415
Rubber-modified epoxy resin such as -1 (manufactured by AC R Co., Ltd.), triglycidyl isocyanurate such as TEPIC (manufactured by Nissan Chemical Co., Ltd.), YX-4000 (manufactured by Yuka Shell Epoxy), etc. , A mixture of a bisphenol type epoxy resin such as YL-6121H and a bixylenol type epoxy resin, and an alicyclic epoxy resin such as Celloxide 2021 (manufactured by Daicel Chemical Industries, Ltd.).

As the bisphenol type epoxy resin,
For example, Epicoat 1009, 1031 (both manufactured by Yuka Shell Epoxy Co., Ltd.), Epicron N-3050,
N-7050 (both from Dainippon Ink and Chemicals, Inc.)
Bisphenol A type epoxy resins such as DER-642U and DER-673MF (both manufactured by Dow Chemical Co., Ltd.), and hydrogenated bisphenols such as ST-2004 and ST-2007 (both manufactured by Toto Kasei Co., Ltd.) A-type epoxy resin, bisphenol F-type epoxy resin such as YDF-2004, YDF-2007 (all manufactured by Toto Kasei Co., Ltd.), SR-BBS, SR-TBA-400 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.) , YDB-600, YDB-7
15 and the like (all manufactured by Toto Kasei Co., Ltd.), a brominated bisphenol A type epoxy resin, Epicron EXA-1514
(Manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

When an epoxy compound is used in the curing component (D), an epoxy resin curing (promoting) agent is used in combination to further improve properties such as adhesion, chemical resistance and heat resistance. Is preferred. As the epoxy resin curing (acceleration) agent, for example, 2MZ, 2E4MZ, C _{11
Z, C 17 Z, 2PZ,} 1B2MZ, 2MZ-CN, 2E
_{4MZ-CN, C 11 Z-} CN, 2PZ-CN, 2PHZ
-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ
-CNS, 2MZ-AZ1NE, 2E4MZ-AZ1N
E, C ₁₁ Z-AZ1NE, 2MA-OK, 2P4MH
Z, 2PHZ, 2P4BHZ or the like (all manufactured by Shikoku Chemicals Co., Ltd.); acetoguanamine;
Guanamines such as benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, melamine, polybasic hydrazide; amine complexes of boron trifluoride; ethyldiamino-S
-Triazine, 2,4-diamino-S-triazine,
Triazine derivatives such as 2,4-diamino-6-xylyl-S-triazine; trimethylamine, triethanolamine, N, N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N- Tertiary amines such as methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine and m-aminophenol; polyphenols such as polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak; Organic phosphines such as tributylphosphine, triphenylphosphine and tris-2-cyanoethylphosphine; diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakisperfluorophore Niruboreto, triphenylsulfonium hexafluorophosphate, Optomer SP
An epoxy resin curing (acceleration) agent such as a photo-cationic polymerization catalyst such as -170 (manufactured by Asahi Denka Kogyo KK) is used alone or in combination of two or more. The amount used is preferably from 0.01 to 25 parts by weight, particularly preferably from 0.1 to 15 parts by weight, based on 100 parts by weight of the epoxy compound.

The composition of the present invention may further contain, if necessary, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc for the purpose of improving properties such as adhesion and hardness. , Clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica powder and the like. Its use amount is preferably 0 to 60% by weight in the composition of the present invention,
Particularly preferably, it is 0 to 40% by weight.

Further, if necessary, coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, hydroquinone, hydroquinone monomethyl ether, phenothiazine, etc. Polymerization inhibitors, thickeners such as asbestos, orben, benton, montmorillonite, defoamers such as silicone, fluorine and polymer, and / or
Alternatively, various additives such as a leveling agent, an imidazole-based adhesion promoter, a thiazole-based adhesion promoter, a triazole-based adhesion promoter, and an adhesion promoter such as a silane coupling agent can be used. When these additives and the like are used, their use amounts are, for example, about 0.5 to 30% by weight in the composition of the present invention, respectively, but may be appropriately increased or decreased according to the purpose of use.

Also, copolymers of ethylenically unsaturated compounds such as acrylates, binder resins such as polyethersulfone resins and polyester resins can be used.

The resin composition of the present invention contains the components (A) and (B), and if necessary, the components (C) and (D), an inorganic filler and other additives, preferably in the proportions described above. Then, it can be prepared by mixing, dissolving, dispersing and the like uniformly with a roll mill or the like.

The resin composition of the present invention is preferably used in a liquid state for a permanent resist. 20 on the printed wiring board
で 60 μm thickness, 60-100 ℃, 10-6
About 0 minutes, heat treatment to remove the solvent, place a mask having a predetermined pattern thereon, irradiate with energy rays such as ultraviolet rays, and develop a pattern by developing an unexposed portion with a developer, and then By irradiating, for example, ultraviolet rays as required, and then performing heat treatment at 100 to 200 ° C., a permanent protective film satisfying various characteristics can be obtained. As the developing solution, an organic solvent such as γ-butyrolactone, triethylene glycol dimethyl ether, and methyl cellosolve, or an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, and potassium hydroxide can be used.

The resin composition of the present invention comprises a roll coater or a doctor bar on a base film (release film).
After applying the composition using a wire bar method, a dipping method, a spin coating method, a gravure method, a doctor blade method, or the like, drying in a drying furnace set at 60 to 100 ° C. to remove a predetermined amount of solvent. And, if necessary, a dry film can be obtained by attaching a release film or the like. At this time, the thickness of the resist on the base film is adjusted to 15 to 150 μm. As the base film, a film of polyethylene terephthalate, polypropylene, or the like is suitably used. In order to use this dry film, for example, the release film may be peeled off, transferred to a substrate, and exposed, developed, and heated in the same manner as described above.

The cured product of the resin composition of the present invention obtained by the above method is used for an electric / electronic component such as a printed wiring board having a through hole as a permanent resist. The thickness of the cured layer of the printed wiring board having the cured layer of the resin composition of the present invention is preferably about 20 to 60 μm.

[0033]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. (Synthesis example of epoxy (meth) acrylate resin (A)) Synthesis example 1 The epoxy resin represented by the general formula (1) (manufactured by Nippon Kayaku Co., Ltd., product name, XD-1000, epoxy equivalent 25)
4. Softening point 73.3 ° C, n is 2.71. ) 254
0 g (10 equivalents), 720.6 g (10 equivalents) of acrylic acid, 5.0 g of methylhydroquinone, 1229 g of carbitol acetate and 526.7 g of solvent naphtha
And heated and stirred at 90 ° C. to dissolve the reaction mixture. Next, the reaction solution was cooled to 60 ° C., charged with 15.0 g of triphenylphosphine, heated to 98 ° C., reacted for about 32 hours, and cooled when the acid value (mg KOH / g) became 3.0 or less. And epoxy acrylate (A-1). The viscosity of the product (25 ° C., poise) was 220.

(Synthesis example of carboxyl group-containing epoxy (meth) acrylate resin (A ')) Synthesis example 2. 5036.3 g of the epoxy acrylate resin (A-1) obtained in Synthesis Example 1, 1218.9 g of tetrahydrophthalic anhydride, and 459.4 g of carbitol acetate
And 196.9 g of solvent naphtha, and reacted at 95 ° C. for 10 hours to obtain a carboxyl group-containing epoxy acrylate resin (A′-1). The solid content acid value (mgKOH / g) of the product is 100, and the viscosity (25 ° C,
Poise) was 410.

Examples 1 to 4 Each component was mixed, dispersed and kneaded in accordance with the composition shown in Table 1 (the numerical values are parts by weight) to obtain the resin composition of the present invention. The obtained resin composition was applied on a laminate at a thickness of 30 μm, dried at 80 ° C. for 60 minutes, then brought into contact with a negative mask on the resist, and irradiated with ultraviolet rays using an ultrahigh pressure mercury lamp. The unexposed portion was treated with triethylin glycol dimethyl ether (Examples 1 and 2) and 1.5% Na ₂
2.0 kg with CO ₃ aqueous solution (Examples 3 and 4) for 60 seconds
/ Cm ^{2 at} a spray pressure. After washing, drying and irradiating the entire surface with ultraviolet rays, a heat treatment was performed at 150 ° C. for 30 minutes. This was immersed in an electroless copper plating solution at 70 ° C. for 10 hours to form an electroless copper plating film of about 20 μm, thereby producing an additive-processed multilayer printed wiring board. Table 1 shows the results of evaluating the characteristics of the resist in the process of obtaining the additive multilayer printed wiring board in this manner.

Evaluation method (Developability) ・ ・ ・: At the time of development, ink was completely removed, and complete development was completed. ×: At the time of development, a little residue remains and there is a part that is not developed. (Solvent resistance) The cured resist film was immersed in acetone for 20 minutes and the state was visually observed. ○ ・ ・ ・ ・ No change at all. ×: blisters and peeling occurred. (Plating resistance) ○ ・ ・ ・ ・ No change is observed in the electroless copper plating process. Δ: Discoloration is slightly observed in the electroless copper plating process. C: Discoloration, blistering, and peeling occurred in the electroless copper plating step.

(Solder Heat Resistance) According to the test method of JIS C 6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds three or two times, and the change in appearance was evaluated. In the table, the state of change in the appearance when immersion for 10 seconds was performed three times is described. ○ ・ ・ ・ ・ No change in appearance. △ ・ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ ・ ・ Floating, peeling and solder dipping of the cured film (Note) Post flux used (rosin type): JIS
Use flux according to C 6481.

(Flux resistance for leveler) The immersion was carried out three times for 10 seconds, and after immersion in boiling water for 10 minutes, the change in appearance was evaluated. ○ ・ ・ ・ No change in appearance △ ・ ・ ・ Discoloration of the cured film is observed × ・ ・ ・ ・ Floating, peeling, and solder dipping of the cured film (Note) Flux for leveler used: manufactured by MEC Corporation , W-121

[0039]

Table 1 Mixing composition and property test Mixing composition Example 12 Epoxy acrylate obtained in Synthesis Example 1 (A-1) 154 154 Carboxyl group-containing epoxy acrylate obtained in Synthesis Example 2 (A'-1) ) 154 154 Propylene glycol monomethyl ether acetate 15 10 25 25 KAYARAD DPHA * 15 55 55 EOCN-104S * 2 15 15 Bisphenol A diglycidyl ether 55 55 55 Benzyl dimethyl ketal 3 33 33. 5 0.5 0.5 0.5 Aerosil 380 * 3 3 3 3 3 Melamine (epoxy curing agent) 3 2 3 2 Dicyandiamide (epoxy curing agent) 2 1 2 1 Silica dioxide 35 35 35 35 ─────────────── ───────────── developability ○ ○ ○ ○ resistance to plating solution ○ ○ ○ △ solder heat resistance post flux resistance ○ △ ○ △ leveler flux resistance ○ ○ ○ ○

Note) * 1 KAYARAD DPH
A: Nippon Kayaku Co., Ltd. mixture of dipentaerythritol penta and hexaacrylate. * 2 EOCN-104S: Nippon Kayaku Co., Ltd., cresol novolak type epoxy resin, epoxy equivalent 2
20, softening point 92 ° C. * 3 Aerosil 380: Japan Aerosil Co., Ltd.
Made, anhydrous silica.

As is clear from the evaluation results in Table 1, the resin composition of the present invention is excellent in developability, and the cured product is excellent in solvent resistance, plating solution resistance and solder heat resistance.

[0042]

The resin composition of the present invention and the cured product thereof are:
Despite high resolution and easy development, isopropyl alcohol, trichloroethylene, methylene chloride,
Excellent resistance to solvents such as acetone, excellent plating solution resistance to electroless plating performed for a long time under high temperature and high alkalinity conditions, and heat resistance that can withstand temperatures around 260 ° C in the soldering process. Particularly suitable as a resist for the manufacture of printed wiring boards.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/027 515 G03F 7/027 515 H05K 3/18 H05K 3/18 D 3/28 3/28 C

Claims (7)

[Claims] (1) Formula (1) (Wherein, n is 0 or a number greater than or equal to 0) and an epoxy resin (a) represented by the formula: and an unsaturated group-containing monocarboxylic acid (b)
A resin composition comprising an epoxy (meth) acrylate resin (A) and a diluent (B), which are reactants with the above. 2. The epoxy resin according to claim 1, (a), an unsaturated group-containing monocarboxylic acid (b) and a polybasic acid anhydride (c).
Carboxyl group-containing epoxy (meth)
A resin composition comprising an acrylate resin (A ') and a diluent (B). 3. The epoxy (meth) acrylate resin (A ') containing a carboxyl group is a reaction product of the epoxy (meth) acrylate resin (A) according to claim 1 and a polybasic acid anhydride (c). 3. The resin composition according to 2. 4. The resin composition according to claim 1, which is used for a permanent resist. 5. A cured product of the resin composition according to claim 1. 6. The cured product according to claim 5, which is a permanent resist. 7. A printed wiring board having the cured product layer according to claim 5.