JPH11242332A - Resin composition, its hardened body and printed circuit board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an easily developable resin compsn. excellent in solvent resistance, plating soln. resistance and electrical characteristics, also provided with heat resistance that can withstand a temp. in a soldering step and suitable particularly for the production of a printed circuit board. SOLUTION: This resin compsn. contains an epoxy (meth)acrylate resin (A) which is the reaction product of an epoxy resin having at least two epoxy groups in the molecule with an unsatd. group-contg. monocarboxylic acid or a carboxyl, group-contg. epoxy (meth)acrylate resin (A') which is the reaction product of the epoxy (meth)acrylate resin A with a polybasic acid anhydride, an ion capturing agent (B) and a didluent (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition, particularly to 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. The difficulty of forming wiring boards, small diameter through holes,
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.

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 flowing power is achieved. It is possible to do. Until now, the additive method has been considered suitable for general consumer use, but it has begun to be used as an industrial, high-density, high-multilayer substrate manufacturing process.

Generally, in an additive method for manufacturing a board for consumer use, a plating resist pattern is transferred by a screen printing method. However, in order to manufacture a printed wiring board having high-density wiring, the plating resist pattern is photographed. It is necessary to form by plate making, that is, to adopt a photoadditive method using a photoresist. A photoresist suitable for the photoadditive 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.

[Problems to be solved by the invention]

Accordingly, it is an object of the present invention to form a resist with high pattern accuracy by a photographic method using an organic solvent (eg, γ-butyrolactone, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether acetate, etc.) It can be developed by using a mixed solution of water or an aqueous alkaline solution (for example, an aqueous solution of Na ₂ CO _3, an aqueous solution of KOH, an aqueous solution of diethanolamine, etc.) and sufficiently withstands the electroless copper plating solution of the full additive method, or a soldering step. Of 260
Resin composition suitable for permanent resist used without removing to the final product, with heat resistance to withstand temperatures around ℃ and solvent resistance to organic solvents for cleaning flux used during soldering It is to provide a cured product.

[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 relates to (1) an epoxy (meth) acrylate resin which is a reaction product of an epoxy resin (a) having at least two epoxy groups in a molecule and an unsaturated group-containing monocarboxylic acid (b) ( A),
A resin composition comprising an ion scavenger (B) and a diluent (C). (2) The epoxy (meth) acrylate resin (A) according to (1) and a polybasic acid anhydride (c) A resin composition containing a carboxyl group-containing epoxy (meth) acrylate resin (A '), an ion scavenger (B), and a diluent (C), which are reactants with (3) a permanent resist (1) or (2), (4) (1) to (3).
A cured product of the resin composition according to any one of the above, (5) a cured product according to (4), which is a permanent resist, and (6) a printed wiring board having a cured product layer according to (4) or (5). , Concerning.

The resin composition of the present invention comprises an epoxy (meth)
It is characterized by containing an acrylate resin (A) or a carboxyl group-containing epoxy (meth) acrylate resin (A '), an ion scavenger (B) and a diluent (C). The proportion of each of the components (A) or (A '), (B) and (C) in the resin composition of the present invention is as follows when the total amount of each component is 100 parts. Is preferably 15 to 75% by weight, particularly preferably 20% by weight.
To 70% by weight, the component (B) is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 10% by weight, and the component (C) is preferably 20 to 80% by weight, particularly preferably 2 to 80% by weight.
5 to 70% by weight.

The epoxy (meth) acrylate resin (A) used in the present invention is obtained by reacting an epoxy resin (a) having at least two epoxy groups in a molecule with an unsaturated group-containing monocarboxylic acid (b). Can be obtained by

The epoxy resin (a) is, for example, a bisphenol type epoxy resin, EPPN-201, EOCN-1
Novolak epoxy resin such as 03, EOCN-1020, BREN (all manufactured by Nippon Kayaku Co., Ltd.), EPPN
-501, EPPN-502 (both Nippon Kayaku Co., Ltd.)
Trisphenol methane type epoxy resin, NC
-3000P (Nippon Kayaku Co., Ltd., epoxy equivalent 270)
-300, softening point 60-75 ° C), dicyclopentadiene-modified epoxy resin such as XD-1000 (Nippon Kayaku Co., Ltd., epoxy equivalent 240-260, softening point 50-80 ° C). , NC-7000
Naphthalene-modified epoxy resin such as Nippon Kayaku Co., Ltd., epoxy equivalent 220/230, softening point 90-100 ° C., and bisphenol A novolak such as Epicron N-880 (manufactured by Dainippon Ink and Chemicals, Inc.) Epoxy resin and the like.

As the bisphenol type epoxy resin,
For example, Epicoat 1001, Epicoat 1004, Epicoat 1009, Epicoat 1031 (all manufactured by Yuka Shell Epoxy Co., Ltd., Epicron N-3050, N-
7050 (all manufactured by Dainippon Ink and Chemicals, Inc.)
Bisphenol A epoxy resins such as DER-642U and DER-673MF (both manufactured by Dow Chemical Co., Ltd.), and hydrogenated bisphenol A epoxy such as ST-2004 and ST-2007 (both manufactured by Toto Kasei Co., Ltd.) 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-71
5 (all manufactured by Toto Kasei Co., Ltd.), such as a brominated bisphenol A type epoxy resin, Epicron EXA-1514
(Manufactured by Dainippon Ink and Chemicals, Inc.) and the like.

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.

Examples of the saturated or unsaturated dibasic anhydride which is a raw material for obtaining the half esters include succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrate and the like. 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.

The saturated or unsaturated dibasic acid which is a raw material for obtaining another half ester includes, for example, 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.

[0014]

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Epoxy (meth) acrylate resin (A)
Is obtained by reacting one equivalent of the epoxy group of the epoxy resin (a) with the unsaturated monocarboxylic acid (b).
Is preferably used in a ratio of about 0.3 to 1.3 mol, particularly preferably about 0.5 to 1.1 mol. The reaction temperature is preferably from 60 to 150C. The reaction time is preferably 5 to 60 hours.
During the reaction, it is preferable to use, for example, the diluent (C) 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 ') is a reaction product of the epoxy resin (a), the unsaturated group-containing monocarboxylic acid (b), and the polybasic anhydride (c). Yes, for example, the epoxy (meth)
It can be obtained by reacting the 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, hexahydrophthalic anhydride, and 4-methyl-hexahydrophthalic anhydride. Acid, endmethylenetetrahydrophthalic anhydride, methylendmethylenetetrahydrophthalic anhydride, trimellitic acid and the like can be mentioned.

Epoxy (meth) acrylate resin (A)
And the polybasic acid anhydride (c) is preferably reacted with 0.1 to 0.9 equivalents 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 acid value (mgKOH / g) of the carboxyl group-containing epoxy (meth) acrylate resin (A ') thus obtained is preferably from 10 to 110, particularly preferably from 50 to 100.

Examples of the ion scavenger (B) used in the present invention include powdery bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, tin-based and mixtures thereof. Examples include inorganic compounds. They are also commercially available. For example, Toa Gosei Co., Ltd., ion scavenger, product name, IXE-300 (antimony),
IXE-500 (bismuth type), IXE-600 (antimony and bismuth mixed type), IXE-700 (magnesium and aluminum mixed type), IXE-1100 (calcium type) and the like can be given. These ion scavengers (B) can be used alone or in combination of two or more. The particle size of the powder is preferably about 1 to 10 μm.

The resin composition of the present invention, ion-trapping agent (B), the monovalent ion of the resin composition and cured product, in particular Na ^+, Ag ^+, Cu ^+, etc. of the metal cation, Cl ^-, B
r ^- electrical properties of the cured product by capturing a halogen anion such as, for example, preventing a reduction of such insulation resistance (Omega), it is possible to improve the reliability. In particular, the effect is remarkably exhibited in the composition using the epoxy (meth) acrylate resin (A).

Examples of the diluent (C) include organic solvents (C-1) and reactive monomers (C-2). Examples of the organic solvent (C-1) include tetones 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. Examples thereof include ethers, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. Examples of the reactive monomers (C-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 (C) are used alone or as a mixture of two or more. The diluent (C) is an epoxy (meth) acrylate resin (A) or a carboxyl group-containing epoxy (meth) acrylate resin (A ')
It may be added at the time of synthesis.

In the resin composition of the present invention, a photopolymerization initiator (D) and a curing component (E) may be used in addition to the components (A) or (A '), (B) and (C). preferable.
The proportion of the photopolymerization initiator (D) used in the composition of the present invention is as follows.
It is preferably from 1 to 20% by weight, particularly preferably from 1 to 10% by weight. The curing component (E) is used alone or as a mixture of two or more types. The amount of the curing component (E) contained in the composition of the present invention is preferably from 0 to 50% by weight, particularly preferably in the composition. Is from 3 to 40% by weight. The purpose of using the hardening component (E) is to improve various properties as a resist such as adhesion and plating resistance.

Examples of the photopolymerization initiator (D) 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-morpholinopropan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 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 and acetophenone Ketals such as dimethyl ketal, benzophenone, methylbenzophenone,
4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, 4-
There are benzophenones such as benzoyl-4'-methyldiphenylsulfide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like, and these can be used alone or in combination of two or more.

The photopolymerization initiator (D) is, for example, N, N
-Dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-
4-dimethylaminobenzoate, triethylamine,
Photosensitizers such as tertiary amines such as triethanolamine can be used alone or in combination of two or more. The amount used is 0 to 100 parts by weight of the component (D).
It is about 100 parts by weight.

As the curing component (E), for example, one having no unsaturated double bond, which itself is cured by heat or ultraviolet rays, or the main component in the composition of the present invention (A) Alternatively, a compound which reacts with a hydroxyl group or a carboxyl group 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 hexamethoxy melamine, hexabutoxylated melamine, condensed hexamethoxy melamine, urea compounds such as dimethylol urea, 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 resin, EPPN-201, EOCN-103, EO
CN-1020, BREN (both Nippon Kayaku Co., Ltd.)
Novolak type epoxy resin, Epicron N-8
Novolac type epoxy resin of bisphenol A such as 80 (manufactured by Dainippon Ink and Chemicals, Inc.), YL-931, Y
Amino group-containing epoxy resins such as L-933 (both manufactured by Yuka Shell Epoxy Co., Ltd.), Epicron TSR-60
1 (manufactured by Dainippon Ink and Chemicals, Inc.), R-1415-
Rubber-modified epoxy resin such as No. 1 (manufactured by AC R Co., Ltd.), triglycidyl isocyanate 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 Gaicel 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 (All are Dainippon Ink and Chemicals, Inc.)
Bisphenol A type epoxy resins such as DER-642U and DER-673MF (all manufactured by Dow Chemical Co., Ltd.), and hydrogenated bisphenols such as ST-2004 and ST-2007 (all manufactured by Toto Kasei Co., Ltd.) A-type epoxy resins, bisphenol-type epoxy resins such as YDF-2004 and YDF-2007 (all manufactured by Toto Kasei Co., Ltd.), SR-BBS, SR-TBA-400 (all manufactured by Sakamoto Pharmaceutical Co., Ltd.), YDB-600, YDB-71
5 (all manufactured by Toto Kasei Co., Ltd.), such as 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 (E), an epoxy resin curing (promoting) agent is used to further improve properties such as adhesion, chemical resistance and heat resistance. Is preferred. Examples of the epoxy resin curing (promoting) agent include imidazole derivatives, guanamines, polyamines, amine complexes of boron trifluoride, triazine derivatives, tertiary amines, polyphenols, organic phosphines, and cationic photopolymerization catalysts. And used alone or in combination of two or more. The amount used is 0.1 to 100 parts by weight of the epoxy compound.
The amount is preferably from 01 to 25 parts by weight, particularly preferably from 0.1 to 25 parts by weight.
15 parts by weight.

Examples of the imidazole derivative which is one type of epoxy resin curing (acceleration) agent include, for example, 2MZ, 2E4M
_{Z, C 11 Z, C 17} Z, 2PZ, 1B2MZ, 2MZ-C
_{N, 2E4MZ-CN, C 11} Z-CN, 2PZ-CN,
2PHZ-CN, 2MZ-CNS, 2E4MZ-CN
S, 2PZ-CNS, 2MZ-AZ1NE, 2E4MZ
_{-AZ1NE, C 11 Z-AZ1NE,} 2MA-OK, 2
P4MHZ, 2PHZ, 2P4BHZ and the like (all manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. Examples of guanamines include acetoguanamine and benzoguanamine. Examples of polyamines include diaminodiphenylmethane and m-phenylenediamine. , M-xylenediamine, diaminodiphenylsulfone, dicyandiamide, urea, melamine, polybasic hydrazide and the like.

The triazine derivatives include, for example, ethyldiamino-S-triazine, 2,4-diamino-
S-triazine, 2,4-diamino-6-xylyl-S
Tertiary amines such as trimethylamine, triethanolamine, N, N
-Dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methylmorpholine, hexa (N-methyl) melamine, 2,4,6-tris (dimethylaminophenol), tetramethylguanidine, m-aminophenol, etc. The polyphenols include, for example, polyvinylphenol, polyvinylphenol bromide, phenol novolak, alkylphenol novolak, and the like, and the organic phosphines include, for example, tributylphosphine, triphenylphosphine, tris-2-cyanoethylphosphine, and the like. Examples of the cationic photopolymerization catalyst include diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakisperfluorophenylborate, and triphenylsulfonium. Hexafluorophosphate, OPTOMER SP-170 (Asahi Denka Kogyo Co.) and the like.

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.

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

The resin composition of the present invention comprises (A) or (A '), (B) and (C) components, and if necessary, (D) and (E) components, inorganic fillers and other additives. Agent
Preferably, they can be blended in the above ratio, and can be prepared by uniform mixing, dissolving, dispersing and the like using a roll mill or the like. The resin composition of the present invention is usually liquid, but may be a dry film.

In order to produce a dry film, for example, a roll coater, a doctor bar, a wire bar system, a dipping system, a spin coating system, a gravure system, a doctor plate system, etc. are used on a base film (release film). After applying the resin composition of the present invention,
It can be obtained by drying in a drying oven set at 60 to 100 ° C. and removing a predetermined amount of solvent, and by attaching a release film or the like as necessary. On this occasion,
The thickness of the resist on the base film is 15-150μ
m, preferably 20 to 60 μm. As the base film, polyethylene terephthalate,
A film such as polypropylene is preferably used.

The resin composition of the present invention is preferably used in the form of a liquid or the above-mentioned dry film for use as a permanent resist. When a liquid product is used, it is applied on a substrate such as a printed wiring board with a thickness of 20 to 60 μm,
A heat treatment is performed for about 10 to 60 minutes to remove the dissolution, a mask having a predetermined pattern is placed thereon and irradiated with ultraviolet rays, and the unexposed portion is developed with a developing solution to form a pattern. Irradiate with UV light, then 100 ~ 2
By performing the heat treatment at 00 ° C., a permanent protective film satisfying various characteristics can be obtained. Examples of the developing solution include organic solvents such as γ-butyrolactone, triethylene glycol dimethyl ether, and methyl cellosolve (when the component (A) is used), or alkaline aqueous solutions such as sodium carbonate, sodium hydroxide, and potassium hydroxide ((A ′ ) In the case of using a component), etc. can be used. In order to use a dry film product, for example, the release film may be peeled off, transferred to the substrate, and exposed, developed, and heat-treated in the same manner as described above.

The cured product of the resin composition of the present invention obtained by the above-mentioned method is used for electric / electronic parts such as printed wiring boards having through holes as permanent resists.

The printed wiring board of the present invention has a cured product layer of the resin composition of the present invention as a permanent resist,
For example, it is manufactured by the above method. The thickness of the cured product layer of the printed wiring board is preferably about 20 to 60 μm.

[0038]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Synthesis Example 1 (Epoxy (meth) acrylate resin (A)
Synthesis Example of Epoxy Resin (NC-3000P: Nippon Kayaku Co., Ltd., Epoxy Equivalent 286, Softening Point 67 ° C.)
n is 2.24 on average. 2860 g (10 equivalents), acrylic acid 720.6 g (10 equivalents), methylhydroquinone 5.5 g, carbitol acetate 134
9.6 g and solvent naphtha 578.4 g were charged,
The mixture was heated and stirred at 90 ° C. to dissolve the reaction mixture. Then, the reaction solution was cooled to 60 ° C., and triphenylphosphine 1 was added.
6.5 g was charged, heated to 98 ° C., reacted for about 32 hours, and when the acid value (mgKOH / g) became 3.0 or less,
After cooling, an epoxy acrylate (A-1) was obtained. The viscosity (25 ° C., poise) of the product was 185.

[0039]

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Synthesis Example 2 (Synthesis of carboxyl group-containing epoxy (meth) acrylate resin (A ')) Epoxy acrylate resin (A-1) 5 obtained in Synthesis Example 1
530.6 g, tetrahydrophthalic anhydride 1338.5
g, 504.5 g of carbitol acetate and 216.2 g of solvent naphtha, and reacted at 95 ° C. for 10 hours to obtain a carboxyl group-containing epoxy acrylate resin (A′-1). Acid value (mg KO) of solid content of product
H / g) is 100 and the viscosity (25 ° C., poise) is 3
75.

Examples 1 to 4 and Comparative Examples 1 and 2 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. Was. 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. Unexposed portions were triethylene glycol dimethyl ether (Examples 1, 2 and Comparative Example 1) and 1.
It was developed with a 5% aqueous solution of Na ₂ CO ₃ (Examples 3, 4 and Comparative Example 2) at a spray pressure of 2.0 kg / cm ² for 60 seconds. After washing, drying and irradiating the entire surface with ultraviolet rays,
Heat treatment was performed at 30 ° 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 manufacturing the additive method multilayer printed wiring board thus obtained.

Evaluation method (developability) ・ ・ ・: At the time of development, the ink was completely removed, and complete development was possible. C: 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. Δ: blisters and peeling occurred. (Plating solution 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-based): JIS
Use flux according to C 6481

(Flux resistance to leveler) The test piece was immersed in a solder bath at 260 ° C. for 10 seconds three times, immersed in boiling water for 10 minutes, and 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

(Electrical Characteristics) The prepared multilayer printed circuit board was placed in a constant temperature / humidity bath at 60 ° C. and 90% RH, a DC voltage of 100 V was applied, and the insulation resistance was measured after 500 hours.

[0046]

Table 1 Table 1 Mixing composition and property test Mixing composition Example Comparative example 1 2 3 4 1 2 Epoxy acrylate obtained in synthesis example 1 (A-1) 154 154 154 154 Carboxyl group-containing epoxy acrylate obtained in synthesis example 2 (A'-1) 154 154 154 Propylene glycol monomethyl ether acetate 20 15 25 25 15 25 KAYARD DPHA * 1 55 5 55 55 EOCN 104S * 2 20 7.5 20 7.5 7.5 7.5 Benzyl dimethyl ketal 3 3 3 3 3 3 Aerosil 380 * 3 3 3 3 3 3 3 2,4-diethylthioxanthone 0.5 0.5 0.5 0.5 0.5 0.5 Melamine (epoxy curing agent) 32 32 22 dicyandiamide (epoxy curing agent) 221-111 IXE-400 * 4 22 IXE-700 * 52 22 IXE-300 * 64 4 Silica dioxide 31 31 31 31 35 35 ────────────────────────── ──現 像 Developability ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ ○ ○ Plating solution ○ ○ ○ △ ○ △ Solder heat resistance Post flux resistance ○ ○ ○ ○ ○ ○ Leveler flux resistance ○ ○ ○ ○ ○ ○ Electrical characteristics Insulation resistance (× 10 ¹¹ Ω) 300 100 80 50 9 5

Note) * 1 KAYARAD DPHA: manufactured by Nippon Kayaku Co., Ltd.
Mixture of dipentaerythritol penta and hexaacrylate. * 2 EOCN-104S: Nippon Kayaku Co., Ltd., cresol novolak type epoxy resin, epoxy equivalent 22
0, softening point 92 ° C. * 3 Aerosil 380: manufactured by Nippon Aerosil Co., Ltd., anhydrous silica. * 4 IXE-400: manufactured by Toagosei Co., Ltd., ion scavenger, powder, titanium-based inorganic compound. * 5 IXE-700: Toa Gosei Co., Ltd., ion scavenger, powder, magnesium-aluminum mixed inorganic compound. * 6 IXE-300: manufactured by Toagosei Co., Ltd., ion scavenger, powder, antimony inorganic compound.

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, solder heat resistance, electrical properties, etc. In particular, it has high insulation resistance and excellent electrical characteristics. In particular, the composition using the epoxy (meth) acrylate resin (A) has high insulation resistance and excellent electrical characteristics.

[0049]

The resin composition of the present invention and the cured product thereof are:
Despite high resolution and easy development, isopropyl alcohol, trichloroethylene, methylene chloride,
It is excellent in solvent resistance to acetone and the like, plating solution resistance to electroless plating performed for a long time under high temperature and high alkalinity conditions, electric properties, and the like.
It has heat resistance to withstand temperatures of around ° C and is particularly suitable for the production of printed wiring boards as a permanent resist.

Claims (6)

[Claims] 1. An epoxy (meth) acrylate resin (A) which is a reaction product of an epoxy resin (a) having at least two epoxy groups in a molecule and an unsaturated group-containing monocarboxylic acid (b), Capture agent (B) and diluent (C)
A resin composition comprising: 2. A carboxyl group-containing epoxy (meth) acrylate resin (A '), which is a reaction product of the epoxy (meth) acrylate resin (A) according to claim 1 and a polybasic acid anhydride (c), ion-trapping A resin composition comprising an agent (B) and a diluent (C). 3. The resin composition according to claim 1, which is used for a permanent resist. 4. A cured product of the resin composition according to any one of claims 1 to 3. 5. The cured product according to claim 4, which is a permanent resist. 6. A printed wiring board having the cured product layer according to claim 4.