JPH03250012A - Solder resist ink composition and cured product thereof - Google Patents

Abstract

PURPOSE:To form a solder resist ink composition having good storage stability and excellent photosensitivity and giving a cured film excellent in adhesion, soldering-heat resistance, etc., by using an unsaturated polycarboxylic acid resin derived from a specified epoxy resin as a base and mixing this base with other specified components. CONSTITUTION:An alkali-developable photosensitive thermosetting solder resist ink composition is formed by mixing an unsaturated polycarboxylic acid resin (A) obtained by reacting a reaction product between an epoxy resin of formula I (wherein R is H or CH3; and (n) is 0 or an integer of 1 or greater) and (meth) acrylic acid with a polybasic carboxylic acid or its anhydride with an epoxy(meth)acrylate (B) which is a reaction product between an epoxy resin of a softening point of 50 deg.C or above and (meth)acrylic acid, a reaction product (C) between a carboxyl- or carboxylic anhydride group-containing polymer and a hydroxy (meth)acrylic ester, tris(2,3-epoxypropyl) isocyanurate (D), an unsaturated monomer and/or an organic solvent (E) as a diluent, and a photopolymerization initiator (F).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is useful as a solder resist for printed wiring boards, has excellent developability, is resistant to developing solutions in exposed areas, has a long pot life, and is suitable for pre-drying. Alkaline-developable photosensitive thermosetting solder resist with excellent thermal stability and photosensitivity, as well as excellent adhesion of the cured film, electrical insulation, soldering heat resistance, chemical resistance, gold plating resistance, etc. The present invention relates to an ink composition and a cured product thereof.

(Prior Art) In recent years, ultraviolet curable compositions have been widely used for reasons such as resource saving, energy saving, improved workability, and improved productivity. In the field of printed wiring board processing, various inks such as solder resist inks and marking inks have been shifting from conventional thermosetting compositions to ultraviolet curable compositions for the same reason. Among these, solder resist inks were the first to transition to UV-curable compositions.

(Problems to be Solved by the Invention) Screen printing methods have often been used to form resist patterns on printed wiring boards, but when such screen printing methods are used, bleed, smearing, or Phenomena such as sag and sag occur, and as a result, it is no longer possible to cope with the recent increase in the density of printed wiring boards.

To solve these problems, there are dry film type photoresists and liquid developable resist inks, but dry film type photoresists tend to produce air bubbles during thermocompression bonding and have poor heat resistance. There are also problems such as concerns about adhesion and high price. On the other hand, currently commercially available liquid resists include those that use organic solvents as developing solutions and those that are developed with dilute alkaline aqueous solutions. However, the solvent is expensive and there are problems with solvent resistance and acid resistance. Also, those that can be developed with dilute alkaline aqueous solution,
The cured product is insufficient in terms of heat resistance, chemical resistance, gold plating resistance, etc., which is a problem.

(Means for Solving the Problems) As a result of intensive research to solve the above-mentioned problems, the present inventors found that the storage stability is good, the thermal stability during pre-drying is excellent, and development is possible with an alkaline aqueous solution. This is an alkali-developable photosensitive thermosetting solder resist that is suitable for solder resists that have excellent photosensitivity, as well as the adhesion of the cured film, electrical insulation, soldering heat resistance, chemical resistance, gold plating resistance, etc. We have succeeded in providing an ink composition and a cured product thereof.

That is, the present invention provides: (1) an epoxy resin represented by the general formula [I] (wherein R is H or CH3, and n is an integer of 0 or 1 or more, preferably an integer of 0-15); , particularly preferably 0-
It is an integer of 10. ) and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride, the unsaturated group-containing polycarboxylic acid resin (A) has a softening point of 50°C or higher, preferably 65°C or higher. Epoxy (meth)acrylate (B) is a reaction product of an epoxy resin and (meth)acrylic acid, a reaction product of a polymer having a carboxyl group or a carboxylic acid anhydride group and a hydroxyl group-containing (meth)acrylic ester (C), tris(2,3-epoxypropyl)isocyanurate (D), an unsaturated group-containing monomer and/or organic solvent (E) as a diluent, and a photopolymerization initiator (F). An alkali-developable photosensitive thermosetting solder resist ink composition, characterized in that: (i) the blending ratio of the unsaturated group-containing polycarboxylic acid resin (A) and the epoxy (meth)acrylate (B) is 100;
: The composition according to (1) above, which is I to 35 (based on weight), (1) the unsaturated group-containing polycarboxylic acid resin (A) and the reactant (
The blending ratio with C) is too: 1 to 50 (based on weight)
The composition according to any one of (1) and (2) above, which is 0) an unsaturated group-containing polycarboxylic acid resin (A) and tris(2,3-epoxypropyl)isocyanurate (D)
The composition according to any one of (1) to (1) above, wherein the blending ratio of the diluent (E) is Ion:Sm2O3 (weight basis), (2) the unsaturated group-containing polycarboxylic acid resin (A) The composition according to any one of (1) to ω) above, which is 10 to 300 parts by weight per 100 parts by weight, [F])
The composition according to any one of (1) to (1) above, which contains an epoxy resin curing agent, (2) The composition according to any one of (1) to (6) above, which contains an inorganic filler, (marked colored pigment) (1) A cured product of the composition described in any one of (1) to (2) above.

In this specification, (meth)acrylic acid means acrylic acid, methacrylic acid, or a mixture thereof, and (meth)acrylic ester means acrylic ester, methacrylic ester, or a mixture thereof.

Unsaturated group-containing polycarboxylic acid resin (A
) is an epoxy resin represented by the general formula [I] and (meth)
It can be obtained by reacting with acrylic acid and then with a polybasic carboxylic acid or its anhydride. The epoxy resin represented by the above formula [I] used in the present invention is, for example, Tuftix-742 (Dow Co., Ltd.
Manufactured by Chemical Company, product name) EPPN-5ol, EPP
It is already commercially available as N-502°E P P N-504 (manufactured by Japan Tohoku Co., Ltd., trade name). Formula [I]
The reaction between the epoxy resin represented by the formula [I] and (meth)acrylic acid is performed when one of the epoxy groups of the epoxy resin represented by the formula [I]
Approximately 0.8 to 1.5 of (meth)acrylic acid per chemical equivalent
The reaction is carried out at a ratio of chemical equivalents, particularly preferably about 0.9 to 1.1 chemical equivalents, and during the reaction, the unsaturated group-containing monomer and/or organic solvent (E
) is preferably used.

Specific examples of unsaturated group-containing monomers include calpitol (
meth)acrylate, phenoxyethyl(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, dipentaerythritol poly
Examples include (meth)acrylate, polypentaerythritol poly(meth)acrylate, and the like. Specific examples of the organic solvent include solvents such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carpitol acetate, diethylene glycol dimethyl ether, and solvent naphtha. Furthermore, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.) to promote the reaction, and the amount of the catalyst used is preferably 0% based on the reaction mixture. .1-10% by weight, particularly preferably 0.3-5% by weight. In order to prevent polymerization during the reaction, it is preferable to use polymerization inhibitors (e.g. methoquinone, hydroquinone, phenothiazine, etc.), the amount of which is preferably used relative to the reaction mixture:
0.01-1% by weight, particularly preferably 0805-0.5
Weight%. The reaction temperature is preferably 6G to 150°C,
Particularly preferably, the temperature is 80 to 1211°C. Further, the reaction time is preferably 5 to 60 hours, particularly preferably 10 to 5 hours.
It is 0 hours.

Specific examples of polybasic carboxylic acids or their anhydrides include:
Examples include maleic acid, succinic acid, phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic acid, and their anhydrides. It will be done.

The reaction between the reaction product of the epoxy resin represented by the general formula [1] obtained by the above method and (meth)acrylic acid and the polybasic carboxylic acid or its anhydride can be performed by the reaction product represented by the general formula [I]. This is an esterification reaction between the hydroxyl group in the reaction product of the epoxy resin and (meth)acrylic acid and the above acid or its anhydride. The reaction temperature is preferably 60-150°C, particularly preferably 80-120°C. The reaction time is preferably 1 to 30 hours, particularly preferably 5 to 20 hours. When carrying out this reaction, the reaction product obtained by reacting the epoxy resin represented by general formula [I] with (meth)acrylic acid as described above may be used as it is as a raw material for this esterification reaction. I can do it.

The acid value (OH/g in ■) of the esterification reaction product [unsaturated group-containing polycarboxylic acid resin (A)] is 30 to 150.
A range of mgKOH/g is preferred.

In the present invention, epoxy (meth)acrylate (B) is used which is a reaction product of an epoxy resin having a softening point of 50° C. or higher and (meth)acrylic acid. Specific examples of epoxy resins with a softening point of 50°C or higher include novolac-type epoxy resins (manufactured by Tobu Kasei Co., Ltd., YDCN-701, YDCN
-702, YDCN -703, YDPN-601
; Manufactured by Nippon Kayaku Co., Ltd., EOCN-102, EOCN-1
04, EPPN-201, BREN; manufactured by Asahi Kasei Industries, Ltd., ECN-168, ECN-273, ECN-28
6 etc.), bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., Epicoat 1001, Epicoat 1
002; Manufactured by Tobu Kasei Co., Ltd., YD B-4011, YD
E
PP N-502, etc.).

In the reaction between an epoxy resin having a softening point of 50°C or higher and (meth)acrylic acid, (meth)acrylic acid is preferably reacted with O18 to 1 chemical equivalent of the epoxy group of the epoxy resin having a softening point of 50°C or higher. .5 chemical equivalents, particularly preferably about 0
．． The reaction is carried out at a ratio of 9 to 1.1 chemical equivalents. During the reaction, it is preferable to use solvents such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carpitol acetate, diethylene glycol dimethyl ether, and solvent naphtha as a diluent, and to accelerate the reaction, a catalyst (for example, triethylamine, It is preferred to use benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.). The amount of catalyst used is preferably 1-10% by weight, particularly preferably 0.3-5% by weight, based on the reaction mixture. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, phenothiazine, etc.), and the amount used is preferably 0 or less, based on the reaction mixture.
．． 01-1% by weight, particularly preferably 0.05-G, 5
Weight%. The reaction temperature is preferably "60 to 150
℃, particularly preferably 80 to 120℃. The reaction time is preferably 5 to 60 hours, particularly preferably 10 to 50 hours.
It's time. Preferred epoxy (meth)acrylates (
Examples of B) include epoxy acrylates of phenol novolac type epoxy resins, epoxy acrylates of cresol novolac type epoxy resins, and the like.

In the present invention, a reaction product (C) of a polymer having a carboxyl group or a carboxylic acid anhydride and a hydroxyl group-containing (meth)acrylic ester is used. Specific examples of polymers having carboxyl groups or carboxylic acid anhydride groups include copolymers of styrene and maleic anhydride (ATOC
I (SMA-1000SSMA-2000 etc. made by EM)
, a copolymer of α-isobutylene and maleic anhydride ((
(manufactured by Kuraray Co., Ltd., Kuraray Soba Sea 04, etc.), a reaction product of a copolymer of styrene and maleic anhydride with an alkyl alcohol (manufactured by ATOCHEM, SMA-1735)
2A, etc.). The average molecular weight of the polymer is preferably 50,000 or less, particularly preferably 10,000 or less.

Preferred polymers include copolymers of styrene and maleic anhydride. Specific examples of hydroxyl group-containing (meth)acrylic esters include 2-
Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, reaction product of 2-hydroxyethyl (meth)acrylate and ε-caprolactone, pentaerythritol tri(meth)acrylate, etc. can be mentioned. Preferred hydroxyl group-containing (
Examples of the meth)acrylic acid ester include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. In the reaction between the polymer and the hydroxyl group-containing (meth)acrylic ester, 0.1 hydroxyl group of the hydroxyl group-containing (meth)acrylic ester per 1 chemical equivalent of carboxyl group of the polymer.
It is preferable to react at a ratio of 0.75 to 0.75 chemical equivalents.

Also, for 1 chemical equivalent of carboxylic acid anhydride in the polymer,
It is preferable to react at a ratio of 0.4 to 0.6 chemical equivalents of hydroxyl groups of the hydroxyl group-containing (meth)acrylic ester. The acid value (■KOH/g) of the product is 50 to 300■
The reaction temperature is preferably about xol (/g).
Preferably 60 to +5 fl °C, particularly preferably 80
~120°C. The reaction time is preferably 5 to 50 hours, particularly preferably 5 to 2 G hours. It is preferable to use the above-mentioned organic solvents as diluents during the reaction.

Tris(2,3-epoxyprobyl) used in the present invention
Isocyanurate (D) can be easily obtained from the market. For example, TEP IC manufactured by Yasan Kagaku Co., Ltd.
-G, TEP I C-P, TEP [C-L, TEP
I C-3, TEP I C-H, etc. can be mentioned.

As the photopolymerization initiator (F) used in the present invention, any known photopolymerization agent can be used, but it is desirable that the photopolymerization initiator (F) has good storage stability after blending. Examples of such photopolymerization initiators include benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2.2-dimethoxy-2-phenylacetophenone, 2.2-jethoxy-2-phenylacetophenone, 1. 1-dichloroacetophenone,
l-Hydroxycyclohexylphenyl ketone, 2-
Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, N,N-dimethylaminoacetophenone, 2-methylanthraquinone, 2
-ethylanthraquinone, 2-jerl butylanthraquinone, l-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2.4-dimethylthioxanthone, 24-diethylthioxanthone, 2
, 4-diisopropylthioxanthone, acetophenone dimethyl ketal benzophenone, methylbenzophenone, 44'-dichlorobenzophenone, tr-bisdiethylaminobenzophenone, Michler's ketone and the like. These can be used alone or in combination of two or more. Furthermore, such a photopolymerization initiator can be used alone with a known and commonly used photosensitizer such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, or triethylamine. Alternatively, two or more types can be used in combination.

Preferred combinations include 2,4-diethylthioxanthone, 2-isopropylthioxanthone and N,N-dimethylaminobenzoic acid ethyl ester, and 2-methyl-
Examples include a combination of 1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one (manufactured by Ciba Geigy, Irgacure 907) and 2,4-diethylthioxanthone or 2-isopropylthioxanthone.

The preferred proportions of each component in the composition of the present invention are as follows. The blending ratio of component (A) and component (B) is 1
00: 1 to 35 (based on weight) is preferred, particularly preferably 10G+ 5 to 30 (based on weight).

The blending ratio of component (A) and component (C) is 100:1~
SG (weight basis) is preferred, particularly preferably +00
:5 to 40 (based on weight).

The blending ratio of component (A) and component (D) is 10025~
100 (by weight) is preferred, particularly preferably,
100:15-7G (weight basis).

The amount of component (E) used is 1 per 100 parts by weight of component (A).
0 to 300 parts by weight is preferred, particularly preferably 40 to 300 parts by weight.
It is 150 parts by weight.

The amount of component (F) used is per 100 parts by weight of component (A).
0.5 to 50 parts by weight is preferable, particularly preferably 4 to 3 parts by weight.
5 parts by weight.

It is preferable to use an epoxy resin curing agent in the composition of the present invention to thermally cure component (D). Specific examples of epoxy resin curing agents include dicyandiamide and its derivatives (e.g., phenylbiguanide, etc.); organic acid hydrazide (e.g., adipic acid hydrazide, etc.); urea, melamine, and their derivatives (diallylmelamine, etc.); imidazole compounds ( For example, 2-ethyl-4-methylimidazole, l-cyanoethyl-2-ethyl-4methylimidazole, 2.4-diamino-6-(2'-methylimidazole(1))-ethyl-8-triazine, 2.
4-diamino-6-(2'-methylimidazolyl-(
1)) -ethyl-8-triazine-isocyanuric acid adduct, 2-methylimidazole, 1-phenyl-2-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.); triazine compounds (for example, 2. 4-diamino-6-vinyl-S-triazine
urea compounds (e.g.
-(3,4-dichlorophenyl) -1,1'-dimethylurea, 1,1'-isophorone-bis(3-methyl3-hydroxyethylurea), 1,1'-tolylene-bis(3,3-dimethyl Aromatic amine compounds (e.g., 4,4′-diamino-diphenylmethane, etc.); Aliphatic amine compounds (e.g., diethylenetriamine, etc.); Polyphenol compounds (e.g., polyvinylphenol, phenol novolak, etc.); Organic acid phosphine compounds (e.g., tributyl, etc.); phosphine, triphenylphosphine, etc.) and photocationic polymerization catalysts (e.g., triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylselenium hexafluorophosphate, triphenylselenium hexafluoroantimonate, diphenyliodonium) Hexafluoroantimonate, diphenyliodonium hexafluorophosphate, 2,4-cyclopentadien-■-yl ((1-
Examples include methylethyl)-benzene)-Fe-hexafluorophosphate (manufactured by Ciba Geigy, Irgacure 261). These known curing agents can be used alone or in combination of two or more.

When using an epoxy resin curing agent, the amount used is (D)
It is preferably 0.5 to 50 parts by weight, particularly preferably 1 to 30 parts by weight, per 100 parts by weight of the components.

The composition of the present invention may further contain inorganic fillers such as talc, silica, alumina, barium sulfate, magnesium oxide, etc. When inorganic fillers are used,
The amount used is 5 to 25 parts per 100 parts by weight of component (A).
It is preferably 0 parts by weight, particularly preferably 10 to 150 parts by weight. In addition, as a coloring pigment, cyanine green,
Cyanine blue etc. can also be used, and when using a colored pigment, the amount used is preferably 0.1 to 10 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of component (A).
~5 parts by weight.

The composition of the present invention may further contain melamine resins such as hexamethoxymelamine and hexabutoxymelamine, MB-3000 (manufactured by Mitsubishi Yuka Co., Ltd.), MB-21, if necessary.
0 (manufactured by Mitsubishi Yuka Co., Ltd.), polyimides such as MP256 (manufactured by Mitsubishi Yuka Co., Ltd.), chicken trope agents such as Aerosil, leveling agents such as silicones, fluorine-based polymers, acrylic copolymers, and antifoaming agents. , ultraviolet absorbers, antioxidants, polymerization inhibitors, etc. can also be used.

The composition of the present invention can be obtained by blending the ingredients preferably in the proportions described above and uniformly mixing them using a roll mill or the like.

The composition of the present invention is cured, for example, as follows to obtain a cured product. That is, screen printing method on printed wiring board,
The composition of the present invention is applied to a film thickness of 10 to 100 m by methods such as spraying, roll coating, electrostatic coating, and curtain flow coating, and after drying the coating at 60 to 80°C, negative The film is brought into direct contact with the paint film, then irradiated with ultraviolet rays, and the unirradiated areas of the paint film are further treated with an alkaline aqueous solution such as a 0.5-2% Na2CO3 aqueous solution, a 11.5-1% aqueous caustic soda solution, or a caustic potash aqueous solution. After dissolving and removing, a cured film is obtained by heating and curing at 120 to 170°C.

[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.

Note that parts in the examples are parts by weight.

[Synthesis of unsaturated group-containing polycarboxylic acid resin (A) (Synthesis Examples 1 to 3) Synthesis Example 1 Epoxy resin (manufactured by Japan Tohoku Co., Ltd.) which is a reaction product of salicylaldehyde, phenol, and epichlorohydrin; E P P N-502, softening point 70°C, epoxy equivalent +67) 53.1 parts, acrylic acid 21.8 parts,
0.05 part of methylhydroquinone, 0.5 part of triphenylstibine, and 34.1 parts of diethylene glycol dimethyl ether were added, and the temperature was raised to 95°C.
(2) The mixture was reacted for about 45 hours until the KOH/g) became 5 or less, and then 27.4 parts of tetrahydrophthalic anhydride was added and the mixture was reacted for 20 hours. 017 g of an unsaturated group-containing polycarboxylic acid resin (A-1) with an acid value (in components excluding the solvent) of 123 .mu.m was obtained.

Synthesis Example 2 The reaction was carried out in the same manner as in Synthesis Example 1, except that 25 parts of phthalic anhydride was used in place of tetrahydrophthalic anhydride in Synthesis Example 1, and 33.9 parts of diethylene glycol dimethyl ether was used. ) is 9
An unsaturated group-containing polycarboxylic acid resin (A-2) having a value of 0 K (IFI/g) was obtained.

Synthesis Example 3 180 parts of epoxy resin (manufactured by Japan Tohoku Co., Ltd., EPPN-504, softening point, 75°C, epoxy equivalent: 111G), which is a reaction product of salicylaldehyde, 0-cresol, and epichlorohydrin, 68 parts of acrylic acid .5 parts, 0.17 parts of methylhydroquinone, 1.6 parts of triphenylstibine, and 99.9 parts of ethyl cellosolve acetate.
8 parts of the reaction solution was added, the temperature was raised to 95°C, and the acid value of the reaction solution (■ was 0).
87 g) was reacted for about 45 hours until it became 5 or less,
Then, 4 g portions of maleic anhydride were added and reacted for 20 hours. Acid value (in components excluding solvent) is 94.3■
xOH/g unsaturated group-containing polycarboxylic acid resin (A-3
) was obtained.

[Synthesis of epoxy (meth)acrylate (B) (Synthesis Examples 4 to 5)] Synthesis Example 4 EPPN-201 (manufactured by Nippon Tohoku Co., Ltd., phenol novolak type epoxy resin, softening point, 65°C, epoxy equivalent 187.1 ) 51.2 parts, 18.7 parts of acrylic acid, 0.05 parts of methylhydroquinone, 0.5 parts of triphenylstibine, and 3 parts of diethylene glycol dimethyl ether
Add part G, raise the temperature to 95℃, and adjust the acid value (■KOH/g)
The reaction was carried out for about 45 hours until the value of 5 was reduced to 5 or less, and epoxy acrylate (B-1) was obtained.

Synthesis Example 5 E OCN-104 (manufactured by Japan Tohoku Co., Ltd., cresol novolac type epoxy resin, softening point gO ℃, epoxy equivalent 220) 220 parts, acrylic acid 69.1 parts, methylhydroquinone 0.2 parts, triphenyls 2.0 parts of Tibin and 124 parts of butyl cellosolve acetate were added, heated to 95°C, and reacted for about 45 hours until the acid value (■KOH/g) became 5 or less, to obtain epoxy acrylate (B-2). .

[Synthesis of reaction product (C) of a polymer having a carboxyl group or a carboxylic acid anhydride group and a hydroxyl group-containing (meth)acrylic ester (Synthesis Example 6)] Synthesis Example 6 Copolymerization of styrene and maleic anhydride Union (ATOCHE)
Manufactured by M company, SMA-10001 acid value (■NOR/g
) 480) 43.4 parts, 21.6 parts of 2-hydroxyethyl acrylate, 35 parts of diethylene glycol dimethyl ether, and 0.05 parts of methoquinone were added, and heated to 90°C.
The reaction was carried out for about 20 hours until the acid value (■ton/g) reached 146, and the reactant (C-1) [a polymer having a carboxyl group or a carboxylic acid anhydride group and a hydroxyl group-containing (meth)acrylic acid ester] A reaction product (C)] was obtained.

Examples 1 to 7, Comparative Examples 1 to 8 Solder resist ink compositions were blended according to the formulation shown in Table 1, and kneaded using a three-roll mill. This was applied to the entire surface of the copper through-hole printed wiring board by screen printing so that the film thickness after drying was 15 to 25.
After pre-drying the coating film at 70°C for 15 minutes, the rear side was similarly printed and pre-dried at 70°C for 25 minutes. The obtained product was tested for [dryness to the touch] as described below. next,
Bring the solder mask pattern film into contact with the coating surface,
Metal halide lamp double-sided simultaneous exposure device (manufactured by Oak Co., Ltd.)
HMW G11l) at a light intensity of 500 m1/cj, and the unirradiated area of the coating was sprayed with a 1% OW sodium carbonate aqueous solution at a spray pressure of 2.5 kg/J1 at a liquid temperature of 25°C.
It was developed for seconds and then dissolved and removed. [Developability] of the obtained product
and [Development resistance] were evaluated as described below. Thereafter, heat curing was performed at 150°C for 611 minutes in a hot air dryer, and the test pieces with the resulting coating film were evaluated as described below.
[Acid resistance] [Gold plating resistance], [Alkali resistance], [
Solvent resistance] and [insulation resistance] tests were conducted. Further, the [exposure sensitivity] test was also conducted as described below. The results are shown in Table 2.

Test method and evaluation method [Dryness to touch] After cooling for 10 minutes, the dryness of the coating film was evaluated according to JIS K540.
Judgment was made according to 0.

◎・・・・・・No tack recognized at all O...
... Slight tack is observed Δ...
Those with noticeable tackiness ×... Those with ink adhering to fingers [Developability] Developability was visually evaluated using a magnifying glass.

○・・・Completely developed Δ・・・Those with thin areas that are not developed××
...Those with a considerable portion that was not developed [Development resistance] The condition of the coating film was visually judged.

O...No change observed Δ...
・・Those where the gloss of the paint film surface has decreased×・・・Those where a part of the paint film has peeled off [Exposure sensitivity] Slower Gri7 Scxlcs (Homll
sr Gripbic manufactured by Arfx, optical density 0.1
A 5.21 step negative film) was adhered to the coating film obtained by pre-drying both sides, and a 7KW metal halide lamp was used to irradiate the film with a light intensity of 5OOsi/aJ (on the substrate). This coating film was developed under the above conditions, and the number of steps remaining on the copper foil was examined.

[Coating Film Hardness] The hardness of the coating film was measured according to JIS K5400.

[Adhesion] In accordance with the test method of JISD-0202, crosscuts were made on the coating film in the shape of the base grains, cut into 100 pieces, and then a peeling test was performed using Sellotape. It was evaluated according to.

[Solder heat resistance] According to the test method of JIS C6481, the test piece was immersed in a 260°C solder bath for 10 seconds 10 times or 4 times,
Changes in appearance were evaluated.

(Bost flux resistance) Dipping for U seconds was performed 10 times, and changes in appearance were evaluated.

0... No change in appearance △... Discoloration of the paint film is observed ×...
...Pooring of the paint film, peeling, and solder sinking Note) Post flux used: JS-64P (manufactured by Sanei Chemical Co., Ltd.) (Resistance to leveler flux) Dip for 10 seconds 4 times to notice changes in appearance. evaluated.

O: No change in appearance △: Discoloration of the paint film is observed ×:
...Pooring, peeling, and solder sinking of the paint film Note) Leveler flux used: 5SF-02 (manufactured by Sanei Chemical Co., Ltd.) [Acid resistance] Test piece was placed in a 10% sulfuric acid aqueous solution at 25°C. After immersion for 15 minutes, changes in the appearance of the coating film were visually observed. The adhesion is
A peeling test was performed on the solder pattern portion using cellophane tape to determine the peeling state of the resist.

○...No change in appearance, no peeling of paint film at all △...No change in appearance, but slight peeling of paint film X......paint film Items with significant peeling in the beering test (resistance to gold plating) The test piece was plated with nickel electrolytically, and then the test piece was plated with nickel electrolytically, using ``Alluna S39'' manufactured by Uezai Kogyo Co., Ltd., at a liquid temperature of 45°C. ℃, current density 2.5A/dd, plating for 5 minutes, 2.
After depositing gold plating with a thickness of Om, the state of the coating film was evaluated in the same manner as in the acid resistance test.

[Alkali resistance] A test piece was placed in a 10v 1% aqueous sodium hydroxide solution at 25°C.
It was immersed for 15 minutes and evaluated by conducting a test similar to the acid resistance test.

[Solvent Resistance] A test piece was immersed in dichloromethane at 25°C for 30 minutes, and changes in appearance were observed.

○...No change in appearance at all X...
Swelling and penetration [Insulation resistance] Using the test piece, the insulation resistance after moisture absorption and electrolytic corrosion after 7 days was measured according to the test method of I PC-3M-1140B (I PC class ■).

KAYARAD R-5027: Manufactured by Nippon Tohoku Co., Ltd., reaction product of phenol novolac type epoxy acrylate and dibasic acid anhydride, product containing 40% by weight of butyl cellosolve acetate, acid value 6g, 5 (■wo
H/g) YARAD ll-5089: Manufactured by Nippon Tohoku Co., Ltd., reaction product of bisphenol A type epoxy acrylate and dibasic acid anhydride, product containing 40% by weight of carpitol acetate, acid value 63 (KOH/g ) KAYARAD R-5100: Manufactured by Japan Tohoku Co., Ltd., reaction product of epoxy acrylate and dibasic acid anhydride of Epicote IO318 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy resin), product containing 35% by weight of butyl cellosolve acetate, acid Value 79 (■KOH/g)T
EPIC-S: manufactured by Nissan Chemical Co., Ltd., tris(2,3-epoxyprobyl) in cyanurate, melting point 95-125°C TEPIC-H: manufactured by Nissan Chemical Co., Ltd., tris(2,3-epoxyprobyl) in cyanurate ) Isocyanurate, melting point 150-156°C TEPIC-L: manufactured by Nissan Chemical Co., Ltd., tris (2,3-epoxypropyl) in cyanurate, melting point IO 1-106°C EPPN-201: manufactured by Nihon Tohoku Co., Ltd., Phenol novolac type epoxy resin, softening point 65°C KAYARAD DPHA: Diventaerythritol polyacrylate KAYARAD DPC^-60, manufactured by Nippon Kayaku Co., Ltd. ε-caprolactone modified product of dipentaerythritol, manufactured by Nippon Kayaku Co., Ltd. Polyacrylate Irgacure 907 manufactured by Ciba Geigy Co., Ltd., photopolymerization initiator KAYACUIIE DETI: manufactured by Nippon Kayaku Co., Ltd., photopolymerization initiator KS-603+ manufactured by Shin-Etsu Chemical Co., Ltd., antifoam agent Taiyo Ink Co., Ltd. Manufacturer: PH0TOFINERPSR-4000H-7 (phenol novolac epoxy acrylate system) [Effects of the invention] The alkaline-developable photosensitive thermosetting solder resist ink composition of the present invention can be selectively linked with ultraviolet rays through a patterned film. In the formation of solder resist patterns by exposing to light and developing the unfogged light areas, it has excellent developability, has resistance to developing solutions in exposed areas, has a long pot life, and has excellent thermal stability during pre-drying. It also has excellent photosensitivity. Furthermore, the resulting cured product has excellent adhesion, electrical insulation, soldering heat resistance, chemical resistance, gold plating resistance, etc.

Claims (9)

[Claims] (1) Epoxy resin represented by the general formula [I]▲Mathematical formula,
There are chemical formulas, tables, etc. ▼ [I] (In the formula, R is H or CH_3, and n is an integer of 0 or 1 or more.) The reaction product of (meth)acrylic acid is a polybasic carboxylic acid or an unsaturated group-containing polycarboxylic acid resin (A) obtained by reacting with the anhydride thereof, an epoxy resin (A) which is a reaction product of an epoxy resin with a softening point of 50°C or higher and (meth)acrylic acid;
meth)acrylate (B), a reaction product of a polymer having a carboxyl group or a carboxylic acid anhydride group and a hydroxyl group-containing (meth)acrylic ester (C), tris(2
, 3-epoxypropyl) isocyanurate (D), an unsaturated group-containing monomer and/or an organic solvent as a diluent (
E) and a photopolymerization initiator (F). An alkali-developable photosensitive thermosetting solder resist ink composition. (2) The blending ratio of unsaturated group-containing polycarboxylic acid resin (A) and epoxy (meth)acrylate (B) is 100:
1 to 35 (by weight). (3) The composition according to claim 1 or 2, wherein the blending ratio of the unsaturated group-containing polycarboxylic acid resin (A) and the reactant (C) is 100:1 to 50 (by weight). (4) Unsaturated group-containing polycarboxylic acid resin (A) and tris(2,3-epoxypropyl)isocyanurate (D)
4. The composition according to claim 1, wherein the composition has a blending ratio of 100:5 to 100 (by weight). (5) The composition according to any one of claims 1 to 4, wherein the amount of the diluent (E) is 10 to 300 parts by weight per 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin (A). (6) The composition according to any one of claims 1 to 5, which contains an epoxy resin curing agent. (7) The composition according to any one of claims 1 to 6, containing an inorganic filler. (8) The composition according to any one of claims 1 to 7, containing a colored pigment. (9) A cured product of the composition according to any one of claims 1 to 8.