JP2817901B2 - Unsaturated group-containing polycarboxylic acid resin, resin composition using the same, solder resist resin composition and cured product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to an unsaturated group-containing polycarboxylic acid resin, a solder-resist resin composition for a printed wiring board containing the resin, which has no tack on the resist surface after predrying. The present invention relates to a resin composition having excellent developability and a cured film having excellent adhesion, electrical insulation, solder heat resistance, and chemical resistance, and a cured product thereof.

[0002]

2. Description of the Related Art In recent years, ultraviolet curable compositions have been frequently used in various fields for reasons such as resource saving, energy saving, improvement in workability and improvement in productivity. In the field of printed wiring board processing, for the same reason, various inks such as solder resist inks and marking inks have been transferred from conventional thermosetting compositions to ultraviolet curable compositions. Among them, the solder-resist ink quickly shifted to an ultraviolet-curable composition.

[0003]

A screen printing method has been widely used as a method for forming a resist pattern on a printed wiring board. However, such a screen printing method often involves the use of a screen printing method. Phenomena such as bleeding, bleeding, or sagging have occurred, and this has become impossible to cope with recent high-density printed wiring boards. In order to solve these problems, dry film type photoresists and liquid developable resist inks have been proposed and used.However, in the case of dry film type photoresists, bubbles are generated during thermocompression bonding. Easy to occur,
There are also problems such as heat resistance and adhesion, and high price. On the other hand, liquid resists that are currently commercially available include those using an organic solvent as a developing solution and those developing with a dilute aqueous alkali solution, but those using an organic solvent have the problem of air pollution. In addition, the solvent is expensive, and the cured product has problems in solvent resistance and acid resistance. For those that can be developed with dilute alkaline aqueous solution, after pre-drying, contact the negative film on the resist coated surface, and after exposing, when peeling the negative film, it is difficult to peel off from the resist coated surface, or the resist adheres to the negative film. However, the negative film may not be reused, which is a problem.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, there is no tack on the surface of the resin composition coated with the pre-dried resin, and after exposure to contact with a negative film. A resin useful as a solder-resist resin composition that easily peels off the negative film, can be developed with an alkaline aqueous solution, and has excellent adhesion, electrical insulation, solder heat resistance, and chemical resistance of the cured film. It succeeded in providing a composition and a cured product thereof. That is, the present invention
(1) An unsaturated group-containing polycarboxylic acid resin which is a reaction product of a phenolated polybutadiene epoxy resin and (meth) acrylic acid and a polybasic carboxylic acid or anhydride thereof. (2) a resin composition comprising the unsaturated group-containing polycarboxylic acid resin described in (1) above, particularly a solder-resist resin composition; and (3) a resin composition described in (2) above. Cured product.

The unsaturated group-containing polycarboxylic acid resin of the present invention is obtained by reacting a phenolated polybutadiene epoxy resin with (meth) acrylic acid and then reacting a polybasic carboxylic acid or an anhydride thereof. Can be obtained by Phenolized polybutadiene is composed of polybutadiene (preferable average molecular weight is 500 to 2,000) and O
-An addition reaction product of phenols which may be substituted with an alkyl group such as cresol, for example, P-LPB
(OH value 340, softening point 170 ° C), P-700-30
0 (OH value: 333, softening point: 130 ° C.) [all manufactured by Nippon Petrochemical Co., Ltd., trade name, addition reaction product of polybutadiene and O-cresol].
Such commercially available products can be used as raw materials. The reaction between phenolated polybutadiene and epihalohydrin such as epichlorohydrin for synthesizing an epoxy resin of phenolated polybutadiene can be carried out by a known method.

[0006] For example, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium chloride or the like is used to prepare a phenolated polybutadiene and an epihalohydrin in an excess molar amount with respect to the hydroxyl equivalent of the phenolated polybutadiene. The reaction is performed in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. When a quaternary ammonium salt or the like is used, the reaction stops at the stage of the ring-opening addition reaction, and then the above-mentioned alkali metal hydroxide is added to cause a ring-closing reaction. When an alkali metal hydroxide is added and reacted from the beginning, a ring-opening addition reaction and a ring-closing reaction are performed at once. The usage ratio of epihalohydrin is usually in the range of 1 to 50 mol, preferably 3 to 15 mol, based on 1 hydroxyl equivalent of phenolated polybutadiene. The amount of the alkali metal hydroxide used is usually 0.8 to 0.8 with respect to 1 hydroxyl equivalent of the phenolated polybutadiene.
When the quaternary ammonium salt is used, the amount of the quaternary ammonium salt is usually 0.1 mol per 1 equivalent of the hydroxyl group of the phenolated polybutadiene. 001 to 1 mol, preferably 0.005 to
It is in the range of 0.5 mole. The reaction temperature is usually 30 to 13
0 ° C, preferably 40 to 120 ° C. The reaction time is usually 5 to 30 hours. Further, the reaction can be allowed to proceed while removing the water generated by the reaction outside the reaction system. After completion of the reaction, by-produced salts are removed by washing with water, filtration, etc., and excess epihalohydrin is distilled off to obtain an epoxy resin of phenolized polybutadiene.

In the reaction of the phenolated polybutadiene epoxy resin with (meth) acrylic acid, (meth) acrylic acid is preferably used in an amount of about 0.8 to 1.5 chemical equivalents per 1 equivalent of epoxy group of the epoxy resin. The reaction is carried out in an equivalent amount, particularly preferably in a ratio of about 0.9 to 1.1 chemical equivalent. During the reaction, as a diluent, solvents such as methyl ethyl ketone, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, diethylene glycol dimethyl ether, and solvent naphtha, or carbitol (meth) acrylate Phenoxyethyl (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropanetri (meth) acrylate, tris (hydroxyethyl) isocyanurate tri (meth) acrylate, dipentaerythri It is preferable to use reactive monomers such as lithol hexa (meth) acrylate and polypentaerythritol poly (meth) acrylate. Further, it is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.) in order to promote the reaction, and the use amount of the catalyst is preferably based on the reaction raw material mixture. Is 0.1 to 10% by weight, particularly preferably 0.3 to 10% by weight.
~ 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (e.g., methoquinone, hydroquinone, phenothiazine, etc.), and the amount thereof is preferably 0.01 to 1 based on the reaction raw material mixture.
%, Particularly preferably 0.05 to 0.5% by weight. The reaction temperature is preferably from 60 to 150 ° C, particularly preferably from 80 to 120 ° C. The reaction time is preferably 5 to 60 hours, particularly preferably 10 to 50 hours.

Next, the reaction product of the obtained phenolated polybutadiene epoxy resin and (meth) acrylic acid is reacted with a polybasic carboxylic acid or its anhydride.
Specific examples of the polybasic carboxylic acid or its anhydride,
Maleic acid, succinic acid, phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, pyromellitic acid, and the like, and anhydrides thereof. Can be

The reaction of a reaction product of a phenolated polybutadiene epoxy resin with (meth) acrylic acid and a polybasic carboxylic acid or an anhydride thereof is carried out by reacting an epoxy resin of phenolated polybutadiene with (meth) acrylic acid. Is an esterification reaction between the hydroxyl group in the reaction product with the above-mentioned acid or its anhydride. The reaction temperature is preferably from 60 to 150 ° C, particularly preferably from 80 to 120 ° C. The reaction time is preferably from 1 to 30 hours, particularly preferably from 5 to 20 hours. In carrying out this reaction, the reaction product obtained by reacting the epoxy resin of phenolated polybutadiene with (meth) acrylic acid as described above can be used as it is as a raw material for this esterification reaction. Acid value of esterification reaction product [unsaturated group-containing polycarboxylic acid resin] (mg
KOH / g) is preferably in the range of 30 to 150 mg KOH / g. The unsaturated group-containing polycarboxylic acid resin of the present invention,
As is clear from the above-mentioned synthesis method, the following structure is attached to the basic skeleton of phenolated polybutadiene in a pendant manner.

[0010]

(Wherein, R represents H or CH ₃ and X represents a residue of a polybasic carboxylic acid.) The resin composition or the solder-resist resin composition of the present invention (hereinafter collectively referred to as “composition ]), The amount of the unsaturated group-containing polycarboxylic acid resin contained in the composition is preferably from 10 to 90% by weight, particularly preferably from 20 to 80% by weight. The composition of the present invention further comprises epoxy resin compounds such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol type epoxy resin and tris (2,3-epoxypropyl) isocyanurate. Epoxy (meth) which is a reaction product of epoxy compound and (meth) acrylic acid
Acrylates and / or the above-mentioned reactive monomers can be contained. These are used in an amount of 0 to 10 based on 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin.
0 parts by weight is preferred. When the epoxy compound is used, an epoxy resin curing agent (for example, dicyandiamide and a derivative thereof, an imidazole compound, a triazine compound, a urea compound, an aromatic amine, a polyphenol compound, and a cationic photopolymerization catalyst) is used. They can be used alone or in combination of two or more. When an epoxy resin curing agent is used, its amount is preferably 0.5 to 50 parts by weight per 100 parts by weight of the epoxy compound.

As a method of curing the composition of the present invention to obtain a cured product, there is a curing method using an electron beam, an ultraviolet ray and heat, but it is preferable to cure with an ultraviolet ray and, if necessary, with heat. When curing with ultraviolet light, a photopolymerization initiator is used. As the photopolymerization initiator, any known photopolymerization initiator can be used, but one having good storage stability after blending is desirable. Examples of such a photopolymerization initiator include, for example, benzoyl, benzyl, benzoin methyl ether, 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, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,4- Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethylketanol, benzophenone, methylbenzophenone, 4,
4'-Dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone and the like can be mentioned. These can be used alone or in combination of two or more. Further, such a photopolymerization initiator may be N, N-dimethylaminobenzoic acid ethyl ester,
N, N-dimethylaminobenzoic acid isoamyl ester,
It can be used alone or in combination with two or more known and commonly used photosensitizers such as triethanolamine and triethylamine.

Preferred combinations are 2,4-diethylthioxanthone or 2-isopropylthioxanthone and N, N
-Combination with dimethylaminobenzoic acid ethyl ester,
2-methyl-1- [4- (methylthio) phenyl] -2
Morpholino-propan-1-one (Ciba Geigy-
And Irgacure-907) and 2,4-diethylthioxanthone or 2,4-isopropylthioxanthone. The proportion of the photopolymerization initiator used is 0 to 100 parts by weight of the unsaturated group-containing polycarboxylic acid resin.
It is preferably 50 parts by weight, particularly preferably 4-35 parts by weight. The composition of the present invention further comprises an inorganic filler, for example, talc, silica, alumina, barium sulfate, magnesium oxide and the like, and a coloring pigment such as cyaning line,
Cyanine blue and the like can be added. Also,
If necessary, melamine resins such as hexamethoxy melamine and hexabutoxy melamine, thixotropic agents such as aerosil, leveling agents such as silicone, fluorine-based polymers, and acrylate copolymers, defoamers, ultraviolet rays, and absorbents ,
An antioxidant, a polymerization inhibitor and the like can be added. The composition of the present invention can be obtained by blending the blended components preferably in the ratio described above and uniformly mixing with a roll mill or the like.

The composition of the present invention is preferably cured by ultraviolet rays and, if necessary, cured by heat to form a cured product. In the case of curing by heat, the heating temperature is preferably from 120 to 170 ° C. 30 minutes to 2 hours is sufficient. When the composition of the present invention is used as a solder-resist resin composition, for example, the composition is cured as follows to obtain a cured product.
That is, a screen printing method and a spray printing method are applied to a printed wiring board.
Method, roll coating method, electrostatic coating method, curtain coating method
After coating the composition of the present invention with a film thickness of 10 to 100 μm by a method such as a method and drying the coating film at 60 to 80 ° C., a negative film is brought into direct contact with the coating film, and then irradiated with ultraviolet light, Furthermore, 0.5-2% Na ₂ CO ₃ aqueous solution and 0.5-1%
After dissolving and removing the unirradiated portion of the coating film with an aqueous alkali solution such as an aqueous caustic soda solution or an aqueous caustic potassium solution,
A cured film is obtained by heating and curing at 170 ° C. for 30 minutes to 1 hour. It is particularly useful as the composition of the present invention and the solder-resist resin composition, but is also useful as an insulating paint, a printing ink, a coating agent and the like. The resin composition containing the novel unsaturated group-containing polycarboxylic acid resin of the present invention has a developability and a hardness of a cured product, solder heat resistance,
Excellent in acid resistance, alkali resistance, solvent resistance and insulation resistance.

[0015]

The present invention will be described below in more detail with reference to examples. Parts in Examples are parts by weight. Example 1 Phenolated polybutadiene (manufactured by Nippon Petrochemical Co., Ltd.
P-LPB, OH equivalent 340, softening point 170 ° C) 340
Was dissolved in 740 parts of epichlorohydrin.
At 8 ° C., 87.5 parts of a 48% aqueous NaOH solution were added dropwise over 5 hours.
During the dropwise addition, at a reaction temperature of 60 ° C. and a pressure of 100 to 150 mmHg, generated water and water from an aqueous solution of sodium hydroxide are continuously removed from the reaction system by azeotropic distillation with epichlorohydrin, and epichlorohydrin is returned to the system. Was. Then, after recovering excess unreacted epichlorohydrin under reduced pressure,
After adding 760 parts of methyl isobutyl ketone and dissolving uniformly, 13.4 parts of a 30% aqueous NaOH solution was added, and
The reaction was performed at 75 ° C. for 1 hour. After the completion of the reaction, 300 parts of water was added and washed with water. Oil-water separation was performed, and methyl isobutyl ketone was distilled and recovered from the oil layer. The epoxy equivalent was 448 and the softening point was 1
390 parts of 55 ° C. epoxy resin were obtained. Next, 448 parts of the epoxy resin obtained above, 68 parts of acrylic acid, 0.3 part of methylhydroquinone, and 3.7 parts of triphenylstibine.
, 155 parts of carbitol acetate and 66.8 parts of solvent naphtha, and the mixture was heated to 95 ° C. and reacted for 40 hours. Then tetrahydrophthalic anhydride 144.4
Parts, 153.5 parts of carbitol acetate and 66.2 parts of solvent naphtha, and reacted at 90 ° C. for 24 hours to obtain an unsaturated group-containing polycarboxylic acid resin (A-1) 1093.
Got a part. The acid value (in the components excluding the solvent) of the obtained product is 80 mgKOH / g, and the viscosity (25 ° C., poise)
230.

Example 2 In place of tetrahydrophthalic anhydride in Example 1, 93.1 parts of maleic anhydride was used. Also, carbitol acetate was used.
153.5 parts to 130 parts, solvent naphtha 66.
Except that 2 parts were changed to 56.2 parts, the reaction was carried out in the same manner as in Example 1, and the unsaturated group-containing polycarboxylic acid resin (A-2) 1
010 parts were obtained. The acid value (in the components excluding the solvent) of the obtained product was 89 mgKOH / g and the viscosity (at 25 ° C.,
Poise) was 190.

Example 3 The phenolated polybutadiene in Example 1 was changed to P-700-300 (OH equivalent: 333, softening point: 130 ° C.) manufactured by Nippon Petrochemical Co., Ltd., and the amount used was changed to 333 parts. 380 parts of an epoxy resin having an epoxy equivalent of 476 and a softening point of 98.4 ° C. were obtained in the same manner as in Example 1 except for the above. Next, 476 parts of the epoxy resin obtained above and acrylic acid 68
Parts, 0.3 parts of methylhydroquinone, 3.9 parts of triphenylstibine, 163 parts of carbitol acetate and 70 parts of solvent naphtha, and the temperature was raised to 95 ° C. to 40 parts.
Allowed to react for hours. Then 133.2 parts of phthalic anhydride, 153 parts of carbitol acetate and solvent naphtha 8
5.5 parts were charged and reacted at 90 ° C. for 24 hours to obtain 1128 parts of an unsaturated group-containing polycarboxylic acid resin (A-3).
Acid value of the obtained product (in components excluding solvent)
Was 75 mg KOH / g and viscosity (25 ° C., poise) was 200.

Example 4 476 parts of the epoxy resin obtained in Example 3 and methacrylic acid 8
2.5 parts, methylhydroquinone 0.3 part, triphenylstibine 4.0 parts, carbitol acetate 167 parts and solvent naphtha 72 parts were added, and the mixture was heated to 95 ° C. and reacted for 40 hours. Next, 146.3 parts of hexahydrophthalic anhydride, 162 parts of carbitol acetate and 69 parts of solvent naphtha were charged, and reacted at 90 ° C. for 24 hours to react with the unsaturated group-containing polycarboxylic acid resin (A-4) 11
55 parts were obtained. The acid value (in the components excluding the solvent) of the obtained product was 75 mgKOH / g, and the viscosity (25 ° C., poise) was 210.

Examples 5 to 8 and Comparative Examples 1 and 2 Solder-resist resin compositions (inks) were blended according to the blending compositions shown in Table 1, and kneaded with a three-roll mill. This is screen-printed to a film thickness of 15 to 2 after drying.
The entire surface was applied to a copper through-hole printed wiring board so as to have a thickness of 5 μm, and the coating film was preliminarily dried at 70 ° C. for 15 minutes. Then, the back surface was similarly printed and preliminarily dried at 70 ° C. for 25 minutes. Next, a solder mask pattern film is brought into contact with the coating film surface, and the “solder mask pattern peeling property” described later is used.
Was tested. Next, a solder mask pattern film was brought into contact with the coating surface, and 500 mJ was applied using a metal halide lamp double-sided simultaneous exposure apparatus (HNW680, manufactured by Oak Corporation).
/ Cm ^{2, and} the unirradiated portion of the coating film was developed with a 1.0 wt% aqueous sodium carbonate solution at a spray pressure of 2.5 kg / cm ^{2 at} a liquid temperature of 25 ° C. for 60 seconds to dissolve and remove. . The developability of the obtained product was evaluated as described below. Then, heat curing is performed at 150 ° C. for 60 minutes using a hot air dryer.
The test piece having the obtained cured film was tested for cured film hardness, solder heat resistance, acid resistance, alkali resistance, solvent resistance and insulation resistance as described below.

The results are shown in Table 2. Test method and evaluation method "Solder-mask pattern peeling property" After cooling for 10 minutes, the solder-mask pattern was peeled off from the coating film, and the state was evaluated. ◎ ──No abnormalities are observed when peeling off.── バ リ Slightly crunchy sound when peeling off. バ リ 顕 著 Slightly crunchy sound when peeling off. -What adheres to the mask pattern

Developability Developability was visually determined with a magnifying glass. ○ ──Completely developed △ ──Thin undeveloped part x × Some undeveloped part Cured film hardness The hardness of the cured film was measured according to JIS K5400.

Solder Heat Resistance According to the test method of JISC6481, the test piece was immersed in a solder bath at 260 ° C. for 10 seconds 10 times or 4 times, and the change in appearance was evaluated. (Post-flux resistance) The immersion for 10 seconds was performed 10 times, and the change in appearance was evaluated. ○ ──No change in appearance △ ──Discoloration of cured film is observed × ──Floating, peeling, solder dipping of cured film Note) Post flux used: JS-64P (Yamaei Chemical Co., Ltd.) (Flux resistance for leveler) The immersion for 10 seconds was performed four times, and the change in appearance was evaluated. ○ ──No change in appearance △ ──Discoloration of cured film is observed × ──Floating, peeling, and solder dipping of cured film Note) Leveler flux used: SSF-832
(Manufactured by Yamaei Chemical Co., Ltd.)

The test piece was immersed in a 10 vol% sulfuric acid aqueous solution at 25 ° C. for 15 minutes, and the appearance of the cured film was visually changed. Adhesion was measured using a cellophane tape for the solder pattern.
A ring test was performed to determine the state of peeling of the resist. ○ ──No change in appearance, no peeling of cured film △ ──No change in appearance, but slight peeling of cured film × ──Floating of cured film, peeling in peeling test Alkali resistance A test piece was placed in a 10 wt% aqueous sodium hydroxide solution at 25 ° C,
After immersion for 5 minutes, the same test as the acid resistance test was performed and evaluated.

Solvent Resistance The test piece was immersed in dichloromethane at 25 ° C. for 30 minutes, and the appearance change was observed. ○ ──No change in appearance × ──Swelled or permeated Insulation resistance The initial insulation resistance was measured using a test piece, and the IPC
According to the test method of -SM-840B (IPC class III), the insulation resistance such as moisture absorption and contact after 7 days was measured.

Table 1 Example Comparative Example 5 6 7 8 1 2 Unsaturated group-containing polycarboxylic acid resin obtained in Example 1 (A-1) 116.7 76.7 Unsaturated group-containing polycarboxylic acid resin obtained in Example 2 (A-2) 116.7 Unsaturated group-containing polycarboxylic acid resin obtained in Example 3 (A-3) 116.7 Unsaturated group-containing polycarboxylic acid resin obtained in Example 4 (A-4) 40 KAYARAD R-5027 * (1) 116.7 〃 R-5089 * (2) 116.7 〃 R-2058 * (3) 20 20 20 20 20 20 TEPIC-S * (4) 30 30 EPPN-201 * (5) 30 KAYARAD DPHA * (6) ) 5 14 8 5 5 14 Carbitol acetate 10 24 10 Irgacure-907 * (7) 8 12 8 8 8 12 KAYACURE DETX * (8) 2 3 2 2 2 3 Dicyandiamide (Epoxy resin curing agent) 5 5 5 Phthalocyanine line (pigment) 22 22 22 KS-603 (antifoaming agent) * (9) 22 22 22 hexamethoxymelamine 10 10 10 Torque 40 60 60 40 40 60

Table 2 Example
Comparative Example 5 6 7
8 1 2 Solder mask pattern film Peelability ◎ ◎ ◎
◎ △ △ Developability ○ ○ ○
○ ○ ○ Hardened film hardness 8H 8H 8H
7H 8H 4H Solder heat resistance Post flux resistance ○ ○ ○
○ ○ ○ Leveler flux resistance ○ ○ ○
○ ○ ○ Acid resistance ○ ○ ○
○ × × Alkali resistance ○ ○ ○
○ △ ○ Solvent resistance ○ ○ ○
○ △ △ insulation resistance (Ω) initial value 1.5x10 ¹⁴ 2.0x10 ¹⁴ 2.7x10 ¹⁴ 1.
0x10 ¹⁴ 3.5x10 ¹³ 2.6x10 ¹³ value after test 3.3x10 ¹³ 4.5x10 ¹³ 2.5x10 ¹³ 3.
6x10 ¹³ 5.1x10 ¹² 4.3x10 ¹²

Notes * (1) KAYARAD R-5027: Phenol novolak type epoxy acryl resin manufactured by Nippon Kayaku Co., Ltd.
Product with dibasic acid anhydride, butyl cellosolve acetate containing 40% by weight, acid value 68.5 (mgKOH / g) * (2) KAYARAD R-5089: Nippon Kayaku Co., Ltd. Carbitol acetate 40, a reaction product of a type A epoxy acrylate and a dibasic acid anhydride
% By weight, acid value 63 (mgKOH / g) * (3) KAYARAD R-2058: Nippon Kayaku Co., Ltd., phenol novolak epoxy acryle
And butyl cellosolve acetate containing 30% by weight. * (4) TEPIC-S: Tris (2,3-epoxypropyl) isocyanurate, manufactured by Nissan Chemical Industries, Ltd., melting point 95 to 125 ° C.

* (5) EPPN-201: phenol novolak type epoxy resin, Nippon Kayaku Co., Ltd., softening point 65 ° C * (6) KAYARAD DPHA: Nippon Kayaku Co., Ltd.
Dipentaerythritol polyacrylate * (7) Irgacure-907: manufactured by Ciba Geigy Corporation
Photopolymerization initiator * (8) KAYACURE DETX: Nippon Kayaku Co., Ltd.
* 9) KS-603: Shin-Etsu Chemical Co., Ltd., defoaming agent

[0029]

The resin composition of the present invention uses a novel unsaturated group-containing polycarboxylic acid resin to selectively expose to ultraviolet light through a pattern-formed film and develop unexposed portions. By doing so, in the formation of a solder resist pattern, the film formed with the pattern has excellent peelability from the coating film and has resistance to the developing solution in the exposed area, and the obtained cured product has good adhesion and electric properties. Insulation,
It has excellent solder heat resistance, chemical resistance, etc., and is suitable as a solder-resist resin composition.

Claims (4)

(57) [Claims] An unsaturated group-containing polycarboxylic acid resin which is a reaction product of a phenolated polybutadiene epoxy resin with (meth) acrylic acid and a polybasic carboxylic acid or anhydride thereof. 2. A resin composition comprising the polycarboxylic acid resin having an unsaturated group according to claim 1. 3. A solder-resist resin composition comprising the unsaturated group-containing polycarboxylic acid resin according to claim 1. 4. A cured product of the resin composition according to claim 2 or 3. [0001]