JPH03237112A - Unsaturated group-containing polycarboxylic acid resin, resin composition containing same resin, solder resist resin composition and cured materials of them - Google Patents

Abstract

PURPOSE:To obtain the subject resin having excellent developing property capable of developing in an aqueous solution of alkali and giving cured material having excellent heat resistance, etc., by further reacting a reaction product of tris(epoxypropyl) isocyanulate and (meth)acrylic acid with a polybasic carboxylic acid, etc. CONSTITUTION:A reaction product of tris(2,3-epoxypropyl) isocyanulate and (math)acrylic acid is further reacted with a polybasic carboxylic acid (e.g. maleic acid, succinic acid or phthalic acid) or anhydride of said acid to afford the aimed resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a polycarboxylic acid resin containing an unsaturated group, and a heat-resistant and chemical-resistant resin used as a permanent protective film for a printed wiring board containing the resin. The present invention also relates to resin compositions suitable for solder resists having excellent electrical insulation properties and cured products 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, bleeds, stains, and stains during printing often occur. Alternatively, a phenomenon such as sagging occurs, and for this reason, conventional ultraviolet curable compositions are no longer able to cope with the recent increase in the density of printed wiring boards.

To solve these problems, there are tri-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 concerns about the adhesion and the high price. On the other hand, currently commercially available liquid resists use organic solvents as developing solutions, which pose problems of air pollution, expensive solvents, and problems with solvent resistance and acid resistance.

(Means for Solving the Problem) As a result of intensive research to solve the problem described in #7, the present inventors have found that the cured product has heat resistance, adhesion, chemical resistance, plating resistance, and electrical insulation properties. We have succeeded in providing a resin composition suitable for solder resist, which has excellent properties and can be developed with a dilute alkaline aqueous solution.

That is, the present invention provides: (1) An unsaturated group-containing polyurethane obtained by further reacting a reaction product of tris(2,3-epoxypropyl)isocyanurate (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. Carboxylic acid resin (2) Resin composition containing the unsaturated group-containing polycarboxylic acid resin described in (1) above (3) Solder resist resin composition containing the unsaturated group-containing polycarboxylic acid resin described in (1) above Thing (4) Above (
Cured product of the unsaturated group-containing polycarboxylic acid resin described in 1) (5) Pertains to a cured product of the resin composition described in (2) or (3) above.

Here, (meth)acrylic acid refers to acrylic acid, methacrylic acid, or a mixture thereof. The unsaturated group-containing polycarboxylic acid resin of the present invention is produced by reacting tris (2,3-epoxypropyl) isocyanurate and (meth)acrylic acid to obtain epoxy (meth)acrylate, and then It can be obtained by reacting acids or their anhydrides. In the reaction between tris(2,3-epoxypropyl)isocyanurate and (meth)acrylic acid, (meth)acrylic acid is preferably used for 1 chemical equivalent of the epoxy group of tris(2,3-epoxypropyl)isocyanurate. are reacted in a ratio of about 0.8 to 1.5 chemical equivalents, particularly preferably about 0.9 to 1.1 chemical equivalents. A diluent (e.g., methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate,
Solvents such as carpitol acetate, benzene, toluene, petroleum ether, or carpitol (meth)acrylate, phenoxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, Reactive monomers such as acryloylmorpholine, trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, etc.) are preferably used, and catalysts (such as triethylamine, benzyl dimethyl amine, methyltriethylammonium chloride, triphenylstibine, etc.), and the amount of the catalyst used is preferably 0.1 to 10% by weight, particularly preferably 1 to 5% by weight, based on the reaction mixture. . Polymerization inhibitors (e.g., methoquinone,
Hydroquinone, phenothiazine, etc.) is preferably used, and the amount used is preferably 0 based on the reaction mixture.
．． 01 to 1% by weight, particularly preferably 0.05 to 0.5% by weight. The reaction temperature is 60-150°C, particularly preferably 80-120°C. The reaction time is preferably 5~
It takes about 50 hours. Further, specific examples of the polybasic carboxylic acid or its anhydride include maleic acid, succinic acid, phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, and hexachlorophthalic acid. Examples include hydrophthalic acid, trimellitic acid, pyromellitic acid, and anhydrides of these acids.

Tris(2,3-epoxypropyl) obtained by the above method
A reaction product of isocyanurate and (meth)acrylic acid (this can be easily obtained from the market, for example, TEPIC-TA manufactured by Yassan Kagaku Co., Ltd.) and a polybasic carboxylic acid or its anhydride. The reaction with tris(2,3-
This is an esterification reaction between the hydroxyl group in the reaction product [epoxy(meth)acrylate] of epoxypropyl)isocyanurate with (meth)acrylic acid and the above acid or its anhydride. The reaction temperature is preferably 60 to 150°C, especially 8
0 to 120°C is preferable. The reaction time is preferably 1 to 5
It takes about 0 hours. A diluent can be used when carrying out the reaction, such as OH among the diluents mentioned above.
Those without groups can be used. In addition, in order to prevent polymerization during the reaction, a polymerization inhibitor as described above can be used, and the amount used is preferably 0.00% relative to the reaction mixture.
01-1% by weight, more preferably 0.05-0.5% by weight.

The acid value (mgKOH/g) of the unsaturated group-containing polycarboxylic acid resin of the present invention thus obtained is preferably about 20 to 150.

The amount of the unsaturated group-containing polycarboxylic acid resin used in the composition of the present invention is 10-100% by weight, especially 20-90% by weight.
% by weight is preferred.

The composition of the present invention further includes epoxy compounds such as phenol/novolac type epoxy resin, cresol/novolac type epoxy resin, bisphenol type epoxy resin,
Epoxy acrylate, which is a reaction product of these epoxy compounds and (meth)acrylic acid, the above-mentioned reactive monomers, etc. can be included. The amount of these used is preferably 0 to 90% by weight, particularly 10 to 80% by weight of the composition.

Preferred methods for curing the composition of the present invention include curing with electron beams, ultraviolet rays, and heat, or curing with ultraviolet rays or heat.

When curing with ultraviolet light, a photoinitiator is used.

As the photopolymerization initiator, any known photopolymerization initiator can be used, but it is preferable to use one that has good storage stability after blending. Examples of such photopolymerization initiators include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl dimethyl ketal, 2-ethylanthraquinone, N,
N-dimethiaminobenzoic acid isoamyl ester, N,
N-dimethylaminobenzoic acid ethyl ester, 2-methyl-[4-(methylthio)phenyl]-2-morphsono-1-propanone, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2- Examples include hydroxy-2-methylpropiophenone. These photopolymerization initiators can be used in one species or in a mixture of two or more in any proportion. Preferred photoinitiators include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-methyl[4-(methylthio)
phenyl]-2-morpholino-1-propanone and the like. The amount of photopolymerization initiator used is 0.1 to 2 of the composition.
It is preferably 0% by weight, particularly 1 to 10% by weight.

When an epoxy group-containing compound is used in the composition of the present invention, it is preferable to use dicyandiamide, an imidazole compound, an aromatic amine compound, or a photocationic polymerization catalyst as the curing agent. The composition of the present invention may further contain melamine resins such as hexamethoxymelamine and hexabutoxymelamine, MB-3000 (manufactured by Mitsubishi Yuka Co., Ltd.), and MP-256 (manufactured by Mitsubishi Yuka Co., Ltd.), if necessary. ), inorganic fillers such as talc, silica, alumina, barium sulfate, and magnesium oxide, coloring pigments such as cyanine green and cyanine blue, thixotropic agents such as Aerosil, silicone, fluorine, and acrylic copolymers. It is also possible to use leveling agents such as, silane coupling agents, antifoaming agents, antioxidants, polymerization inhibitors, etc. The composition of the present invention is applied to a printed wiring board to a thickness of 10 to 100 μm by a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain flow coating method, etc., and then a coating film is formed. The negative film is dried at 60 to 80°C, then UV rays are irradiated through the negative film with or without direct contact with the coating film, and then 1 to
After dissolving and removing the unirradiated parts of the coating film with an alkaline aqueous solution such as a 2% 5zcos aqueous solution, if necessary, add 120 to 1
The cured product of the present invention can be obtained by heating and curing at 70°C. The composition of the present invention is particularly useful as a solder resist resin composition, and can also be used as an insulating material, an impregnating material, a surface coating material, a paint, an overcoat agent for color filters, an adhesive, and the like.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Note that parts in the examples are parts by weight.

[Examples 1 to 7 of unsaturated group-containing polycarboxylic acid resin] Example 1 Reaction product of tris (2,3-epoxypropyl) isocyanurate and acrylic acid (manufactured by Nissan Chemical Co., Ltd., TEPIC)
-TA100O1 semi-solid) 300 parts, butyl cellosolve acetate 165.5 parts, tetrahydrophthalic anhydride 8
5.9 parts and 0.2 parts of methoquinone were added, the temperature was raised to 90°C, and the reaction was carried out for 15 hours until the viscosity was 345 poise (25
°C), acid value (components excluding solvent) 82mgKOH/
The product g (unsaturated group-containing polycarboxylic acid resin of the present invention) was obtained.

Example 2 The reaction was carried out in the same manner as in Example 1, except that 55.3 parts of maleic anhydride was used instead of tetrahydrophthalic anhydride and the number of parts of butyrocellosolve acetate was changed to 152.4 parts. A product with a viscosity of 310 poise (25°C) and an acid value (component excluding the solvent) of 89 mgKOH/g was obtained.

Example 3 Example 1 except that 125.5 parts of phthalic anhydride was used instead of tetrahydrophthalic anhydride and the number of parts of butyl cellosolve acetate was changed to 182.6 parts.
The reaction was carried out in the same manner as above to obtain a product having a viscosity of 450 poise (at 25°C) and an acid value (components excluding the solvent) of 112 mgKOH/g.

Example 4 In Example 1, instead of tetrahydrofucric anhydride,
The reaction was carried out in the same manner as in Example 1, except that 43.5 parts of hexahydrophthalic anhydride was used and 147 parts of carpitol acetate was used instead of butyl cellosolve acetate.
A product with a viscosity of 250 boids (25°C) and an acid value (components excluding the solvent) of 46 mgKOH/g was obtained.

Example 5 Tris (2,3-epoxypropyl) isocyanurate (manufactured by Nissan Chemical Co., Ltd., TEPIC-P, epoxy equivalent weight 105) 315 parts, methacrylic acid 245 parts, methylhydroquinone 0.56 parts, methyltriethylammonium chloride 2 .0 parts and ethyl cellosolve acetate)
After adding 282.2 parts of maleic anhydride and raising the temperature to 95°C and reacting for 35 hours, 98 parts of maleic anhydride was added and 90 parts of maleic anhydride was added.
The reaction was carried out for 15 hours at
C), acid value (components excluding solvent) 85mgKOH/
H product was obtained.

Example 6 In Example 1, instead of tetrahydrophthalic anhydride,
Example 1 except that 56.4 parts of succinic anhydride was used and the number of parts of butyl cellosolve acetate was changed to 152.7 parts.
The reaction was carried out in the same manner as above to obtain a product having a viscosity of 320 poise (at 25°C) and an acid value (components excluding the solvent) of 88 mgKOH/g.

Example 7 The reaction was carried out in the same manner as in Example 1, except that 54.1 parts of trimellitic anhydride was used in place of tetrahydrophthalic anhydride in Example 1, and the number of parts of butyl cellosolve acetate was changed to 151.7 parts. Viscosity: 290 poise (25℃)
A product with an acid value (components excluding the solvent) of 89.3 mgKOH/H was obtained.

Examples 8 to 12 Solder resist resin compositions were blended according to the blending compositions shown in Table 1, and various performance tests were conducted as follows. The results are shown in Table 1.

A. (Solubility and developability) After applying each formulation (solder resist resin composition) to a copper through-hole printed wiring board with a film thickness of 20 μm by screen printing method, the coating film was dried at 70°C for 60 minutes. After that, a negative film is applied to the paint film in direct contact or without contact.Then, it is irradiated with ultraviolet light using a 5KW ultra-high pressure mercury lamp, and then exposed to 1.5% NazCOs at 30°C.
The unirradiated portion of the coating film was dissolved and removed using an aqueous solution at a spray pressure of 2.5 kg/d to determine solubility, and the number of seconds required for development (developability) was measured.

Determination of solubility ○・−・・−・Dissolution rate is fast.

X--1.- Does not dissolve or dissolves extremely slowly.

B1 Next, the material obtained in the [Solubility and Developability] section was heated and cured in a hot air dryer at 150° C. for 130 minutes, and the following tests were conducted using each of the obtained specimens.

[Solder resistance]

The state of the coating film was determined after the specimen was immersed in molten solder at 260° C. for 30 seconds three times.

○−−−−−・−−−−No abnormality in the appearance of the coating film.

×・・−−−−−Blistering, melting, and peeling.

[Adhesion]

The coating film of the specimen before and after the solder resistance test was cut with 100 goblets of 1×1 mm in size and peeled off with cellophane tape, and then the adhesion was evaluated.

[Insulating resistance]

The specimen was left in an atmosphere of 80° C. and 195% RH for 240 hours, and the insulation resistance of the coating film was measured.

*■Epoxy acrylate EPPN-201 (manufactured by Nippon Kayaku Co., Ltd., phenol novolac type epoxy resin) is reacted with 0.5 chemical equivalent of acrylic acid per 1 chemical equivalent of epoxy group, and diluted with 30% butyl cellosolve acetate. thing.

*EPPN-201: Phenol novolac type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.).

*■KAYARAD DP)IA Manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol penta and hexaacrylate.

*KAYACtJRE DETX: manufactured by Bhonkayaku Co., Ltd., photopolymerization initiator, 2,4-diethylthioxanthone.

*■ IRGACURE 907 manufactured by Ciba Geigy, photopolymerization initiator, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone [Effects of the invention] Unsaturated group-containing polycarboxylic acid resin of the present invention The composition using the compound can be developed with an alkaline aqueous solution and has excellent developability, and the cured product thereof has good heat resistance, solvent resistance, adhesion, and electrical insulation, and is suitable for a solder resist resin composition.

Claims (1)

[Claims] 1. An unsaturated group-containing polyurethane obtained by further reacting a reaction product of tris(2,3-epoxypropyl)isocyanurate and (meth)acrylic acid with a polybasic carboxylic acid or its anhydride. Carboxylic acid resin. 2. A resin composition containing the unsaturated group-containing polycarboxylic acid resin according to claim 1. 3. A solder resist resin composition containing the unsaturated group-containing polycarboxylic acid resin according to claim 1. 4. A cured product of the unsaturated group-containing polycarboxylic acid resin according to claim 1. 5. A cured product of the resin composition according to claim 2 or 3.