JPH02209912A - Unsaturated group-containing polycarboxylic resin, resin composition containing same and solder resist resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin excellent in resistance to heat and chemicals and electrical insulation, thus useful for the permanent protective film for printed wiring boards by reaction with a polybasic carboxylic acid (anhydride) of a reaction product of a tetraglycidyl ether and (meth)acrylic acid. CONSTITUTION:The objective resin can be obtained by reaction with (A) a polybasic carboxylic acid (e.g. maleic acid, phthalic acid) or its anhydride of (B) a reaction product of a tetraglycidyl ether of the formula and (meth)acrylic acid. The reaction ratio for the compound of the formula and the (meth)acrylic acid is pref. such as to be 0.9-1.1 chemical equivalent of the (meth)acrylic acid per chemical equivalent of the epoxy group in said compound of the formula.

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 a resin composition suitable for a solder resist having excellent electrical insulation properties.

(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. Solder resist inks quickly transitioned to ultraviolet curable compositions.

(Problems to be Solved by the Invention) However, the applications to which this ultraviolet curable composition is currently applied are limited to fields called consumer substrates used in radios, videos, televisions, etc. 1. The reality is that it has not yet been applied to the field of industrial boards such as controllers and control equipment. This is the solder resist ink used for industrial boards.
Solder resist inks for consumer boards -1/Cyst inks are required to have high performance such as high electrical insulation, solder heat resistance that can be washed under humidified conditions, and plating resistance, which are not required for current solder resist inks for consumer boards. This is because the performance level has not been reached. Due to the recent downsizing and increasing functionality of electronics equipment, there is a growing demand for improved precision in circuit pattern density even for industrial boards, and screen printing using conventional ultraviolet-curable solder resist ink has become more difficult. With this method, satisfactory results have not been obtained due to limitations in printing accuracy.

In addition, conventional ultraviolet curable solder-resist ink is
Contains mono- to trifunctional monomers such as -hydroxyethyl methacrylate, l-rimethylolbroban triacrylate, and various acrylate oligomers, and these substances ooze out during screen printing.・
・There are some problems such as not being able to print properly. Efforts have been made to improve the above-mentioned problem 1-1. For example, in JP-A-60-208377, a resin composition consisting of a photopolymerizable epoxy vinyl ester resin, a photopolymerization initiator, and an amine-based epoxy curing agent was proposed. It is heat resistant,
It has excellent adhesion, chemical resistance, and electrical insulation properties, but
Since it uses an amine-based epoxy curing agent, it has disadvantages such as poor storage stability (and the need to develop with an organic solvent).
-I am.

(Means for Solving the Problems) In order to solve the above-mentioned problems, the present inventors have conducted extensive research and found that the present inventors have good storage stability, can be developed with an alkaline aqueous solution, have heat resistance, and have good adhesion. The present invention has succeeded in providing a resin composition suitable for a fulder resist having excellent chemical resistance and electrical insulation properties◇ That is, the present invention has the following features: 1) Tetraglycidyl ether represented by formula (1) and (meth) An unsaturated group-containing polycarboxylic acid resin obtained by further reacting a reaction product with acrylic acid with a polybasic carboxylic acid or its anhydride; 2) a tetraglycidyl ether of the formula (1) and (meth)acrylic acid; The present invention relates to a resin composition, particularly a solder resist resin composition, characterized in that it contains an unsaturated group-containing polycarboxylic acid resin obtained by reacting the reactant of the above with a polybasic carboxylic acid or an anhydride thereof. here (meta)
Acrylic acid refers to acrylic acid or methacrylic acid or mixtures thereof.

The unsaturated group-containing polycarboxylic acid resin of the present invention is obtained by reacting the tetraglycidyl ether represented by formula (1) with (meth)acrylic acid to obtain epoxy (meth)acrylate. It can then be obtained by reacting a polybasic carboxylic acid or its anhydride. The tetraglycidyl ether represented by the formula (1) used in the present invention has various trade names, such as Epicote YL-93.
1. Mopon 1031. (Both oil-based shell epoxy
, trade name) etc., the present invention can be carried out using such commercial products.

The reaction with the tetraglycidyl nitrate (meth)acrylic acid represented by the formula (1) is carried out with respect to 1 chemical equivalent of the epoxy group of the tetraglycidyl ether represented by the formula (1).
The reaction is carried out at a ratio of about 0.8 to 1.5 chemical equivalents of meth)acrylic acid, particularly preferably about 0.9 to 1.1 chemical equivalents, and a diluent (for example, methyl ethyl ketone, methyl isobutyl ketone) is used in the reaction. , butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, benzene,
Solvents such as toluene and petroleum ether, or carpitol (meth)acrylate, phenoxyethyl (meth)acrylate, pentaerythritol tri(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, tris(hydroxyethyl)in It is preferable to use reactive monomers such as cyanurate tri(meth)acrylate, acryloylmorpholine, trimethylolpropane tri(meth)acrylate, dipentaerythritol poly(meth)acrylate, etc.), and to further accelerate the reaction. It is preferable to use a catalyst (for example, triethylamine, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, etc.), and the amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction mixture. is 1 to 5% by weight.

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 0% based on the reaction mixture.
．． 01-1% by weight, particularly preferably 0.05-0.5% by weight. The reaction temperature is 60-150°C 1%, preferably 80-120°C. Specific examples of polybasic carboxylic acids or their anhydrides include maleic acid, succinic acid,
Phthalic acid, tetrachlorophthalic acid, tetrabromophthalic acid, endomethylenetetrahydrophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid,
Examples include pyromellitic acid and anhydrides of these acids.

The reaction of the reaction product of the tetraglycidyl ether represented by the formula (1) obtained by the above method with (meth)acrylic acid and a polybasic carboxylic acid or its anhydride is (epoxy (
Esterification reaction of hydroxyl group in meth)acrylate) is
With respect to the hydroxyl groups in the reaction product of the tetraglycidyl ether represented by formula (1) and (meth)acrylic acid, 0.0 of the above acid or its anhydride per chemical equivalent of hydroxyl group.
5 to 1.00 chemical equivalents are reacted.

The acid value (rngKOH/g) of the product is preferably about 30 to 150. Reaction temperature is 60-150℃
, particularly preferably 80 to 120°C. The amount of the unsaturated group-containing polycarboxylic acid resin used in the composition of the present invention is preferably 10 to 100% by weight, particularly 20 to 90% by weight.

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

Methods for curing the composition of the present invention include curing methods using electron beams, ultraviolet rays, and heat, with ultraviolet rays and heat curing being preferred.

When curing with ultraviolet light, a photoinitiator is used.

As the photopolymerization initiator, any known photopolymerization initiator can be used, but it is desirable that the photopolymerization initiator has good storage stability after being blended.

Examples of such photopolymerization initiators include 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyl dimethyl ketal, 2-ethylanthraquinone, N,N-dimethylbenzoic acid isoamyl ester, N,N- -dimethylbenzoic acid ethyl ester, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and the like. These photopolymerization initiators can be used alone or in a mixture of two or more in any proportion. Preferred photoinitiators include:
Examples include 2.4-DIA/thioxanthone and 2-isopropylthioxanthone. The amount of photopolymerization initiator used is preferably 0.1 to 20% by weight, particularly 1 to 10% by weight of the composition.

When adding an epoxy group-containing compound to the composition of the present invention, diphenyliodonium-
・Nsafluorantimone), )'J Fueni, 5th,
'-'': It is preferable to use a photocationic polymerization catalyst such as nium hexafluorophosphate or triphnynylsulfonium hexafluoroantimosute. Commercially available products include, for example, 5P-150 and 5P-17 manufactured by Asahi Denka ■.
0, Irugaki Tamer 261 manufactured by Ciba Geigy ■, etc. The amount used is 0.01 to 1 of the composition.
．． Preferably it is 0% by weight, especially 0.02-0.2% by weight.

The resin composition of the present invention may further contain various additives, such as extender pigments such as Merck, silica, alumina, barium sulfate, and magnesium oxide, chicken tropic agents such as Aerosil, silicones, fluorine-based acrylic copolymers, etc. It is also possible to add a resetting agent, an antifoaming agent, a coloring agent, etc. Further, the above-mentioned solvents may be further added to facilitate handling of the composition.

The composition of the present invention is particularly useful as a solder resist resin composition, but can also be used as an insulating material, an impregnating material, a surface coating material, a paint, 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.

[Example of unsaturated group-containing polycarboxylic acid resin] Example 1
゜2100 parts of tetraglycidyl ether represented by the above formula (1) (manufactured by Yuka Shell Epoxy ■, Epon 1031, epoxy equivalent 210), 685 parts of acrylic acid, 1.4 parts of methylhydroquinone, 25 parts of triphenylstibine, and butyl cellosolve. Add 1407 parts of acetate and heat to 95℃
After raising the temperature to 90° C. and reacting for 30 hours, 472 parts of phthalic anhydride was added, and the mixture was reacted at 90° C. for 20 hours. A product with a viscosity of 6800 cps (25° C.) and an acid value (components excluding the solvent) of 56 mgKOH/g was obtained.

Example 2 Maleic anhydride 4 was used instead of phthalic anhydride in Example 1.
The reaction was carried out in the same manner as in Example 1 except that 1,407 parts and butyl cellosolve acetate) were changed to 1,398 parts, and the reaction was carried out in the same manner as in Example 1. The product was obtained.

Example 3 Example 1 except that 8.6 parts of tetrahydrophthalic anhydride 9 was used instead of phthalic anhydride in Example 1, and 1598.4 parts of butyl cellosolve acetate was used instead of 1407 parts.
The viscosity was 23100 cps (25
°C), acid value (components excluding solvent) 95 mgKOH
/g of product was obtained.

Example 4 Example 1 except that 1,104 parts of hexahydrophthalic anhydride and 1,407 parts of butyl cellosolve acetate were used instead of phthalic anhydride, and 2,610 parts of butyl cellosolve acetate were used instead of phthalic anhydride.
The viscosity was 11,000 cps (at 25°C).
), acid value (components excluding solvent) 107 mgKOH
/g of product was obtained.

Example 5 1950 parts of tetraglycidyl ether represented by the above formula (1) (manufactured by Yuka Shell Epoxy ■, Epicoat YL-931, epoxy equivalent: 195), 817 parts of methacrylic acid,
Methylhydroquinone to i, 2 parts of methyltriethylammonium chloride and 1393 parts of butyl cellosolve acetate were added, the temperature was raised to 95°C and the mixture was reacted for 3 parts, and then 470 parts of phthalic anhydride was added and 9 parts of phthalic anhydride was added.
The reaction was carried out at 0°C for 20 hours. Viscosity 7100cps (2
5℃), acid value (solvent component) 57 mgKO
A H/H product was obtained.

Application Example 6 ~] 0゜ A solder resist resin composition was blended according to the composition shown in Table 1, and the coating was applied to a copper through-hole printed wiring board with a film thickness of 20 to 100 μm using a screen printing method. After drying at 70'C for 60 minutes, a negative film is applied with or without direct contact with the coating. Next, it was irradiated with ultraviolet rays using a 5-meter ultra-high-pressure mercury lamp, and then the unirradiated portions of the coating film were dissolved and removed with an alkaline aqueous solution such as a 1.5% Na2COs aqueous solution. Thereafter, heat curing was performed at 150° C. for 30 minutes in a hot air dryer, and 6 performance tests were conducted on each of the obtained specimens. The results are shown in Table 1.

[Storage stability]

The resin composition was left at 30° C., and the number of days until it thickened or gelled was measured.

[Solubility]

Using a 5-item ultra-high pressure mercury lamp, irradiate with ultraviolet rays and then heat for 30 minutes.
The unirradiated portion was dissolved and removed with a 1.5% Naz CCh aqueous solution at 1.5° C., and the solubility was determined.

○...Dissolution rate is fast.

×: Does not dissolve or dissolves extremely slowly.

[Solder resistance]

The state of the coating film after being immersed in molten solder at 260° C. for 2 minutes was evaluated.

○...No abnormality in the appearance of the paint film.

×...Blistering, melting, peeling.

[Adhesion]

1xIII on the coating film of the specimen! 1 Goban of size m
The adhesion after peeling off with cellophane tape in 00 pieces was evaluated.

[Insulating resistance]

Leave it in an atmosphere of 80°C and 95% RH for 240 hours, The insulation resistance of the coating film was measured.

Yuzu epoxy acrylate: EPPN-201 (manufactured by Nippon Kayaku ■, phenol/novolac type epoxy resin) reacted with 0.5 chemical equivalent of acrylic acid per chemical equivalent of epoxy group, diluted with 30% butyl cellosolve acetate. .

Ao ■EPPN-201: Phenol/novolac type epoxy resin (manufactured by Nippon Kayaku ■) Material ■5P-170: Manufactured by Denka ■, photo cationic polymerization catalyst.

Q DETX: Manufactured by Nippon Kayaku ■, photopolymerization initiator, suitable for compositions.

Claims (1)

[Claims] 1) Formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) The reaction product of tetraglycidyl ether and (meth)acrylic acid is further reacted with a polybasic carboxylic acid or An unsaturated group-containing polycarboxylic acid resin made by reacting with the anhydride. 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.