JPS63150315A - Resin composition and solder resist resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition suitable as a photographically developable solder resist excellent in heat resistance, chemical resistance and electrical insulation property, by mixing a polymer with a resin, a monomer, an initiator, a catalyst precursor and a solvent each specified. CONSTITUTION:A resin precursor prepared by mixing a poly(vinylphenol) (A1) and/or a vinylphenol/alkyl (meth)acrylate copolymer compound (A2) with an epoxy vinyl ester resin (B) obtained by reacting 1 chemical equivalent of a novolak epoxy resin with 0.1-0.7 chemical equivalent of (meth)acrylic acid, an unsaturated monomer (C), a photopolymerization initiator (D) and a radiation- sensitive catalyst precursor (E) which, upon irradiation with electron beams or ultraviolet rays, can decompose to give a Lewis acid effective in initiating the polymerization of the epoxy substance in the composition and an organic solvent (F). This composition can be cured by irradiation with ultraviolet rays and preferably subsequent heating to 50-200 deg.C.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is suitable for a photo-developable solder resist with excellent heat resistance, chemical resistance, and electrical insulation properties, which is used as a water-immersion protective film for printed wiring boards. The present invention relates to a resin composition.

(Prior Art) In recent years, ultraviolet curable compositions have been used for reasons such as resource saving, energy saving, improved workability, and improved productivity. In the field of printed wiring board processing, for similar reasons, inks such as solder resist inks and marking inks are shifting from conventional thermosetting compositions to ultraviolet curable compositions. Solder resist inks quickly transitioned to UV-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. The reality is that it has not yet been applied to the field of industrial substrates for computers, control equipment, etc. This is not required for solder resist inks used for industrial boards, but is not required for solder resist inks for consumer boards.
This is because high performance such as high electrical insulation, solder heat resistance under humid conditions, and plating resistance is required, and current solder resist inks for consumer boards do not reach the required performance level. With the recent miniaturization and increased functionality of electronic devices, there is a growing demand for improved accuracy in circuit pattern density even for industrial boards, and the conventional screen printing method using ultraviolet-curable solder resist ink has Satisfactory results have not been obtained due to limitations in printing accuracy. In addition, conventional ultraviolet curable solder resist inks contain mono- to trifunctional monomers such as 2-hydroxyethyl methacrylate and trimethylolpropane triacrylate, and various acrylate oligomers.
During screen printing, these substances ooze out, causing problems such as solder failure. Efforts have been made to improve the above-mentioned problems; 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. Although it has excellent heat resistance, adhesion, chemical resistance, and electrical insulation properties, it does not have storage stability because it uses an amine-based epoxy curing agent, and it has the disadvantage of having to be heated and cured at high temperatures. .

(Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted intensive research and found that the present invention has good storage stability, heat resistance and adhesive properties that can be heat-cured at relatively low temperatures. We have succeeded in providing a resin composition suitable for solder resists that have poor chemical resistance and electrical insulation properties.

That is, the present invention provides: (1) polyvinylphenol (AJ and/or a copolymer compound (A2) of vinylphenol and alkyl (meth)acrylate), 1 chemical equivalent of novolac type epoxy resin, and 0.1 of (meth)acrylic acid; Epoxy vinyl ester resin (BJ, unsaturated group-containing monomer (C), and photopolymerization initiator Q) obtained by reacting with ~0.7 chemical equivalent and decomposes when irradiated with an electron beam or ultraviolet rays. A resin composition comprising a radiation-sensitive catalyst precursor (D) and an organic solvent (F') which provide a Lewis acid effective for initiating polymerization of an epoxy-based material in the composition.

(2) Copolymer compound (A2) of polyvinylphenol (At and/or vinylphenol and alkyl (meth)acrylate, 1 chemical equivalent of novolak type epoxy resin, and 0.1 to 0.7 chemical equivalent of (meth)acrylic acid) The epoxy vinyl ester resin (B) obtained by reacting the unsaturated group-containing monomer (C) with the photopolymerization initiator The present invention relates to a solder resist resin composition comprising a radiation-sensitive catalyst precursor (E) that provides a Lewis acid effective for initiating polymerization of an epoxy material and an organic solvent (F').

Polyvinylphenol (At
) and the copolymer compound (A2) of vinylphenol and alkyl (meth)acrylate can be easily obtained from the market. For example, polyvinylphenol (manufactured by Marukubi Petrochemical ■, Resin M), p-vinylphenol methyl methacrylate and copolymer (manufactured by Marukubi Petrochemical ■,
Resin CM ht ), polybarabinyl brominated phenol (Resin BM, manufactured by Marukubi Petrochemical Co., Ltd.), and the like.

The epoxy vinyl ester resin used as component (B) is a novolac type epoxy resin, for example, a phenol novolac type epoxy resin (manufactured by Shell Chemical ■, Epikote 1
54, Dow Chemical (ceramic, DEN-438, Nippon Kayaku ■, EPPN-201, etc.), cresol novolac type epoxy resin (Nippon Kayaku ■, EOCN-104, etc.)
etc.) and (meth)acrylic acid (acrylic acid or methacrylic acid) in the presence of an esterification catalyst, usually 60 to 130
It can be obtained by reacting at a temperature of preferably 80 to 110°C. When extruding novolak type epoxy resin and (meth)acrylic acid, 0.1 of (meth)acrylic acid is used for 1 chemical proportion of novolak type epoxy resin.
-07 chemical equivalent, preferably O51-05 chemical equivalent. As the esterification catalyst, known catalysts such as triphenylstibine and methyltriethylammonium chloride can be used, and the amount used is 0.0% based on the weight of the reaction solution.
It is preferably used in an amount of 0.05 to 20%, particularly preferably 0.1 to 5%.

By the way, when preparing the epoxy vinyl ester resin, it is preferable to add a polymerization inhibitor, and such polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6 -1-butyl phenol, α-nitrone-β-naphthol, p-benzoquinone, naphthoquinone, phenothiazine, N-nitron phenyl amine, copper salts, etc. are mentioned. Its usage is
It is usually 0.01 to 1% by weight based on the reaction mixture.

The reaction can also be carried out in an organic solvent which is inert under the reaction conditions and which also acts as a viscosity reducing agent.

Examples of these organic solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters fm such as ethyl cellosolve acetate, butyl cellosolve acetate, ethyl acetate, and butyl acetate, 1,4-dioxane, and tetrahydrofuran. Ethers, glycol derivatives such as Cellosolve and Ochilselonlube, aromatic hydrocarbons such as toluene and xylene,
There are a number of suitable solvents including petroleum based solvents such as petroleum ether, petroleum naphtha and the like.

These organic solvents can be used as the (F''ll component) in the composition of the present invention.Specific examples of unsaturated group-containing monomers used as the (Q component) include, for example, 2-hydroxy Ethyl (meth)acrylate, carpitol (
meth)acrylate, phenoxyethyl (meth)acrylate, neopentyl hydroxypivalate glycol di(meth)acrylate, dioxane glycol di(meth)acrylate (manufactured by Nippon Kayaku ■, KAYARAD n
-604, etc.), trimethylolpropane tri(meth)acrylate, trimethylolpropane polypropoxy triacrylate, trimethylolpropane polyethoxy triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like.

Particularly preferred (q component includes dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane polypropoxy triacrylate).

As the photopolymerization initiator (D+, any known photopolymerization initiator can be used, but one with good storage stability after blending is preferable. As such a photopolymerization initiator,
For example, benzoin ethyl ether, benzoin alkyl ether of benzoin butyl ether, 2
, 2-jetoxyacetophenone, 4-7 enoxy 2
．． Acetophenone such as 2-dichloroacetophenone, 2-hydroxy-2-methylglopiophenone, 4-
Propiophenones such as isopropyl-2-hydroxy-2-methylglopiophenone; anthraquinones such as benzyl dimethyl ketal, 1-hydroxycyclo-\xylphenyl ketone; and 2-ethylanthraquinone and 2-chloroanthraquinone; Examples include thioxanthone photopolymerization initiators such as -chlorothioxanthone and 2,4-diethylthioxanthone. These photopolymerization initiators (D) can be used alone or in a mixture of two or more in any ratio. Preferred photopolymerization initiators (D) include 2-ethylanthraquinone and 2,4-diethylthioxanthone.

Radiation-sensitive catalyst precursors (as El, diallyliodonium salts, e.g. phenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, 4-chlorophenyliodonium f
Toy fluoroborate, di(4-methoxyphenyl)
Iodonium chloride, (4-methylphenyl) phenyl iodonium, etc., triallylsulfonium salts, e.g.
Triphenyl sulfonium tetrafluoroborate, triphenyl sulfonium hexafluorophosphate, p-(phenylthio)phenyldiphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroatimonate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate etc., triallylselenium salts, e.g., triphenylselenium hexafluorophosphate, triphenylselenium hexafluoroantimonate, etc., and (2,
Examples include 4-cyclopentadien-1-yl)[(1-methylethyl)-benzene]-iron-hexafluorophosphate (CG24-61, manufactured by Chipa Geigy). Preferred precursors (El as triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, (2,
Examples include 4-cyclopentadien-1-yl)[(l-methylethyl)-benzene]-iron-hexafluorophosphate.

As organic solvent CF) it is possible to use a large number of the solvents mentioned above. Preferred organic solvents include butyl selon lupus acetate, ethyl cellosolve acetate, petroleum ether, and the like.

Further, the above-mentioned solvents may be used alone or as a mixture of two or more. In addition, the concentration of these organic solvents is not particularly limited, but from the viewpoint of workability it should be 10 to 5.
0% by weight is preferred.

Prisoner used in the composition of the present invention (Bl, fc)
,■l, (The amount of El used is (In the composition excluding the P component, the amount of the prisoner component is preferably 2 to 30% by weight to 20% by weight, and the amount of the Bl component is is 95-40% by weight
Particularly preferred is 90 to 50% by weight. (C) The amount of component is
It is preferably 0.5 to 30% by weight, particularly 1 to 20% by weight. (To) The amount of ingredients is 0.5-10%, especially 1
It is preferably 5% by weight.

(The amount of the El component is preferably 0.1 to 5% by weight, particularly 0.5 to 3% by weight.

The resin composition of the present invention may contain various additives, such as extender pigments such as Merck, silica, alumina, barium sulfate magnesium oxide, thixotropic agents such as Aerosil,
Silicone, fluorine-based leveling agents, antifoaming agents, coloring agents, etc. may be added.

The composition of the present invention is particularly useful as a solder resist resin composition, but it can also be used as a coating agent for metals such as copper, tinplate, and aluminum.

The composition of the present invention is cured by irradiation with ultraviolet rays in a conventional manner, followed by heating preferably to 50 to 150°C, particularly preferably 70 to 100°C.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. Note that parts in the examples are parts by weight.

Epoxy vinyl ester resin (Synthesis Example 1 of Synthesis B: Phenol novolac type epoxy resin rEPPN-201 with epoxy equivalent weight 187, softening point 65°C) (manufactured by Nippon Kayaku ■, 1870 parts of epoxy resin (10 equivalents of epoxy group) ), 432 parts of acrylic acid (equivalent to 6 carboxyl groups), 1.15 parts of hydroquinone, 716.5 parts of triphenyl stipi, and 579.9 parts of butyl cellosolve acetate were added, and the temperature was raised to 90°C =! By continuing the reaction for 13 hours, acid value 1, epoxy "Nt57"
An epoxy vinyl ester tree IIW (B-1) containing 20% of butyl cellosolve acetate of No. 9 was obtained.

Synthesis Example 2 Cresol novolak type epoxy resin r EOCN-102 with epoxy equivalent weight 214, softening point 65°C (manufactured by Nippon Kayaku ■, epoxy resin) 2140 parts (equivalent to 10 equivalents of epoxy group), 144 parts acrylic acid ( (equivalent to 2 equivalents of carboxyl groups), 1.14 parts of hydroquinone, 16.4 parts of triphenyl stipine, and 575.4 parts of butyl cellosolve acetate were added, the temperature was raised to 90°C, and the reaction was continued for 7 hours to obtain an acid value of l. , epoxy equivalent weight 287.6
An epoxy vinyl ester resin (B-2) containing 20% butyl cellosolve acetate was obtained.

Synthesis Example 3, cresol novolac type epoxy resin r EOCN-104 with epoxy equivalent weight 220, softening point 900CJ (manufactured by Nippon Kayaku ■, epoxy resin) 2200 parts (epoxy group 10 equivalent proportion), acrylic acid 288 parts (carboxyl group 4 equivalents), 1.24 parts of hydroquinone, 17.9 parts of triphenyl stipine, and 626.8 parts of butyl cellosolve acetate were added, the temperature was raised to 90°C, and the reaction was continued for 10 hours to obtain an acid value of 1 and an epoxy equivalent. A resin (B-3) was obtained from epoxy vinyl ester 1 containing 20% of butylseron lupacetate of t417.5.

Examples 1 to 4 and Comparative Example 1.2 Holivinylphenol, copolymer of vinyl phenol and alkyl (meth)acrylate, epoxy vinyl ester resin, unsaturated group-containing monomer, photopolymerization initiator, radiation sensitivity A solder resist resin composition was mixed with a catalyst precursor, an amine curing agent, and an organic solvent according to the compounding ratios shown in Table 1, and a film thickness of 20 to 50 μm was formed on a copper through-hole printed wiring board by screen printing. After applying,
After drying the coating film at 70° C. for 30 minutes, a negative film is applied in direct contact with the coating film. Next, 5KW
@Using a high-pressure mercury lamp, ultraviolet rays were irradiated, and then the unirradiated parts of the coating were removed using an organic solvent such as trichlorethylene. Thereafter, heat curing was performed at a predetermined temperature for 30 minutes using a hot air dryer, and various performance tests were conducted on each of the obtained specimens. The results are shown in Table 1.

The various performance tests shown in the table were conducted as follows.

[Storage stability]

The formulation was left to stand at 60°C in a hot air dryer, and the number of days until it thickened or gelled was measured.

[M agent resistance]

After irradiating with ultraviolet rays using a 5KW, I high-pressure mercury lamp and removing the unirradiated areas with trichlene, the state of the film in the irradiated areas was evaluated. The criteria for this judgment are as follows.

○: No abnormality, X: Dissolution or swelling.

[Solder resistance]

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

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

×...Blistering, melting, peeling.

[Adhesion]

The coating film of the specimen was cut with 100 goblets with a size of I x l mm, and the adhesion after peeling off with cellophane tape was evaluated.

[Insulation resistance]

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

(Effects of the Invention) The composition of the present invention has a coating film whose surface after drying with a solvent is similar to that of a tank.
It is free, has good storage stability, can be heat-cured even at relatively low temperatures, has excellent heat resistance, solvent properties, adhesion and electrical insulation properties, and is suitable for solder resist (ffJ) resin compositions.

Claims (2)

[Claims] (1) Polyvinylphenol (A_1) and/or copolymer compound of vinylphenol and alkyl (meth)acrylate (A_2), 1 chemical equivalent of novolac type epoxy resin, and 0.1 to 0.7 chemical equivalent of (meth)acrylic acid Epoxy vinyl ester resin (B) obtained by reacting with an equivalent amount
, an unsaturated group-containing monomer (C), a photopolymerization initiator (D), and a Lewis acid that is effective to decompose upon irradiation with an electron beam or ultraviolet rays and to initiate polymerization of the epoxy substance in the composition. 1. A resin composition comprising a radiation-sensitive catalyst precursor (E) and an organic solvent (F). (2) Polyvinylphenol (A_1) and/or copolymer compound of vinylphenol and alkyl (meth)acrylate (A_2), 1 chemical equivalent of novolac type epoxy resin, and 0.1 to 0.7 chemical equivalent of (meth)acrylic acid Epoxy vinyl ester resin (B) obtained by reacting with an equivalent amount
, an unsaturated group-containing monomer (C), a photopolymerization initiator (D), and a Lewis acid that is effective to decompose upon irradiation with an electron beam or ultraviolet rays and to initiate polymerization of the epoxy substance in the composition. 1. A solder resist resin composition comprising a radiation-sensitive catalyst precursor (E) and an organic solvent (F).