JPH0519470A - Resist ink composition - Google Patents

Abstract

PURPOSE:To obtain the compsn. which yields an excellent cured coating film by using a specific epoxy resin and is suitable for production of printed circuit boards. CONSTITUTION:This liquid compsn. contains a UV curing resin obtd. by bringing unsatd. carboxylic acid of 0.8 to 1.2mol per 1 epoxy equiv. of the epoxy resin expressed by formula I into reaction, then bringing polybasic anhydride of 0.2 to 1.0mol per 1mol hydroxyl group of the resulted resin into reaction, a photopolymn. initiator, a diluent, and an epoxy compd. In the formula, n denotes 0 to 10. This compsn. can be developed by a thin aq. alkaline soln. after the compsn. is cured by UV rays. Further, the compsn. can be cured by heat as well. The initiator is exemplified by benzoin, benzoin methyl ether, etc. Photopolymerizable monomers and/or org. solvents are usable as the diluent. The thermosetting component consisting of the epoxy compd. having the epoxy group is exemplified by a bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel and useful resist ink composition, more specifically, solvent resistance,
The present invention relates to a liquid resist ink composition that can be developed with an alkaline aqueous solution and is suitable for producing a printed wiring board having excellent acid resistance.

[0002]

2. Description of the Related Art Conventionally, a screen printing method has been widely used as a resist pattern forming method for various consumer and industrial printed wiring boards. However, the screen printing method has a low resolution and causes ink bleeding during printing. In addition, defective filling of the ink between the lines occurs, which makes it impossible to cope with the recent high density. In order to solve these problems, dry film and liquid developable resist inks have been developed, and among them, those developable with an alkaline aqueous solution are attracting attention.

As such a liquid resist ink composition, Japanese Examined Patent Publication No. 56-40329 and Japanese Examined Patent Publication No. 57-45785.
The epoxy resin with unsaturated monocarboxylic acid,
Further, a composition containing a reaction product to which a polybasic acid anhydride is added as an essential component is shown. In addition, JP-A-61-24
No. 3869, a weak alkali containing a resin soluble in a dilute alkaline aqueous solution obtained by adding an acid anhydride to a novolac type epoxy acrylate, a photopolymerization initiator, a diluent, and a thermosetting component resin containing an epoxy compound. A photosensitive resin composition for a developable liquid resist ink is disclosed.
However, under the present circumstances, liquid resist inks are required to have better performance such as resolution and gold plating resistance, and development of those satisfying these performances is desired.

[0004]

The object of the present invention is that the resolution, adhesion, heat resistance, and gold plating resistance are particularly good, and the photocurability, thermosetting property, hardness, solvent resistance, and acid resistance are good. Etc., and can obtain a hardened coating film with various physical properties such as electrical characteristics. Especially, it can be developed with a dilute alkaline aqueous solution suitable for the production of consumer printed wiring boards and industrial printed wiring boards. Another object of the present invention is to provide a liquid resist ink composition.

[0005]

A liquid resist ink composition according to the present invention comprises (A)

[Chemical 2]

After reacting 0.8 to 1.2 mol of unsaturated carboxylic acid per 1 epoxy equivalent of the epoxy resin represented by the above structural formula [1], the resulting resin has a pH of 0. UV curable resin obtained by reacting 2 to 1.0 mol of polybasic acid anhydride (B) Photopolymerization initiator (C) Diluent and (D) Thermosetting component composed of epoxy compound having epoxy group A liquid resist ink composition developable with a dilute alkaline solution containing

The preferred range of the acid value of the ultraviolet curable resin (A) thus obtained is 45 to 160 mgKOH.
/ G is preferably 60 to 150 mg KOH / g.
If the acid value is less than 60, the alkali solubility will be poor, and on the other hand, if the acid value is excessively greater than 150, it will be a factor of deteriorating the properties of the cured film as a resist such as alkali resistance and electrical properties. Absent. Further, when the number of ethylenically unsaturated bonds present in one molecule of the ultraviolet curable resin (A) is small, the photocurability is slow, and therefore the characteristics of the cured film such as alkali resistance and electrical characteristics as a resist are reduced. This is also unfavorable because it causes a decrease. The ultraviolet curable resin (A) is a resin obtained by reacting 0.8 to 1.2 mol of acrylic acid or methacrylic acid per epoxy equivalent of the epoxy resin represented by the structural formula [1] by a conventional method. It is obtained by reacting 0.2 to 1.0 mol of a polybasic acid anhydride per 1 mol of the hydroxyl group.

Typical examples of the initiator (B) are benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; acetophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxy-2-phenylacetophenone,
1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-propan-1-one and other acetophenones; 2-methylanthraquinone, 2-amylanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-
Diethylthioxanthone, 2-chlorothioxanthone,
There are thioxanthones such as 2,4-diisopropylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone or xanthones. The photopolymerization initiator B is benzoic acid-based or tertiary It may be used in combination with one or more known photopolymerization accelerators such as amines. A suitable range of the amount of the photopolymerization initiator B used is 0.1 to 30 parts by weight, preferably 1 to 25 parts by weight, based on 100 parts by weight of the ultraviolet curable resin A.

Further, as the above-mentioned diluent (C), a photopolymerizable monomer and / or an organic solvent can be used. Typical examples of the photopolymerizable monomer are 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate,
Methoxy polyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethylacrylamide, N-methylolacrylamide, N, N
-Water-soluble monomers (C-1) such as dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, and each methacrylate corresponding to the above acrylate; and diethylene glycol di Acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, phenoxyethyl acrylate tetrahydrofurfuryl acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetra Acrylate, dipentaerythritol pentaacryle DOO, dipentaerythritol hexaacrylate, isobornyl acrylate, cyclopentadiene, mono- - or each methacrylates corresponding to Gee acrylate or the acrylate, the polybasic acid and hydroxyalkyl (meth) acrylate mono -,
There are water-insoluble monomers (C-2) such as di-, tri- or higher polyesters, and polyester acrylate, urethane acrylate, bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate, cresol novolac type epoxy acrylate, etc. High molecular weight acrylate monomer (C-3)
Also includes. On the other hand, as the organic solvent (C-4),
Ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, carbitols such as carbitol and butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate. , Butyl carbitol acetate, and other acetic acid esters. The above diluent (C) is used alone or as a mixture of two or more kinds. A suitable range of the amount used is 30 to 350 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the ultraviolet curable resin (A).
Here, the purpose of using the water-soluble monomer (C-1), the water-insoluble monomer (C-2) and the high molecular weight acrylate monomer (C-3) is to dilute the ultraviolet curable resin so that it can be easily applied. In addition to adjusting the acid value and imparting photopolymerizability, a water-soluble monomer (C-
When the compounding ratio of 1) is large, the solubility in an alkaline aqueous solution is good, but when it is used extremely excessively, the water resistance of the completely cured resist material is lost, so that the water-insoluble monomer (C-
The combination of 2) is an effective means. Further, a water-insoluble monomer (C-2) and a high molecular weight acrylate monomer (C-
If the combined amount of 3) is too large, it becomes insoluble in an alkaline aqueous solution.
It is desirable that the content be 00% by weight or less. Also, an organic solvent (C-4)
The purpose of use is to dissolve and dilute the ultraviolet curable resin A, apply it as a liquid thereby, and then dry it to form a film.

The thermosetting component (D) comprising an epoxy compound having an epoxy group is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, an N-glycidyl type epoxy resin or an alicyclic epoxy resin. There are epoxy compounds having two or more epoxy groups in one molecule.
The blending amount of the thermosetting component is the photocurable resin 100.
10 to 150 parts by weight, preferably 30 to 1 to parts by weight
It is 00 parts by weight. The photocurable liquid resist ink composition of the present invention thus obtained, if necessary, further dicyandiamide, imidazole-based, triazine-based known epoxy resin curing agent, barium sulfate, silicon oxide, talc, clay, Known conventional fillers such as calcium carbonate, phthalocyanine blue, phthalocyanine green, titanium oxide, known conventional pigments such as carbon black, various additives such as defoaming agents, adhesion promoters or leveling agents, Alternatively, known polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol, and phenothiazine may be added. The method of using the liquid resist ink composition of the present invention is, for example, 70 ° C. to 9 ° C. in order to volatilize the solvent after being applied to a printed wiring board by spraying, a roll coater or screen printing.
Precure was performed at 0 ° C., and then a patterned mask was applied to the dried ink surface to give 200 mj.
A target resist film can be formed by forming a pattern by irradiating ultraviolet rays of ˜1500 mj, developing the pattern, and then heating the pattern again. Further, not only can it be used as a solder resist, but it can also be used as an etching resist by not applying post-curing by heat. Suitable irradiation light sources for photocuring the composition of the present invention include chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps and metal halide lamps.

[0011]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples. All parts and% are based on weight unless otherwise specified.

Example 1

[Chemical 3] An epoxy acrylate was obtained by reacting 1 mol of acrylic acid with 1 epoxy equivalent of the epoxy resin represented by the structural formula [1] using diethylene glycol monoethyl ether acetate as a solvent. 0.5 mol of tetrahydrophthalic anhydride was reacted with 1 mol of hydroxyl groups of this epoxy acrylate until the acid value reached the theoretical value. This is a viscous liquid containing 30% by weight of diethylene glycol monoethyl ether acetate, 55 mgK as a mixture.
An acid value of OH / g was shown. Hereinafter, this is a resin (A-1)
Is abbreviated. After preparing the weak alkaline developing type liquid resist ink by kneading the above-mentioned components with a three-stage roll, a copper-clad laminate of glass epoxy base material of copper foil 35 μm and a copper-clad laminate of the same were pre-etched to form a pattern. It was applied by screen printing on the entire surface of the formed printed wiring board and precured at 90 ° C. for 20 minutes to volatilize the solvent to obtain a dry coating film with a film thickness of 20 μm, and then a mask with a pattern drawn on it. Was directly applied to the surface of the coating film, and a pattern was formed by irradiating with ultraviolet rays of 500 mj to develop.

[0012]

Example 2 The above compounding ingredients were used in the same manner as in Example 1. An ink was prepared by kneading in the same manner as described above, and similarly, the ink was used to form a copper-clad laminate of glass epoxy base material of copper foil 35 μm and the entire surface of a printed wiring board on which a pattern was formed by etching the same in advance. Example 1 was applied by a spray method. I made a test piece in the same way as.

[0013]

Comparative Example 1 Epicoat 154 (phenolic novolac type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd. with an epoxy equivalent of 178) 1 epoxy equivalent of 1.05 mol of acrylic acid was reacted with epoxy acrylate 0.8 mol of phthalic anhydride cellosolve The reaction was carried out by a conventional method using acetate as a solvent. This is a viscous liquid containing 30 parts by weight of cellosolve acetate, which is 8
An acid value of 5 mgKOH / g was shown. This resin was used in Example 2. Was prepared by substituting the resin (A-1) with the above composition. Then, in Example 1. In the same manner as in Example 1, a copper-clad laminate of 35 μm of copper foil and a copper-clad laminate and a printed wiring board on which a pattern was formed by etching this in advance were applied by screen printing to Example 1. Created a test piece in the same way as

The results of various physical property tests of the liquid resist ink compositions of Examples and Comparative Examples are shown in the following table.

[0015]

[Table 1]

[0016]

[Table 2]

[0017]

[Table 3]

[0018]

As described above, the liquid resist ink composition of the present invention has good resolution, heat resistance, adhesion and gold plating resistance, and also has photocurability, thermosetting property, hardness, solvent resistance,
A cured coating film having excellent properties such as acid resistance and various physical properties such as electrical properties and plating resistance can be obtained. Further, it can be easily developed with a dilute alkaline aqueous solution and has excellent resolution. Due to this effect, the liquid resist ink composition of the present invention is suitable as a solder resist ink, and particularly as an etching resist ink for producing a consumer printed wiring board, an industrial printed wiring board and the like.

[Procedure amendment]

[Submission date] February 28, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

[0011]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples. All parts and% are based on weight unless otherwise specified.

Example 1

## STR00003 ## An epoxy acrylate was obtained by reacting 1 mol of acrylic acid with 1 epoxy equivalent of the epoxy resin of the above structural formula [1] using diethylene glycol monoethyl ether acetate as a solvent. Tetrahydrophthalic anhydride was added to 1 mol of the hydroxyl group of this epoxy acrylate.
5 mol was reacted until the acid value reached the theoretical value. This is a viscous liquid containing 30% by weight of diethylene glycol monoethyl ether acetate, and the mixture is 5%.
An acid value of 5 mgKOH / g was shown. Hereinafter, this is abbreviated as resin (A-1). Resin (A-1) 40 parts Epicoat 154 (Oilized shell having an epoxy equivalent of 178, Phenolic nopolak type epoxy resin manufactured by Epoxy) 18 〃 Benzyl dimethyl ketal 3 〃 "Modaflow" (Leveling agent manufactured by Monsanto UK) 1 〃 Silica (Average particle size 1 μ) 25 〃 Phthalocyanine Green 0.5 〃 Swazol 1500 (manufactured by Maruzen Petrochemical Co., Ltd.) 12 〃 Dicyandiamide 0.5 〃 −−−−−−−−−−−−−−−−−−−−− ----------------------------- One compounding component Total 100 parts The above compounding components are kneaded with a three-stage roll to prepare a weak alkaline developing type liquid resist ink, and then this ink is A copper-clad laminate of 35 μm copper foil on a glass-epoxy substrate and a printed wiring board on which a pattern is formed by etching the same in advance. Coating by screen printing and precuring at 90 ° C. for 20 minutes to volatilize the solvent to obtain a dry coating film with a thickness of 20 μm. Then, a patterned mask is directly applied to the coating film surface, 500 mj Of UV light , and then a 1% aqueous solution of sodium carbonate is used as a developer.
And develop it to form a pattern,
Heat cure at 0 ° C for 30 minutes to form a test piece
It was

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location G03F 7/032 501 9019-2H 7/038 501 7124-2H H01L 21/027 H05K 3/00 F 6921 −4E // H05K 3/18 D 6736-4E 3/28 D 6736-4E (72) Inventor Toshikazu Oda 58 Ijiri, Iseta-cho, Uji-shi, Kyoto Prefecture

Claims (1)

Claims (Claim 1) (A) After reacting 0.8 to 1.2 mol of unsaturated carboxylic acid per 1 epoxy equivalent of the epoxy resin represented by the structural formula [1], 0.2 per mol of hydroxyl group of the resin obtained.
A thermosetting component composed of an ultraviolet curable resin (B) photopolymerization initiator (C) diluent and (D) an epoxy compound having an epoxy group, obtained by reacting 1 to 1.0 mol of a polybasic acid anhydride. A liquid resist ink composition developable with a dilute alkaline solution containing.