JPH06157965A - Liquid resist ink composition and printed circuit board - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a specific UV light- curable resin, excellent in resolution, solvent resistance, electric characteristics, etc., extremely good in heat resistance, capable of forming a good pattern even in a low UV light exposure, and capable of being developed with a dilute alkali aqueous solution. CONSTITUTION:The objective composition contains (A) a UV light-curable resin produced by reacting an (un)saturated polybasic acid anhydride (e.g. maleic anhydride) with the reactional product of a compound of the formula (R is the residue of an organic compound having K¦¦X¦¦ active hydrogen atoms; n1-nk are 0-50, their sum being 1-50) with an unsaturated monocarboxylic acid (preferably acrylic acid), (B) a photopolymerization initiator (e.g. benzoin), (C) a diluent (e.g. 2-hydroxyethyl acrylate), and (D) a thermally curable epoxy compound (e.g. bisphenol A epoxy resin). The compound of the formula is produced e.g. by the ring-opening polymerization of 4-vinylcyclohexene-1-oxide in the presence of a triol such as glycerol, methanol, propanol, etc., as a polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid resist ink composition which is suitable for producing a printed wiring board and which can be developed with a dilute aqueous alkaline solution, and a printed circuit board using the same.

[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, in recent years, the wiring density of printed wiring boards has increased, and strict dimensional accuracy has been required for pattern formation. Therefore, the resolution is low, and ink bleeding during printing and ink filling between lines are difficult. The screen printing method, which is prone to defects, cannot support the recent increase in density. Therefore, in order to solve such a problem, a dry film or a liquid developable resist ink has been developed, and among them, ones that can be developed with a dilute alkaline aqueous solution are attracting attention.

As such a liquid resist ink composition, JP-B-56-40329 and JP-B-57-457.
Japanese Patent Publication No. 85 discloses a composition containing a reaction product obtained by reacting an epoxy resin with an unsaturated monocarboxylic acid and adding a polybasic acid anhydride as an essential component (hereinafter referred to as "acid anhydride addition type"). "Epoxy acrylate"). Also,
Japanese Patent Application Laid-Open No. 61-243869 discloses a weak alkali developing type containing a thermosetting component consisting of an acid anhydride addition type epoxy acrylate derived from a novolac type epoxy resin, a photopolymerization initiator, a diluent and an epoxy compound. A photosensitive resin composition for a liquid resist ink is disclosed.

However, the acid anhydride-added type epoxy acrylate used in the above liquid resist ink composition has aromaticity and is easily colored by heating, so that it has insufficient heat resistance and light resistance. The current situation is that a sufficiently high molecular weight has not been obtained.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to have good resolution and solvent resistance, excellent electrical properties such as plating resistance and galvanic corrosion resistance, flexibility and substrate adhesion. In particular, it is intended to provide a photosensitive resin composition for a dilute alkali developable liquid resist ink, which has extremely good heat resistance and can form a good pattern even by exposure with a low light amount, and a printed circuit board using the same. is there.

[0006]

A liquid resist ink composition developable with a dilute aqueous alkali solution according to the present invention comprises: The following general formula (I)

[0007]

[Chemical 3]

[Wherein R is an organic compound residue having k active hydrogens, n ₁ , n ₂ ... N _k is 0 or 1 to 5]
It is an integer of 0 and the sum is 1 to 50. In addition, the following functional groups in the formula

[0009]

[Chemical 4]

[0010]

(However, R'represents a hydrogen atom, an alkyl group, an alkylcarbonyl group or an arylcarbonyl group)
May be replaced with ] An ultraviolet curable resin obtained by reacting a saturated or unsaturated polybasic acid anhydride with a reaction product of a compound represented by and an unsaturated monocarboxylic acid,

B. A photopolymerization initiator, C.I. Diluent and D.I. It is characterized by containing a thermosetting epoxy compound.

The present invention will be described in detail below. <A. About UV-Curable Resin> As described above, the UV-curable resin is obtained by reacting a reaction product of the compound represented by the general formula (I) with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride. Although it can be obtained by
An isocyanate compound having at least two isocyanate groups in the molecule, such as isophorone diisocyanate, may be reacted together with the saturated or unsaturated polybasic acid anhydride.

The alicyclic epoxy compound represented by the general formula (I) used in the present invention can be synthesized by a known method. For example, in the general formula (I), k = 3
Ring-opening polymerization of 4-vinylcyclohexene-1-oxide with triols such as glycerin and trimethylolpropane, and k = 1 with methanol, ethanol, propanol, butanol, etc. as initiators. It is obtained by

In the preparation of the liquid resist ink composition according to the present invention, particularly high film strength is obtained when k ≧ 2 in the general formula (I) is used, and k =
When the compound of No. 1 is used, the adhesion to the printed board is particularly good.

Examples of unsaturated monocarboxylic acids include:
Acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and the like can be mentioned, but acrylic acid is particularly preferable.

Examples of the isocyanate compound include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate and toluidine. Examples thereof include diisocyanate, lysine diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, triphenylmethane triisocyanate and polymethylene polyphenyl polyisocyanate, but especially isophorone diisocyanate, hydrogenated xylylene diisocyanate. Isocyanates, tolylene diisocyanates and xylylene diisocyanates And the like, and among them, those having no aromatic ring, such as isophorone diisocyanate and hydrogenated xylylene diisocyanate, are the most suitable because there are few problems of coloring at high temperature.

Further, as the saturated or unsaturated polybasic acid anhydride, for example, maleic anhydride, succinic anhydride,
Dibasic acid anhydrides such as itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride, and trimellitic anhydride, anhydrous An acid anhydride having three or more basic acids such as pyromellitic acid, benzophenone tetracarboxylic acid anhydride, and methylcyclohexene tetracarboxylic acid anhydride can be mentioned.

The method for producing the ultraviolet curable resin will be described in detail. For example, the compound represented by the general formula (I) is dissolved in an organic solvent such as carbitol acetate, cellosolve acetate and methyl ethyl ketone to prepare hydroquinone and hydroquinone monomethyl ether. Such as a thermal polymerization inhibitor, tertiary amines such as benzyldimethylamine and triethylamine, quaternary ammonium salts such as trimethylbenzylammonium chloride and methyltriethylammonium chloride, or a catalyst such as triphenylstibine. Then, the unsaturated monocarboxylic acid such as acrylic acid is preferably about 0.7 to 1.3 chemical equivalents, and particularly preferably about 0.9 to 1.1 chemical equivalents per one chemical equivalent of the epoxy group. By a conventional method, the ratio is preferably 60 to 50 ° C., particularly preferably 80 to
The reaction is carried out at a reaction temperature of 120 ° C. to obtain a first reaction product composed of epoxy acrylate. Subsequently, the first reaction product is reacted with an acid anhydride in a ratio of 0.99 to 0.10 chemical equivalent of acid anhydride to 1 chemical equivalent of hydroxyl group in the first reaction product. At this time, as the acid anhydride, at least one kind is selected from the saturated or unsaturated polybasic acid anhydrides, and they are reacted by heating and stirring at a reaction temperature of 70 to 120 ° C. by a conventional method to obtain the required UV curability. Get the resin.

When an isocyanate compound such as isophorone diisocyanate is used for synthesizing an ultraviolet-curable resin, first, the above-mentioned first reaction product is obtained, and then the isocyanate compound is mixed with 1 chemical equivalent of the former secondary hydroxyl group. With respect to the isocyanate group is preferably 0.01 to 0.90 chemical equivalent, particularly preferably the isocyanate group 0.05 to
With a ratio of 0.40 chemical equivalent, by a conventional method, an organotin compound such as dibutyltin dilaurate or a tertiary amine such as benzyldimethylamine was added as a catalyst or a catalyst compounded in the above reaction with or without a tertiary amine, 20-100 ° C
The second reaction product is obtained by reacting at a reaction temperature of 1 by heating and stirring. The reaction amount of the isocyanate group with respect to 1 chemical equivalent of the hydroxyl group in the first reaction product was 0.90.
If it is more than the chemical equivalent, the solubility of the ultraviolet curable resin in the diluent tends to be poor, and in particular 0.05 to 0.40.
The best use properties are obtained in the stoichiometric range.

Subsequently, an acid anhydride is added to the second reaction product, and the acid anhydride is added in an amount of 0.99 to 0.10 chemical equivalent to 1 chemical equivalent of the hydroxyl group in the first reaction product. React in a ratio. At this time, as the acid anhydride, at least one kind is selected from the above-mentioned saturated or unsaturated polybasic acid anhydrides and reacted by a conventional method, preferably by heating and stirring at 70 to 120 ° C. to obtain an ultraviolet curable resin.

When the UV-curable resin is partially crosslinked with an isocyanate compound as described above, it can be made into a non-tacky solid at room temperature, so that excellent film characteristics can be obtained after pre-cure and pattern formation Contact exposure is easily possible, and the molecular weight of the ultraviolet curable resin is high, so that it is possible to obtain a resist ink composition that enables good pattern formation even with low light exposure.

The UV-curable resin is not limited to the above-mentioned synthetic examples, and can be synthesized by various ordinary synthetic methods. For example, the compound represented by the general formula (I) may be a compound such as acrylic acid or the like. It can also be synthesized by reacting a saturated monocarboxylic acid to form an epoxy acrylate, first reacting with an acid anhydride, and then reacting with an isocyanate compound or the like.

The acid value of the obtained ultraviolet curable resin is 30.
It is preferably about 160 mgKOH / g. If the acid value is less than 30, the solubility in an alkali developing solution will be poor, and if it is more than 160, it will be a factor that deteriorates the properties such as chemical resistance of the cured resist film.

The UV-curable resin is prepared by the same method as the UV-curable resin according to the present invention from a known epoxy acrylate to which a polybasic acid anhydride is added and an epoxy compound other than a hydrogenated epoxy compound. The derived ultraviolet curable resin can also be used in combination.

<B. Photopolymerization Initiator> Examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoins and their alkyl ethers, and acetophenone and 2,2-dimethoxy-2.
-Phenylacetophenone, 2,2-diethoxy-2-
Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl]-
Acetophenones such as 2-morpholino-propan-1-one, and anthraquinones such as 2-methylanthraquinone and 2-amylanthraquinone, and 2,4
-Dimethylthioxanthone, 2,4-diethylthioxanthone, thioxanthones such as 2-chlorothioxanthone and 2,4-diisopropylthioxanthone, and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, and benzophenones such as benzophenone or xanthones, And Lucillin TP
O (2,4,6-trimethylbenzoyldiphenylphosphine oxide manufactured by BASF) and the like can be mentioned, and these may be used in combination with a known photopolymerization accelerator such as a benzoic acid type or a tertiary amine type. These photopolymerization initiators are preferably added in an amount of 0.1 to 30 parts by weight, particularly preferably 1 to 25 parts by weight, based on 100 parts by weight of the ultraviolet curable resin.

<C. About diluent> As a diluent,
A photopolymerizable monomer and / or an organic solvent can be used. As the photopolymerizable monomer, for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, N-vinylpyrrolidone, acryloylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate,
Polyethylene glycol diacrylate, N, N-dimethyl acrylamide, N-methylol acrylamide,
N, N-dimethylaminopropyl acrylamide, N,
Water-soluble monomers such as N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate and melamine acrylate, or each methacrylate corresponding to the acrylate, and diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tri Propylene glycol diacrylate, phenoxyethyl acrylate tetrahydrofurfuryl acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate,
Pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isobonyl acrylate, cyclopentanyl (mono or di) acrylate, cyclopentenyl (mono or di) acrylate, or corresponding acrylate Water-insoluble monomers such as mono-, di-, tri- or higher polyesters of each of the methacrylates and polybasic acids and hydroxyalkyl (meth) acrylates, and polyester acrylates, urethane acrylates,
Epoxy acrylates such as bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate and cresol novolac type epoxy acrylate (These epoxy acrylates are partially crosslinked with a compound having at least two isocyanate groups in the molecule or a polybasic acid anhydride). May be used), high molecular weight acrylate monomers such as polyester acrylate and urethane acrylate, and the like. The water-soluble monomer, water-insoluble monomer, high molecular weight acrylate monomer and the like can be used alone or in combination with each other as appropriate.

Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone,
And aromatic hydrocarbons such as toluene and xylene; cellosolves such as cellosolve and butyl cellosolve; carbitols such as carbitol and butyl carbitol; and ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate and butyl carbitol. Acetates such as acetate and propylene glycol monomethyl ether acetate may be mentioned.

The photopolymerizable monomers such as the water-soluble monomer, the water-insoluble monomer and the high molecular weight acrylate monomer are used to dilute the UV-curable resin to make it easy to apply and adjust the acid value to improve the photopolymerizability. give. When a water-soluble monomer is used alone or in combination with a water-insoluble monomer or a high molecular weight acrylate monomer, the solubility in an alkaline aqueous solution is improved when the mixing ratio of the water-soluble monomer is increased. Since the water resistance of the completely cured resist film is lowered, it may be added in an amount of 100% by weight or less with respect to the ultraviolet curable resin, to the extent that the resist film is hardly soluble in an alkaline aqueous solution. In addition, the organic solvent dissolves and dilutes the ultraviolet curable resin so that it can be applied as a liquid and dried to form a film.

Although depending on the coating method, the diluent is preferably used alone or as a mixture of two or more kinds in the range of 10 to 95% by weight based on the total amount of the liquid resist ink composition.

<D. About thermosetting epoxy compounds>
Examples of the thermosetting epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, or alicyclic ring. Formula epoxy resin, triglycidyl isocyanurate, "Y
X-4000 ”(epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) and the like having two or more epoxy groups in one molecule can be mentioned. These are preferably mixed in an amount of 10 to 150 parts by weight, particularly preferably 30 to 100 parts by weight, based on 100 parts by weight of the ultraviolet curable resin.

The liquid resist ink composition prepared by blending the above components A to D, if necessary, may include an imidazole derivative, a polyamine, a guanamine, and a tertiary amine.
Epoxy resin curing agents and curing accelerators such as quaternary ammonium salts, polyphenols and polybasic acid anhydrides, and fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, phthalocyanine blue, phthalocyanine green, Coloring pigments such as titanium oxide and carbon black, and various additives such as defoaming agents, adhesion promoters or leveling agents, dispersion stabilizers, or hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butyl catechol and phenothiazine. The polymerization inhibitor and the like may be added.

The liquid resist ink composition according to the present invention is prepared by kneading the respective components and additives together with, for example, a three-roll mill, a ball mill, a sand mill or the like. As a method of using it, for example, after applying the composition to a printed wiring board by spraying, a roll coater, screen printing or the like, precure is performed at 70 to 90 ° C. to volatilize the solvent, and then draw a pattern. A dry mask with or without contact with a dry ink surface, chemical lamp, low pressure mercury lamp,
It is possible to form a pattern by irradiating with ultraviolet rays using a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like to develop a pattern, and then heat to form a desired resist film. Further, this composition can be used not only as a solder resist but also as an etching resist by not applying post-curing by heat.

[0034]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Reference Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. All "parts" and "%" used below are based on weight.

Synthesis Example 1 The following general formula (II)

[0036]

[Chemical 5]

(However, in the formula, n ₁ , n ₂ , and n ₃ are 1 to 1
It is an integer of 0 and the sum is 10-20. ) EHPE-3150 (Epoxy resin manufactured by Daicel Chemical Co., Ltd., epoxy equivalent 185) 185 parts dissolved by heating in 60 parts carbitol acetate, 74 parts acrylic acid, 0.1 part hydroquinone and benzyl under stirring Dimethylamine (0.7 part) was added, and the mixture was reacted at 90 to 100 ° C for 24 hours by a conventional method. After cooling the reaction solution, 65 parts of carbitol acetate, 53 parts of Swazol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) and 76 parts of tetrahydrophthalic anhydride were added, and the temperature was raised to 100 ° C. and about 3 with stirring. The reaction was carried out for a time to obtain an ultraviolet curable resin (A-1).

Synthesis Example 2 The following general formula (III)

[0039]

[Chemical 6]

(In the formula, n is an integer of 10 to 20) 172 parts of EHPE-1150 (Epoxy resin manufactured by Daicel Chemical Co., Ltd., epoxy equivalent 172) is dissolved in 60 parts of carbitol acetate by heating. While stirring, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine were added to the prepared mixture, and 90 parts were added by a conventional method.
The reaction was carried out at -100 ° C for 24 hours. After the reaction solution was cooled, 60 parts of carbitol acetate and 150 parts of SWAZOL
53 parts of 0 (Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) and 76 parts of tetrahydrophthalic anhydride were added, and the temperature was raised to 100 ° C. and the reaction was continued for about 3 hours under stirring to give an ultraviolet curable resin (A-2). Obtained.

[Synthesis Example 3] EHPE-used in Synthesis Example 1
3150 (Epoxy resin manufactured by Daicel Chemical Industries, epoxy equivalent 185) 185 parts dissolved in 60 parts carbitol acetate by heating were mixed with 74 parts acrylic acid, 0.1 part hydroquinone and benzyldimethylamine 1.4 while stirring.
Parts were added and reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction liquid, 60 parts of carbitol acetate, 63 parts of Swazol 1500 (an aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.), 5 parts of 2,4-tolylene diisocyanate and 0.1 part of dibutyltin dilaurate were added,
The reaction was carried out at 50 ° C. for 4 hours with stirring. Further, 76 parts of tetrahydrophthalic anhydride was added to the reaction product to obtain 10
The temperature was raised to 0 ° C. and the reaction was carried out for about 3 hours with stirring to obtain an ultraviolet curable resin (A-3).

[Synthesis Example 4] 172 parts of EHPE-1150 (Epoxy resin manufactured by Daicel Chemical Co., Ltd., epoxy equivalent 172) used in Synthesis Example 2 instead of EHPE-3150 (epoxy resin manufactured by Daicel Chemical Co., Ltd., epoxy equivalent 185) UV curable resin (A-4) was obtained in the same manner as in Synthesis Example 3 except that the blending amount of SWAZOL 1500 was changed to 56 parts.

Synthesis Example 5 Instead of 5 parts of 2,4-tolylene diisocyanate, isophorone diisocyanate 7 was used.
Parts, and except that the blending amount of Swazol 1500 was changed to 64 parts, an ultraviolet curable resin (A-5) was obtained by the same operation as in Synthesis Example 3.

[Synthesis Example 6] EHPE-used in Synthesis Example 1
3150 (Epoxy resin manufactured by Daicel Chemical Industries, epoxy equivalent 185) 90.5 parts and EHPE-used in Synthesis Example 2
86 parts of 1150 (Epoxy resin manufactured by Daicel Chemical Industries, epoxy equivalent 172) heated and dissolved in 60 parts of carbitol acetate, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine under stirring. In addition, the reaction was carried out at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, carbitol acetate 65
Parts, 50 parts of Swasol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) and 76 parts of tetrahydrophthalic anhydride are added, and the mixture is heated to 100 ° C. and reacted for about 3 hours under stirring to obtain an ultraviolet curable resin (A- 6) was obtained.

[Synthesis Example 7] 214 parts of Epicuron N-680 (cresol novolac epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 214) was dissolved by heating in 60 parts of carbitol acetate, and 74 parts of acrylic acid was stirred. Parts, 0.1 parts of hydroquinone and 0.7 parts of benzyldimethylamine were added, and the reaction was carried out at 90 to 100 ° C. for 24 hours by a conventional method. Swasol 1500 is added to this reaction solution.
(Aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) 94 parts was added and the mixture was stirred and cooled to obtain an epoxy acrylate (B-1).

[Reference Example 1] 212 parts of Epicron N-673 (cresol novolac resin manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 212) was added to carbitol acetate 6
What was heated and dissolved in 0 part, and acrylic acid 74 with stirring
Parts, 0.1 parts of hydroquinone and 0.7 parts of benzyldimethylamine were added and reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 65 parts of carbitol acetate, 70 parts of Swazol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) and 76 parts of tetrahydrophthalic anhydride were added, and the temperature was raised to 100 ° C. and stirred for about 3 hours. It was made to react below and the ultraviolet curable resin (C-1) was obtained.

Reference Example 2 178 parts of Epicoat 154 (Novolak epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent 178) dissolved in 63 parts of carbitol acetate by heating, 74 parts of acrylic acid and 0 parts of hydroquinone with stirring. 1 part and benzyl dimethylamine 0.7 part were added, and it was made to react by a conventional method at 90-100 degreeC for 24 hours. After cooling the reaction solution, 25 parts of carbitol acetate, 88 parts of Swazol 1500 (aromatic solvent manufactured by Maruzen Petrochemical Co., Ltd.) and 76 parts of tetrahydrophthalic anhydride were added, and the temperature was raised to 100 ° C. and stirred for about 3 hours. It was made to react below and the ultraviolet curable resin (C-2) was obtained.

[Examples 1 to 7 and Comparative Examples 1 and 2] The composition components shown in Table 1 below were kneaded with each composition by a three-stage roll, and a diluted alkali developing type liquid resist ink composition according to each example and comparative example. The thing was prepared.

[0049]

[Table 1]

[Test Results] The dilute alkali development type liquid resist ink compositions according to the above Examples and Comparative Examples were used to form a copper clad laminate made of a glass epoxy base material of copper foil 35 μ and a pattern obtained by previously etching the same. It is applied by screen printing on the entire surface of the printed wiring board on which the resin has been formed, and a precure is applied at 90 ° C. to evaporate the solvent.
After 0 minutes, a dry coating film having a thickness of 20 μm was obtained. Then, apply a patterned mask directly to the coating surface,
A pattern is formed by irradiating ultraviolet rays of mj and then developing with a 1% sodium carbonate aqueous solution as a developer.
Furthermore, it heat-cured for 30 minutes at 150 degreeC, and created the test piece. Table 2 shows the results of various physical property tests relating to the obtained test piece.

[0051]

[Table 2]

The evaluation method of the test results is as follows. ◎ ---- It is extremely excellent. ○ ---- Excellent. △ ---- Slightly inferior. × −−− Inferior.

[0053]

INDUSTRIAL APPLICABILITY As described above, the liquid resist ink composition according to the present invention has excellent resolution and solvent resistance, electrical characteristics such as plating resistance and electrolytic corrosion resistance, flexibility and a substrate. It has excellent adhesiveness and the like, and in particular has extremely good heat resistance and enables formation of a good pattern even with a low exposure amount. Further, particularly in the case of using an ultraviolet curable resin partially cross-linked with an isocyanate compound, excellent film properties can be obtained after precure and contact exposure of a pattern can be easily performed, and good pattern formation even in exposure with a low light amount. A resist ink composition that enables the above can be obtained.

Therefore, this liquid resist ink composition can be suitably used as a solder resist ink or an etching resist ink, particularly for the production of consumer or industrial printed wiring boards.

Claims (5)

[Claims] 1. A. The following general formula (I): [Wherein, R is an organic compound residue having k active hydrogens, n ₁ , n ₂ ... N _k are 0 or an integer of 1 to 50,
The sum is 1 to 50. In addition, the following functional groups in the formula: (However, R'represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group). ] An ultraviolet-curable resin obtained by reacting a reaction product of a compound represented by the above with an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, B. A photopolymerization initiator, C.I. Diluent and D.I. A liquid resist ink composition containing a thermosetting epoxy compound, which is developable with a dilute aqueous alkali solution. 2. As the component A, a reaction product of a compound represented by the general formula (I) and an unsaturated monocarboxylic acid, a compound having at least two isocyanate groups in the molecule, and a saturated or unsaturated polybasic acid. The liquid resist ink composition according to claim 1, which uses an ultraviolet curable resin obtained by reacting an anhydride. 3. Component C comprises epoxy acrylate as the high molecular weight acrylate monomer.
Alternatively, the liquid resist ink composition according to claim 2. 4. The liquid resist ink composition according to claim 3, wherein the epoxy acrylate is partially crosslinked with a compound having at least two isocyanate groups in the molecule or a polybasic acid anhydride. 5. A printed circuit board manufactured by using the liquid resist ink composition according to claim 1.