JPH0693221A - Liquid resist ink composition and printed circuit board - Google Patents

Abstract

(57) [Summary] [Structure] A. An ultraviolet-curable resin obtained by reacting a reaction product of an epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, B. A photopolymerization initiator, C.I. Diluent, D.I. Ammonia and / or amines, E. A thermosetting epoxy compound and F.I. An aqueous liquid resist ink composition containing water, which can be developed with a dilute alkaline aqueous solution. [Effect] While maintaining the resolution, solvent resistance, plating resistance, etc. of the conventional liquid resist ink, the above environmental problems,
It can contribute to the improvement of work environment problems and reduce the burden on manufacturing equipment, transportation and fire protection.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous liquid resist ink composition which can be developed with a dilute alkaline aqueous solution, and a printed wiring board manufactured 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. Among them, environmental problems,
From the standpoint of work environment problems, what can be developed with a dilute aqueous alkaline solution has been 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. Further, in JP-A-61-243869, a thermosetting component comprising 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 an epoxy compound is disclosed. Disclosed is a photosensitive resin composition for a liquid resist ink of dilute alkali development type, which contains.

However, these above-mentioned compositions themselves are so-called solvent-based ones, and by including an organic diluent, for example, an organic solvent or a diluent such as a diluting monomer,
It is necessary to adjust the fluidity of the composition so as to facilitate and uniformize the coating on the substrate.

Among the diluents, examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, and carbitol and butyl. Carbitols such as carbitol and acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate and butyl carbitol acetate are used. When using these organic solvents, by removing by drying after applying the composition to the substrate,
Since it becomes possible to impart sufficient hardness and strength to the coating film after drying, there is an advantage that the contact exposure of the pattern becomes easy. Therefore, a large amount of organic solvent was used in the conventional dilute alkaline developing type liquid resist ink composition, but in this case, due to environmental problems, work environment problems, and further problems such as flammability, it occurs during coating and drying. The treatment of organic solvent vapor requires careful attention to equipment and fire prevention.

Therefore, it is possible to solve these problems by making the coating system water-based by making the liquid resist ink water-based. However, although the above-mentioned aqueousization is progressing in thermosetting paints, ultraviolet curable printing inks, etc., it is still under development in the field of printed circuit manufacturing inks, and in particular, both ultraviolet curability and thermosetting are required. It is expected to develop a liquid resist ink that can be used practically.

[0007]

The object of the present invention contributes to the improvement of the above environmental problems and work environment problems while maintaining the resolution, solvent resistance, plating resistance and the like of conventional liquid resist inks. However, it is another object of the present invention to provide a dilute alkali developable aqueous photosensitive resin composition for a liquid resist ink, which can reduce the burden on manufacturing equipment, transportation and fire protection.

[0008]

The aqueous liquid resist ink composition developable with a dilute aqueous alkaline solution according to the present invention comprises: A reaction product of an epoxy resin and an unsaturated monocarboxylic acid is reacted with a saturated or unsaturated polybasic acid anhydride, or a reaction product of an epoxy resin and an unsaturated monocarboxylic acid has an isocyanate group such as isophorone diisocyanate in the molecule. A UV-curable resin obtained by reacting an isocyanate compound having at least two and a saturated or unsaturated polybasic acid anhydride with B. A photopolymerization initiator, C.I. Diluent, D.I. Ammonia and / or amines, E. A thermosetting epoxy compound and G. It is characterized by containing water.

Further, the printed circuit board according to the present invention is manufactured by using the aqueous liquid resist ink composition developable with the above dilute alkaline aqueous solution.

<A. UV curable resin> As described above, the UV curable resin is obtained by reacting a reaction product of an epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride or an epoxy resin and an unsaturated resin. It is obtained by reacting a reaction product with a monocarboxylic acid with an isocyanate compound having at least two isocyanate groups in the molecule, such as isophorone diisocyanate, and a saturated or unsaturated polybasic acid anhydride.

Examples of the epoxy resin include bisphenol F type epoxy resin, novolac type epoxy resin (phenol novolac type, cresol novolac type), bisphenol A novolac resin, cyclic aliphatic epoxy resin (for example, EHPE manufactured by Daicel Chemical Industries, Ltd.). -1
150 or 3150), tris (hydroxyphenyl) methane-based multifunctional epoxy resin (EPPN-501, 502 and 502H manufactured by Nippon Kayaku Co., Ltd., and Tactex-742 and XD-9053 manufactured by Dow Chemical Co.).
Etc.) and an epoxy resin corresponding to Epicoat 157 series manufactured by Yuka Shell Epoxy Co., a glycidyl ether type epoxy resin such as polybutadiene modified epoxy resin, etc.
Examples thereof include those having at least two epoxy groups. At least one kind of the epoxy resin may be selected and used.

As the unsaturated monocarboxylic acid, for example,
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 Etc. are preferred.

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, an epoxy resin is dissolved in an organic solvent such as carbitol acetate, cellosolve acetate and methyl ethyl ketone, and a thermal polymerization inhibitor such as hydroquinone and hydroquinone monomethyl ether, and Tertiary amines such as benzyldimethylamine and triethylamine, and tertiary amines such as trimethylbenzylammonium chloride and methyltriethylammonium chloride
An unsaturated monocarboxylic acid such as acrylic acid is preferably used in an amount of about 0.7 to 1.3 chemical equivalents relative to 1 chemical equivalent of the epoxy group, using a primary ammonium salt or a catalyst such as triphenylstibine. Particularly preferably about 0.9-
The ratio is 1.1 chemical equivalents, and is preferably 6 by a conventional method.
The reaction is carried out at a reaction temperature of 0 to 150 ° C., particularly preferably 80 to 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 selected from the saturated or unsaturated polybasic acid anhydride,
By a conventional method, the reaction is carried out by heating and stirring at a reaction temperature of 70 to 120 ° C. to obtain the required UV curable 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.

Then, 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 one 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 they are reacted by heating and stirring at 70 to 120 ° C. by a conventional method to obtain an ultraviolet curable resin.

When the ultraviolet curable resin is partially cross-linked with an isocyanate compound as described above, the high molecular weight makes it possible to obtain excellent film characteristics after precure and to easily carry out contact exposure of a pattern. Further, the ultraviolet curable resin having a high molecular weight can be cured in a low light amount.

The UV-curable resin is not limited to the above-mentioned synthetic examples, and can be synthesized by various conventional synthetic methods. For example, epoxy resin is reacted with unsaturated monocarboxylic acid such as acrylic acid. After making epoxy acrylate,
It is also possible to synthesize by first reacting an acid anhydride and then reacting 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.

<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 may be used either individually or in combination with each other, but the total amount thereof is preferably 0.1 to 30 parts by weight, particularly preferably 1 part by weight, relative to 100 parts by weight of the ultraviolet curable resin. -25 parts by weight are blended.

<C. About diluent> As a diluent,
A photopolymerizable monomer and / or an organic solvent can be used. Examples of the photopolymerizable monomer include 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-dimethylaminopropylacrylamide,
N, N-dimethylaminoethyl acrylate, N, N-
Water-soluble monomers such as dimethylaminopropyl acrylate and melamine acrylate, or methacrylates corresponding to the above acrylates, and diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, phenoxyethyl acrylate, tetrahydrofuran Furyl acrylate, cyclohexyl acrylate, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, isobornyl acrylate, cyclopentanyl (mono or ) Acrylate, cyclopentenyl (mono or di) acrylate, or each methacrylate corresponding to the acrylate and a non-polyester such as a mono-, di-, tri- or higher polyester of hydroxyalkyl (meth) acrylate with a polybasic acid. Water-soluble monomer,
And epoxy acrylates such as polyester acrylate, urethane acrylate, bisphenol A type epoxy acrylate, phenol novolac type epoxy acrylate and cresol novolac type epoxy acrylate (these epoxy acrylates are compounds having at least two isocyanate groups in the molecule or polybasic acid anhydride). (May be partially crosslinked with a polymer), and high molecular weight acrylate monomers such as polyester acrylate and urethane acrylate. 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 ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol,
Linear, branched, secondary or polyhydric alcohols such as ethylene glycol, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, and cellosolves such as cellosolve and butyl cellosolve, and carbi. Examples thereof include carbitols such as tol and butyl carbitol, and acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate and butyl carbitol acetate, and propylene glycol monomethyl ether acetate.

Photopolymerizable monomers such as the water-soluble monomers, water-insoluble monomers and high molecular weight acrylate monomers are prepared by diluting the UV-curable resin to make it easy to apply and adjusting 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.

The above-mentioned diluent may be added 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 photosensitive resin composition, although it depends on the coating method.

<D. Ammonia and / or amines> As ammonia and / or amines, in addition to ammonia, for example, alkylamines such as trimethylamine, triethylamine and tributylamine, and the following general formula (I)

[0027]

Embedded image R ³ R ² N—R ¹ —OH (I)

(Wherein R ¹ is a divalent hydrocarbon residue, R ¹ is
² and R ³ each represent a monovalent alkyl group or a hydroxyl group-containing alkyl group. ) Compounds represented by, for example, 2-dimethylaminoethanol, diethylaminoethanol, dibutylaminoethanol, dimethylaminopropanols, alkanolamines such as methyldiethanolamine, ethyldiethanolamine, dimethylaminomethylpropanol, and morpholine, piperidine, piperazine, etc. Heterocyclic amines and the like can be mentioned. Suitable amines include those capable of imparting large water solubility and water dispersibility to ultraviolet curable resins and diluents having an acid value, such as alkanolamines, and those having an appropriate boiling point, that is, precure. It is desirable that it has a high volatility and does not cause the epoxy to harden under the conditions during pre-cure.

These ammonia and amines may be used alone or in combination with each other as appropriate, and the total amount thereof is 0.3 to 1.3 with respect to the total amount of carboxyl groups present in the composition of the present invention. The chemical equivalent is preferable, and a particularly preferable range is 0.5 to 1.1 chemical equivalent. When the amount used is less than 0.3 chemical equivalent, the resin becomes poor in water solubility and water dispersibility, and 1.
When it is more than 3 chemical equivalents, the developability is deteriorated due to curing of the epoxy during precure.

<E. Thermosetting Epoxy Compound> Examples of the thermosetting epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin and alicyclic compounds. Epoxy resin (eg Daicel Chemical Co. EH
PE-3150), "YX-4000" (epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.), hydrogenated bisphenol A type epoxy resin, triglycidyl isocyanurate and the like, but especially triglycidyl isocyanurate, Y
X-4000, cresol novolac type epoxy resin and the like are desirable. These epoxy resins are preferably added or the like to be emulsified or dispersed. As the additive, there are known and commonly used emulsifiers, dispersants and the like, for example, nonionic surfactants and ionic surfactants, for example, epoxy resin emulsifiers ADEKANOL NK-511 and NK-961S.
(Manufactured by Asahi Denka Co., Ltd.) and the like.

As a method for adjusting these, usually, a method in which an epoxy resin and an aqueous phase containing an additive are combined and stirred at high speed, and an epoxy resin is dropped or gradually added to the phase of the additive and water which are stirred at high speed. There is a method, or a method in which water is added little by little to the mixed phase of the epoxy resin and the additive. At this time, a diluent, that is, a photopolymerizable monomer and / or an organic solvent may be used.

<F. The blending amount of water> water varies depending on which coating method is used, for example, a dipping method, a spray, a spin coater, a roll coater or screen printing, but is in the range of 4 to 95% by weight relative to the total amount of the resist ink composition. It is preferable to blend in.

The photosensitive resin composition according to the present invention may further contain, if necessary, an imidazole derivative, polyamines, guanamines, tertiary amines, quaternary ammonium salts, polyphenols and polybasic acid anhydrides. Adhesive properties such as epoxy resin curing agents and curing accelerators, etc., and fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, pigments or dyes as colorants, defoaming agents, silane coupling agents, etc. Various additives such as an imparting agent, a leveling agent and an antihalation agent, or a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol and phenothiazine, and a surfactant for improving dispersion stability. A polymer dispersant or the like may be added.

The photosensitive resin 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. Also,
For example, first, each of the above-mentioned A to C or A to D, E and F or each of the compounding components of E, F and C, if necessary, is added with an additive and the like and previously emulsified or dispersed before use. Sometimes, a method of mixing and preparing so as to finally obtain the liquid resist ink composition of the present invention may be adopted.

The photosensitive resin composition according to the present invention can be used, for example, by dipping on a glass substrate, spraying,
After coating with a spin coater, a roll coater, screen printing, or the like, heating and drying are performed, for example, at 60 to 120 ° C. to volatilize water and an organic solvent that is a diluent,
Then, a patterned mask is applied to the dried coating surface with or without contact, a chemical lamp,
Low-pressure mercury lamp, medium-pressure mercury lamp, high-pressure mercury lamp, super-high pressure mercury lamp,
A desired resist film can be formed by forming a pattern by irradiating with ultraviolet rays using a xenon lamp or a metal halide lamp and then developing to form a pattern, and then by heating. 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. Further, these compositions can be used for forming a color filter protective film and for preparing a color filter element by adding an appropriate pigment or dye as a colorant.

[0036]

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] 212 parts of Epiclon N-673 (cresol novolac resin, Dainippon Ink and Chemicals, Inc., epoxy equivalent 212) dissolved in 60 parts of carbitol acetate by heating were added to 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 and 76 parts of tetrahydrophthalic anhydride were used.
Then, 70 parts of butyl cellosolve was added and stirred to obtain an ultraviolet curable resin (A-1).

Synthesis Example 2 The following general formula (II)

[0039]

[Chemical 3]

Epoxy resin represented by (manufactured by Nippon Kayaku Co.,
EPPN-502H, epoxy equivalent 166) To 166 parts of carbitol acetate heated and dissolved in 166 parts,
While stirring, 74 parts of acrylic acid, 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine were added and reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 50 parts of carbitol acetate and 76 parts of tetrahydrophthalic anhydride were added, the temperature was raised to 100 ° C., and the reaction was continued for about 3 hours with stirring. Then, futyl cellosolve 60 was added.
Parts were added and stirred to obtain an ultraviolet curable resin (A-2).

Synthesis Example 3 The following general formula (III)

[0042]

[Chemical 4]

(However, n ₁ , n ₂ , and n ₃ are integers of 1 to 10, and the sum thereof is 10 to 20.) Epoxy resin (EHPE-3150 manufactured by Daicel Chemical Co., Ltd., epoxy equivalent 185) ) 185 parts of 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 the reaction was carried out at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 65 parts of carbitol acetate and 76 parts of tetrahydrophthalic anhydride were added, the temperature was raised to 100 ° C., and the reaction was continued for about 3 hours under stirring. Then, 55 parts of butyl cellosolve was added and stirred, and UV curing was carried out. Resin (A-3) was obtained.

[Synthesis Example 4] 212 parts of Epicuron N-673 (cresol novolac resin manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent 212) was dissolved in 60 parts of carbitol acetate by heating, and 74 parts of acrylic acid was added with stirring.
Part, hydroquinone 0.1 part and benzyldimethylamine 1.4 part were added and reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 60 parts of carbitol acetate, 5 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added, and the mixture was heated to 50 ° C.
And reacted for 4 hours under stirring. Further, 76 parts of tetrahydrophthalic anhydride was added to this reaction product, the temperature was raised to 100 ° C., and the reaction was carried out under stirring for about 3 hours. Then, 77 parts of butyl cellosolve was added and stirred to obtain an ultraviolet curable resin (A
-4) was obtained. [Synthesis example 5]

Epoxy resin represented by the general formula (II) (manufactured by Nippon Kayaku Co., EPPN-502H, epoxy equivalent 1
66) To a solution prepared by heating and dissolving 166 parts of carbitol acetate in 60 parts, 74 parts of acrylic acid, 0.1 part of hydroquinone and 1.4 parts of benzyldimethylamine were added with stirring, and the mixture was stirred at 90 to 100 ° C. for 24 hours. It was made to react by the method. After cooling this reaction liquid, 60 parts of carbitol acetate, 5 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added, and the reaction was carried out at 50 ° C. for 4 hours with stirring. Further, 76 parts of tetrahydrophthalic anhydride was added to this reaction product, the temperature was raised to 100 ° C., and the reaction was carried out with stirring for about 3 hours, and then butyl cellosolve 5 was added.
3 parts were added and stirred to obtain an ultraviolet curable resin (A-5).

[Synthesis Example 6] 185 parts of the compound represented by the general formula (III) (EHPE-3150, manufactured by Daicel Chemical Industries Ltd., epoxy equivalent 185) was added to carbitol acetate 6
What was heated and dissolved in 0 part, and acrylic acid 74 with stirring
Part, hydroquinone 0.1 part and benzyldimethylamine 1.4 part were added and reacted at 90 to 100 ° C. for 24 hours by a conventional method. After cooling the reaction solution, 60 parts of carbitol acetate, 5 parts of isophorone diisocyanate and 0.1 part of dibutyltin dilaurate were added, and the mixture was heated to 50 ° C.
And reacted for 4 hours under stirring. Further, 76 parts of tetrahydrophthalic anhydride was added to this reaction product, and the mixture was heated to 100 ° C. and reacted for about 3 hours under stirring, and then 63 parts of butyl cellosolve was added and stirred to obtain an ultraviolet curable resin (A-
6) was obtained.

[Reference Example 1] 214 parts of Epicuron N-680 (cresol novolac epoxy resin, epoxy equivalent 214, manufactured by Dainippon Ink and Chemicals, Inc.) was dissolved in 60 parts of carbitol acetate by heating, and 74 parts of acrylic acid was stirred. , 0.1 part of hydroquinone and 0.7 part of benzyldimethylamine were added, and 90-100 by a conventional method.
The reaction was performed at 24 ° C. for 24 hours. Carbitol acetate (60 parts) and butyl cellosolve (35 parts) were added to the reaction solution, and the mixture was stirred and cooled to obtain epoxy acrylate (B-1).

[Examples 1 to 16 and Comparative Examples 1 to 2] The compounding ingredients of the respective compositions shown in Tables 1 and 2 below were kneaded by a three-stage roll to obtain the diluted alkali developing type of each Example and Comparative Example. A liquid resist ink of was prepared.

[0049]

[Table 1]

[0050]

[Table 2]

[Test Results] The dilute alkali development type liquid resist inks of the above-mentioned Examples and Comparative Examples were respectively applied to copper foil 3
A copper clad laminate made of 5μ glass epoxy base material and a printed wiring board which has been pre-etched to form a pattern on the entire surface of the printed wiring board by screen printing and pre-cured at 80 ° C. to volatilize water and solvent. Was performed for 20 minutes to obtain a dry coating film having a film thickness of 20 μm. After that, apply a mask with a pattern directly to the surface of the coating film, 300 mj
The sample was irradiated with the ultraviolet rays of No. 1 and then developed by using a 1% aqueous solution of sodium carbonate as a developing solution to form a pattern, which was further heat-cured at 150 ° C. for 30 minutes to prepare a test piece.

Tables 3 and 4 show the results of various physical property tests on the obtained test piece. These tables show that the test pieces according to the examples of the present invention have excellent performance for all test items.

[0053]

[Table 3]

[0054]

[Table 4]

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

[0056]

As described above, the water-based liquid resist ink composition according to the present invention retains the resolution, solvent resistance, plating resistance and the like of the conventional liquid resist ink, Contributing to the improvement of work environment problems, manufacturing equipment,
The burden on transportation and fire protection can be reduced.

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

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Claims (5)

[Claims] 1. A. An ultraviolet-curable resin obtained by reacting a reaction product of an epoxy resin and an unsaturated monocarboxylic acid with a saturated or unsaturated polybasic acid anhydride, B. A photopolymerization initiator, C.I. Diluent, D.I. Ammonia and / or amines, E. A thermosetting epoxy compound and F. A water-based liquid resist ink composition containing water, which can be developed with a dilute alkaline aqueous solution. 2. A. An ultraviolet-curable resin obtained by reacting a reaction product of an epoxy resin and an unsaturated monocarboxylic acid with an isocyanate compound having at least two isocyanate groups in the molecule and a saturated or unsaturated polybasic acid anhydride, B. A photopolymerization initiator, C.I. Diluent, D.I. Ammonia and / or amines, E. A thermosetting epoxy compound and F. A water-based liquid resist ink composition containing water, which can be developed with a dilute alkaline aqueous solution. 3. A component D is represented by the following general formula (I): embedded image R ³ R ² N—R ¹ —OH (I) (wherein R ¹ is a divalent hydrocarbon residue, R ^2. The aqueous liquid resist ink composition according to claim 1 or ² , wherein each of R ² and R ³ represents a monovalent alkyl group or a hydroxyl group-containing alkyl group. 4. The aqueous liquid resist ink composition according to claim 1, wherein the component D is 2-dimethylaminoethanol. 5. A printed circuit board manufactured using the aqueous liquid resist ink composition according to claim 1.