JPH08225631A - Photosensitive resin and photosensitive resin composition containing the same - Google Patents

Abstract

PURPOSE: To obtain a photosensitive developable with water and excellent is various properties by reacting a specified alicyclic epoxy resin with an unsaturated monocarboxylic acid, a saturated monocarboxylic acid and a sulfide compound. CONSTITUTION: One equivalent (in terms of epoxy group) of an alicyclic epoxy resin (molecular weight of 500-300000) of formula I is reacted with X equivalent (0<X<=1) of an unsaturated monocarboxylic acid, (1-X) equivalent of saturated monocarboxylic acid and a equivalent (0<a<=1) of a sulfide compound of formula II (wherein R1 and R2 are each 1-8C alkyl or 1-8C alkenyl in which OH, alkoxy or an ester group may be substituted) to obtain a tert.-sulfonium-salt- containing photosensitive resin. A solder resist composition containing this photosensitive resin is excellent in photocurability and developable with water and can give a cured product excellent in soldering-heat resistance, resistance to nickel plating and electrical properties.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful photosensitive resin which can be developed with water, and a photosensitive resin composition containing the same, and particularly to a composition useful as a photo solder resist for printed wiring boards. It is about.

[0002]

2. Description of the Related Art Solder resists are used to prevent troubles when soldering components to printed wiring boards and to protect the circuit board after the components are mounted for a long period of time. With the miniaturization of printed circuit boards, the density of printed wiring boards and the surface mounting of components are increasing. In order to cope with such high density of the printed wiring board, the conventional screen printing type resist has been changed to the photo developing type. Even among the photo-developing type, it is especially good to improve the working environment,
From the viewpoint of environmental protection, the use of an alkaline aqueous solution for development has become the mainstream. Such an alkali development type photo solder resist is obtained by reacting a reaction product of a novolac type epoxy compound and an unsaturated monocarboxylic acid with Japanese Patent Publication No. 1-54390 and a saturated or unsaturated polybasic acid anhydride. A photocurable and thermosetting liquid resist ink composition comprising an active energy ray curable resin, a photopolymerization initiator, a diluent, and an epoxy compound is disclosed.
In this case, the characteristics as a solder resist can be satisfied, but when applying by a method such as spray coating or curtain coating, it must be diluted with a large amount of organic solvent, which causes problems such as environmental pollution and ignition. There is
Improvement is desired. JP-A-2-120308 and JP-A-6-157965 disclose a solder resist ink composition which is made from an alicyclic epoxy compound as a raw material and which can be developed in an alkaline aqueous solution. However, since all of these are developed with a dilute alkaline aqueous solution, not only the preparation of the developing solution and the control of the concentration are necessary, but also the neutralization is necessary to treat the tired developing solution. Furthermore, the alkaline ion component of the developing solution remains in the resist coating film, which may cause a problem in the electrical characteristics thereafter. Therefore, it was essential to provide a washing step after the developing step.

In order to solve such problems, some water diluting type and / or water developing type liquid photo solder resists have been proposed. For example, JP-A-4-29435
For 2, a photosensitive oligomer obtained by reacting an aromatic epoxy resin with an unsaturated monocarboxylic acid and then reacting an unsaturated polybasic acid anhydride with an amine to neutralize a reaction product with the amine, thermosetting A photosensitive aqueous resin composition comprising a compound, a photopolymerization initiator and a reactive diluent is disclosed in JP-A-4-2943.
Reference numeral 54 denotes a photosensitive oligomer obtained by neutralizing a reaction product of a copolymer of (meth) acrylic acid ester and (meth) acrylic acid and an epoxy group-containing (meth) acrylic acid ester with an amine, a photopolymerization initiator, and a reaction. A photosensitive water-based resin composition comprising a hydrophilic diluent is disclosed. These can be diluted with water, but a dilute alkaline aqueous solution is required for development, and the amine used for neutralization in the drying process to obtain a tack-free film volatilizes, and the developability during this process There is a problem in that the phenomenon of decreasing the temperature (heat fog) is likely to occur.

On the other hand, USP 3697398, 39364
No. 05, 3962165 discloses a cationic electrodeposition coating comprising an epoxy resin containing an onium compound such as a quaternary ammonium salt, a tertiary sulfonium salt and a quaternary phosphonium salt. Also, USP433823
2 discloses an epoxy resin derivative having a photosensitive group and a tertiary sulfonium salt, and an example in which a similar aromatic epoxy resin derivative is used for a photo-solder resist that can be diluted with water and developed with water is particularly preferable. It is disclosed in Kaihei 2-1858. Since such an aromatic epoxy resin usually reacts the phenolic hydroxyl group of the phenol novolac resin or the cresol novolac resin with epichlorohydrin under alkaline conditions, impurities such as sodium and chlorine remain in the product epoxy resin. Tended to. Photosolder resists used for printed wiring boards with advanced fine patterning today are required to have excellent heat resistance and plating resistance as well as high electrical characteristics. There was nothing satisfactory. Further, when the main component is an aromatic epoxy resin derivative, the absorption of active rays such as ultraviolet rays used in the exposure step is absorbed by the aromatic ring, so that the transmittance of active rays is poor and the energy is effective for photocuring. It was not used. Therefore, an exposure amount of about 300 mJ / cm ² or more is required for the photo solder resist.

[0005]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a water-dilutable, water-developable photosolder-resist composition having excellent properties as a solder-resist.

[0006]

[Means for Solving the Problems] The inventors of the present invention have diligently studied in order to solve the above-mentioned problems, and do not contain impurities such as sodium and chlorine, have excellent electric characteristics and heat resistance, and have a small absorption of active rays. The present invention has been completed by focusing on an alicyclic epoxy resin. That is, the present invention provides (A) (1) the following general formula 4

[Chemical 4] (However, n is a positive integer) With respect to 1 equivalent of the epoxy group of the alicyclic epoxy resin (molecular weight 500 to 300,000) having a structure represented by (a) unsaturated monocarboxylic acid x equivalent (0 < x ≦ 1), (b) saturated monocarboxylic acid (1-
x) equivalent weight and (c) the following general formula 5

Embedded image (In the formula, R ₁ and R ₂ represent a hydroxyl group, an alkoxy group, or an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 1 to 8 carbon atoms which may be substituted with an ester group.
₁ and R ₂ may be different or the same. )
An unsaturated monocarboxylic acid b to a photosensitive resin containing a tertiary sulfonium salt and / or (2) 1 equivalent of an epoxy group obtained by reacting an equivalent (0 <a ≦ 1) of a sulfide compound represented by Unsaturated and / or saturated monocarboxylic acid (1-b) equivalents to the residual epoxy groups of the compound obtained by reacting equivalents (0 <b <1) and the following general formula 6

[Chemical 6] (In the formula, R ₃ , R ₄ and R ₅ represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms, which may be substituted with a hydroxyl group, an alkoxy group, or an ester group.
R ₃ , R ₄ and R ₅ may be the same or different from each other. ) A tertiary amine compound (1
-B) a photosensitive resin containing a quaternary ammonium salt, which is obtained by reacting an equivalent amount (B) a photosolder resist composition containing a photopolymerization initiator as an essential component. Use is made of an epoxy resin having a structure represented by crosslinking modification with a polyisocyanate compound and / or a compound having at least two silanol groups or alkoxysilyl groups in some or all of the hydroxyl groups of the alicyclic epoxy resin. By doing so, various characteristics as a photo solder resist are greatly improved. Each component will be specifically described below.

In the composition of the present invention, the alicyclic epoxy resin having the structure represented by the general formula 4 as the starting material of the component (A) is prepared by using 4-vinylcyclohexene oxide as a suitable alcohol as an initiator. It is obtained by ring-opening polymerization by epoxidation and further epoxidation of the vinyl group of the side chain. EHPE-3150 from Daicel Chemical Industries, Ltd.
As commercially available.

Further, the above alicyclic epoxy resin and a compound having at least two isocyanate groups,
An epoxy resin obtained by reacting a value of (isocyanate equivalent) / (hydroxyl group equivalent of alicyclic epoxy resin) in a range of more than 0 and 1.0 or less is also a starting material of the component (A). Examples of the compound having at least two isocyanate groups include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and their trimers, methylene bisphenyl isocyanate, polymethylene polyphenyl polyisocyanate, and the like. The reaction is 40-100 in an organic solvent.
It can be carried out by a known method such as using a tertiary amine or an organic tin compound as a catalyst in the temperature range of ° C. Examples of the organic solvent include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and tetramethylbenzene, esters such as acetic acid esterified products of ethyl acetate and methyl cellosolve, glycol ethers such as methyl carbitol, octane and the like. Examples thereof include petroleum-based solvents such as aliphatic hydrocarbons, petroleum naphtha and solvent naphtha.

Furthermore, the value of (silanol group or alkoxysilyl group equivalent) / (hydroxyl group equivalent of alicyclic epoxy resin) is determined by comparing the alicyclic epoxy resin and the compound having at least two silanol groups or alkoxysilyl groups. The epoxy resin obtained by reacting the compound with the ratio of 1.0 or less can also be used as the starting material of the component (A). Examples of the compound having at least two silanol groups or alkoxysilyl groups include KR manufactured by Shin-Etsu Chemical Co., Ltd.
Examples thereof include silicone varnishes for modification such as 211 to 217, and SH6018 silicone resin intermediates manufactured by Toray Dow Corning Silicone Co., Ltd. The reaction is 120-
Using organic titanate compound as catalyst under heating at 180 ℃
Dehydration or dealcoholization condensation is performed for ~ 15 hours.

In order to introduce a polymerizable unsaturated group and a water-soluble tertiary sulfonium salt into the alicyclic epoxy resin as described above, 1 equivalent of epoxy group and x equivalent of unsaturated monocarboxylic acid (0 <X ≦ 1), saturated monocarboxylic acid (1-x)
An equivalent amount and an equivalent amount of the sulfide compound represented by the general formula 5 (0 <a ≦ 1) are reacted. It is possible to carry out the reaction simultaneously, or it is also possible to introduce an onium salt after first reacting an unsaturated or saturated carboxylic acid with a part of the epoxy group. The reaction is completed in 2 to 30 hours under heating at 50 to 85 ° C. Examples of the unsaturated monocarboxylic acid used include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylamide-N-glycolic acid and the like, with acrylic acid being particularly preferred. Of the monocarboxylic acids to be reacted with the epoxy groups of the alicyclic epoxy resin in an equivalent amount, the amount of the unsaturated monocarboxylic acid used is preferably in the range of 0.2 to 1 equivalent from the viewpoint of photocurability. As the saturated monocarboxylic acid which may be used in combination with the unsaturated monocarboxylic acid, known and conventional ones can be used, and examples thereof include acetic acid, formic acid, glycolic acid, lactic acid and propionic acid.

In order to introduce a polymerizable unsaturated group and a water-soluble quaternary ammonium salt into an alicyclic epoxy resin, b equivalent (0 <b <1) of unsaturated monoamine is added to 1 equivalent of epoxy group. Obtained by reacting the residual epoxy group of the compound obtained by reacting the carboxylic acid with the monocarboxylic acid (1-b) equivalent and the tertiary amine compound (1-b) equivalent represented by the general formula 6. . The introduction reaction of the onium salt is carried out after the reaction with the unsaturated monocarboxylic acid for the ease of reaction control. To react with unsaturated monocarboxylic acid in advance, a catalyst such as triphenylphosphine or dimethylbenzylamine is used at 80 to 120 ° C.
Under heating for 2 to 12 hours. As the unsaturated monocarboxylic acid to be used, acrylic acid is particularly preferable as described above. The onium salt introduction reaction can be carried out under the same conditions as in the case of the tertiary sulfonium salt.

The sulfide compound and the tertiary amine compound, which react with the monocarboxylic acid at the same time to form an onium salt structure, are not particularly limited as long as they do not substantially interfere with the onium chloride, and are represented by the general formula 5 And chemical formula 6. Where R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Is a C1-C8 alkyl group which may be substituted by a hydroxyl group, an alkoxy group, or an ester group, or a C1-C1 group.
8 represents an alkenyl group represented by R _1, R ₂ or R ₃ ,
R ₄ and R ₅ may be different or the same.
The optimum introduction rate of the onium salt for water-solubilizing the photosensitive resin is determined depending on the water solubility of the sulfide compound or the tertiary amine compound and the monocarboxylic acid used. Or 3
The reaction amount of the primary amine compound is not more than the epoxy group equivalent of the alicyclic epoxy resin, and generally, it is preferably in the range of 0.1 to 0.8 equivalent.

The reaction for synthesizing the photosensitive resin is preferably carried out in an organic solvent. Examples of the organic solvent include ketones such as methyl ethyl ketone, aromatic hydrocarbons such as toluene and tetramethylbenzene, glycol ethers such as methyl cellosolve, methyl carbitol, triethylene glycol monoethyl ether, ethyl acetate and the above glycol ethers. Examples thereof include esters such as acetic acid esterification products, alcohols such as ethylene glycol and propylene glycol, aliphatic hydrocarbons such as octane, and petroleum solvents such as petroleum naphtha and solvent naphtha. These solvents may be used alone or in admixture of two or more, and the preferred amount range is 5-4 with respect to 100 parts by weight of the photosensitive resin.
It is 00 parts by weight.

The photopolymerization initiator (B) used in the present invention includes benzoin, benzyl and benzoin methyl ether.
Benzoins and benzoin alkyl ethers such as ter 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-morphono-propan-1-one, acetophenones such as N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2
Anthraquinones such as -ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2- Chlorothioxanthone,
2,4-Diisopropylthioxanthone and other thioxanthones, acetophenone dimethyl ketal, benzyl dimethyl ketal and other ketals, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis There are benzophenones such as diethylaminobenzophenone and Michler's ketone, and xanthones, which can be used alone or in combination of two or more kinds. Further, such a photopolymerization initiator is ethyl-
Known or conventional photosensitizers such as benzoic acid esters such as 4-dimethylaminobenzoate and 2- (dimethylamino) ethylbenzoate, and tertiary amines such as triethylamine and triethanolamine, alone or in combination with 2 A combination of two or more species can be used.

The preferred range of the amount of the photopolymerization initiator used is 0.2 to 3 with respect to 100 parts by weight of the photosensitive resin (A).
It is 0 part by weight, preferably 2 to 20 parts by weight. If it is less than this range, the sensitivity tends to be poor. Further, a well-known and commonly used heat radical generator such as a peroxide such as benzoyl peroxide and an azo compound such as azobisisobutyronitrile may be used in combination.

In preparation of the solder resist ink of the present invention, a diluent may be used in addition to the above essential components.
As the diluent, an organic solvent and / or water and / or a photopolymerizable vinyl-based monomer can be used. Examples of the organic solvent include those used in the synthesis reaction, and examples of the photopolymerizable vinyl-based monomer include acrylamides, acrylates, and methacrylates. These reactive diluents, especially polyfunctional acrylates, are used for the purpose of improving the sensitivity of the solder resist ink composition. Such a diluent is used alone or as a mixture of two or more kinds, and the preferable range of the amount used is
5 to 250 relative to 100 parts by weight of the photosensitive resin (A)
Parts by weight.

A thermosetting resin may be added to the composition of the present invention for use. As the thermosetting resin, epoxy resin, melamine resin, blocked isocyanate and the like are used. The amount of these used is preferably 0 to 60% by weight of the composition, and at this time, these curing agents can be used in combination.

Further, in the present invention, known and commonly used additives may be added and used. For example, as an inorganic filler, known conventional materials such as barium sulfate, barium titanate, silicon oxide powder, finely powdered silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Can be used, and the mixing ratio is 0 to 100 of the resin composition.
%, Preferably 5 to 60% by weight. Further, if necessary, known conventional colorants such as phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, crystal violet, titanium oxide, carbon black and naphthalene black, hydroquinone, hydroquinone monomethyl. Ether, phenothiazine and other known thermal polymerization inhibitors, asbestos, orben, benton and other known thickeners, silicone-based, fluorine-based, polymer-based defoaming agents and / or leveling agents Known additives such as adhesion promoters such as imidazole-based, thiazole-based, triazole-based, and silane coupling agents can be used.

The solder resist composition of the present invention is a three-roll mill in which components (A) and (B) and, if necessary, additives such as a diluent, a thermosetting resin, a filler, a pigment and a thixotropic agent are added. It is prepared by thoroughly mixing with a suitable device such as a ball mill. Such a solder resist composition is applied to, for example, a circuit-formed printed wiring board,
Screen printing, Carter coater, Spin coater,
The coating film can be formed by a method of coating the entire surface with a spray or the like. After that, direct irradiation of laser light or through a photomask on which a pattern is formed is selectively exposed to actinic rays such as a high pressure mercury lamp and a metal halide lamp.
The unexposed portion can be developed with water to form a pattern. Since the photosensitive resin of the present invention has a low absorption of actinic rays and a high transmittance, the actinic rays such as ultraviolet rays have a wavelength of 50 to 200 m.
With J / cm ² and a relatively low exposure amount as a solder resist, sufficient photocuring is possible. Therefore, the exposure process is shortened and the productivity is improved. Then, after development, heat treatment at 100 to 200 ° C. and post-exposure as necessary are performed to obtain a permanent protective film satisfying various properties as a solder resist. Since water can be used as the developer, it is very effective in terms of management and environment as described above. Further, since the jig used for applying the resist ink can be washed with tap water, it is very preferable in the working environment.

The composition of the present invention is particularly useful as a solder resist composition, but can also be used as a plating resist, various insulating materials, surface coating agents, paints, adhesives and the like.

[0021]

EXAMPLES The present invention will be specifically described below with reference to production examples, examples and comparative examples, but the present invention is not limited thereto. In addition, "part" and "%" are
All are by weight unless otherwise noted.

[0022]

[Production Example 1] 178 parts of alicyclic epoxy resin EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., epoxy equivalent 178, hydrolyzable chlorine 1 ppm or less) was attached to a reactor equipped with a cooling pipe, a stirrer, and a thermometer. Methyl carbitol 1
15 parts was added and the mixture was heated and stirred at 90 ° C. to dissolve it. next,
Acrylic acid (57 parts), hydroquinone (0.1 parts) and dimethylbenzylamine (0.7 parts) were added, and the mixture was stirred and reacted at 110 ° C. for 4 hours to obtain an epoxy acrylate. Then, the mixture was cooled to 70 ° C., 18 parts of dimethylaminoethanol and 15 parts of acrylic acid were further added, and the mixture was heated and stirred for 12 hours to obtain 384 parts of a resin solution having a nonvolatile content of 70%.

[0023]

[Production Example 2] 100 parts of alicyclic epoxy resin EHPE-3150 (epoxy equivalent 178) and carbitol acetate 4 were placed in a reactor equipped with a cooling pipe, a stirrer and a thermometer.
6 parts was added and the mixture was heated and stirred at 90 ° C. to dissolve it. Next, the reaction temperature was lowered to 70 ° C., and 7 parts of 2,4-tolylene diisocyanate and 0.02 of dibutyltin dilaurate were added to this solution.
1 part was dropped and the mixture was heated and stirred for 3 hours to obtain 153 parts of an isocyanate-modified epoxy resin solution. Then, at the same temperature, 40 parts of acrylic acid, 0.1 part of hydroquinone, 24 parts of thiodiethanol, and 27 parts of methyl carbitol were added, and the mixture was heated and stirred for 24 hours to give a nonvolatile content of 70%.
244 parts of a resin solution of

[0024]

[Production Example 3] An alicyclic epoxy resin EHPE was attached to a reactor equipped with a cooling pipe, a stirring device, and an inert gas blowing device.
-3150 (epoxy equivalent 178) 100 parts, and modifying silicone varnish KR213 (manufactured by Shin-Etsu Chemical Co., Ltd., methoxy group equivalent 160) 15 parts were put, and the mixture was heated and stirred at 170 ° C. for 4 hours while passing nitrogen gas to volatilize. The incoming methanol was removed. Next, the temperature was lowered to 100 ° C., and 45 parts of carbitol acetate was added to obtain 157 parts of a silicone-modified epoxy resin solution. Then 28 parts of acrylic acid,
Hydroquinone 0.1 part, dimethylbenzylamine 0.
After adding 3 parts and stirring and reacting at 110 ° C. for 4 hours to obtain an epoxy acrylate, it was cooled to 70 ° C. and further 23 parts of acrylic acid 2- (N, N-dimethylamino) ethyl ester,
Acrylic acid (12 parts) and methyl carbitol (30 parts) were added, and the mixture was heated and stirred for 12 hours to obtain 250 parts of a resin solution having a nonvolatile content of 70%.

[0025]

[Comparative Production Example 1] A cresol novolac type epoxy resin (epoxy equivalent 224, hydrolyzable chlorine 120 ppm) 22 was attached to a reactor equipped with a cooling pipe, a stirrer and a thermometer.
4 parts and 170 parts of methyl carbitol were put and heated and stirred at 100 ° C. for dissolution. Next, 51 parts of acrylic acid, 0.1 part of hydroquinone, and 0.7 part of dimethylbenzylamine were added, and the mixture was stirred and reacted at 110 ° C. for 6 hours to obtain an epoxy acrylate. Then, the mixture was cooled to 70 ° C., 27 parts of dimethylaminoethanol and 18 parts of acetic acid were further added, and the mixture was heated and stirred for 12 hours to give a resin solution 4 having a nonvolatile content of 65%
91 parts were obtained.

[0026]

[Comparative Production Example 2] 224 parts of cresol novolac type epoxy resin (epoxy equivalent 224) and methyl carbitol 14 were placed in a reactor equipped with a cooling pipe, a stirrer and a thermometer.
8 parts was added, and the mixture was heated and stirred at 100 ° C. to dissolve it. next,
72 parts of acrylic acid, 0.1 parts of hydroquinone, and 50 parts of thiodiethanol were added at a reaction temperature of 70 ° C., and the mixture was heated and stirred for 24 hours to give a resin solution 49 having a nonvolatile content of 70% 49.
I got 4 parts.

[0027]

Example 1 45 parts of the resin solution obtained in Production Example 1 2-methyl-1- [4- (methylthio) phenyl] -2-morphopropan-1-one 3.2 parts Diethylthioxanthone 0.5 part Barium sulfate 18 parts Aerosil 1.2 parts Phthalocyanine lean 0.5 parts Silicone antifoaming agent 1 part After pre-kneading the above-mentioned compounding ingredients, kneading with a three-roll mill three times to prepare a solder resist composition. . This solder resist composition was applied on the entire surface of a printed circuit board in a thickness of 20 μm by a screen printing method to prepare a test piece.

[0028]

Example 2 Resin solution obtained in Production Example 2 45 parts SP-4060 (Novolak type epoxy acrylate manufactured by Showa Highpolymer Co., Ltd.) 5 parts 2-Methyl-1- [4- (methylthio) phenyl] -2 -Morphonopropan-one 3.2 parts Diethylthioxanthone 0.5 parts Barium sulfate 12 parts Silica 6 parts Aerosil 1.2 parts Phthalocyanine line 0.5 parts Silicone antifoam 1 part Kneading and coating were carried out in the same manner as in Example 1 to prepare a test piece.

[0029]

Example 3 Resin solution obtained in Production Example 3 45 parts Dipentaerythritol hexaacrylate 2 parts Cymel 303 (Methylated melamine manufactured by Mitsui Cyanamid Co., Ltd.) 5 parts 2-Methyl-1- [4- (methylthio) Phenyl] -2-morphopropan-1-one 3.2 parts Diethylthioxanthone 0.5 parts Barium sulfate 12 parts Talc 6 parts Aerosil 1.2 parts Phthalocyanine lean 0.5 parts Silicone antifoam 1 part Above The compounding ingredients were kneaded and coated in the same manner as in Example 1 to prepare a test piece.

[0030]

Comparative Example 1 Resin solution obtained in Comparative Production Example 1 50 parts 2-Methyl-1- [4- (methylthio) phenyl] -2-morphopropan-1-one 3.2 parts Diethylthioxanthone 0.5 Parts Barium sulfate 18 parts Aerosil 1.2 parts Phthalocyanine lean 0.5 parts Silicone antifoam 1 part The above compounding ingredients were kneaded and coated in the same manner as in Example 1 to prepare test pieces.

[0031]

Comparative Example 2 Resin solution obtained in Comparative Production Example 2 45 parts SP-4060 (Novolak type epoxy acrylate manufactured by Showa Highpolymer Co., Ltd.) 5 parts 2-Methyl-1- [4- (methylthio) phenyl]- 2-Morphonopropan-1-one 3.2 parts Diethylthioxanthone 0.5 parts Barium sulfate 12 parts Silica 6 parts Aerosil 1.2 parts Phthalocyanine line 0.5 parts Silicone antifoam 1 part Kneading and coating were carried out in the same manner as in Example 1 to prepare a test piece.

The resin solutions obtained in the above Production Examples 1 to 3 and Comparative Production Examples 1 and 2, and the above Example 2 and Comparative Example 2
The ultraviolet transmittance of the following 1) was measured for the resin composition obtained in 1.

1) Measurement of Ultraviolet Transmittance Each resin solution and resin composition was coated on a polyethylene terephthalate film so that the dry film thickness was 20 μm, and ultraviolet rays were irradiated from the film side using a metal halide lamp manufactured by Oak Manufacturing Co., Ltd. . The amount of transmitted ultraviolet rays is in the wavelength range of 320 to 390 nm (peak wavelength sensitivity 360
(nm) with an ultraviolet photometer, and the value was measured only for the film, and the transmittance was expressed in%.

The test pieces obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were evaluated in the following 2) to 9).

2) Finger touch dryness test Each test piece was put in a hot air drying oven, dried at 75 ° C. for 20 minutes, cooled to room temperature, and touched with a finger to determine the tack of the coating film and evaluate it. ○: No tack is observed at all △: Fingerprints remain slightly ×: Ink adheres to fingers

3) Photocuring test After the above drying process, a photomask having a pattern including 21 stuffer step guides was brought into contact with the surface of the coating film, and 150 ultraviolet rays were emitted through a metal halide lamp manufactured by Oak Manufacturing Co., Ltd. Irradiation was performed at 500 mJ / cm ² . Next, using water at 30 ° C. as a developing solution, development was carried out for 1 minute under a water pressure of ² kg / cm ² , and the sensitivity remaining in the exposed area was indicated by the number of steps.

4) Adhesion Test After the above-mentioned development process, the test piece was placed in a hot air drying oven heated to 150 ° C. for 30 minutes for post cure. The adhesion test is performed according to the test method of JIS D 0202.
Cross-cuts were put in a grid pattern, and then the number of peeled grid patterns after the peeling test with cellophane tape was observed. ◯; 100/100 Δ; 50/100 to 99/100 ×; 0/100 to 49/100

5) Pencil hardness test Each of the same test pieces as the adhesion test was JIS K 5
Hardness was measured according to the 400 test method.

6) Solder resistance test The same test pieces as in the adhesiveness test were respectively tested according to JIS C.
According to the test method of 6481, the number of times of dipping for 15 seconds in a solder bath at 260 ° C. was measured until the coating film had abnormalities such as chipping and swelling.

7) Nickel Plating Resistance Using the same test pieces as in the adhesion test, an electroless nickel plating solution ICP Nicoron manufactured by Okuno Seiyaku Kogyo was used.
The state of the coating film and the adhesion after plating for 30 minutes at a liquid temperature of 85 ° C. were comprehensively evaluated for evaluation. ◯: No change observed at all △: Slight change ×: Swelling or swelling loss in the coating film

8) Insulation resistance test Using the comb-shaped electrodes of the IPC-SM-840B B-25 test coupon, test pieces were prepared under the same conditions as in the adhesion test, and the insulation resistance after applying 100 V for 1 minute was measured. It was measured.

9) Electrolytic corrosion test Using the comb-shaped electrodes of the IPC-SM-840B B-25 test coupon, test pieces were prepared under the same conditions as in the adhesion test, and the temperature was 85 ° C. and the humidity was 85%. 1
The presence or absence of discoloration of the coating film after application of 00 V for 500 hours was observed.

The resin solutions obtained in the above Production Examples 1 to 3 and Comparative Production Examples 1 and 2, and the above Example 2 and Comparative Example 2
Table 1 shows the results obtained by measuring the ultraviolet transmittance of the resin composition obtained in 1.

[0044]

[Table 1]

It is clear from the table that the photosensitive resin and the resin composition of the present invention are excellent in ultraviolet transmittance. This is because the photosensitive resin mainly has an alicyclic structure, unlike the aromatic epoxy resin derivative as in the comparative example.
This is due to the low UV absorption. Than this,
The following advantages in photocurability are derived.

The test pieces obtained in Examples 1 and 3 and Comparative Example 1 were subjected to the respective tests 2) to 8) described above in Example 2
Table 2 shows the results of performing the tests 2) to 9) in Comparative Example 2.

[0047]

[Table 2]

It is apparent from the table that the solder resist composition of the present invention has excellent photocurability and cured product properties. Further, in the case of using the polyisocyanate or the silicone-modified alicyclic epoxy resin as in Examples 2 and 3, various physical properties were further improved. Since the solder resist composition of the present invention exhibits sufficient characteristics with a small exposure amount, it leads to shortening of the exposure step, that is, improvement of productivity. On the other hand, those using an aromatic epoxy resin as in Comparative Examples 1 and 2 are 150 mJ /
With an exposure amount of cm ² , the photo-curing property was not in the practical range of 3 steps, and the properties of the cured product were not satisfactory in solder resistance and nickel plating resistance. The electrical characteristics are inferior because they contain impurities such as sodium and chlorine, and this becomes a more serious problem as the density of printed wiring boards increases.

[0049]

As described above, when the solder resist composition containing the photosensitive resin of the present invention is used, it is excellent in photocurability and can be developed with water.
Excellent nickel plating resistance and electrical characteristics. Further, it can be said that the use of the solder resist composition of the present invention is very useful in environmental problems because it can be diluted with water.

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Claims (5)

[Claims] 1. The following general formula 1 (However, n is a positive integer) With respect to 1 equivalent of the epoxy group of the alicyclic epoxy resin (molecular weight 500 to 300,000) having a structure represented by (a) unsaturated monocarboxylic acid x equivalent (0 < x ≦ 1), (b) saturated monocarboxylic acid (1-
x) equivalent and (c) the following general formula 2 (In the formula, R ₁ and R ₂ represent a hydroxyl group, an alkoxy group, or an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 1 to 8 carbon atoms which may be substituted with an ester group.
₁ and R ₂ may be different or the same. )
A photosensitive resin containing a tertiary sulfonium salt obtained by reacting an equivalent of a sulfide compound represented by (0 <a ≦ 1). 2. An unsaturated monocarboxylic acid b equivalent (0 <b <is equivalent to 1 equivalent of an epoxy group of the alicyclic epoxy resin (molecular weight 500 to 300,000) having the structure represented by the general formula 1. 1) to the residual epoxy group of the compound obtained by the reaction, unsaturated and / or saturated monocarboxylic acid (1-
b) Equivalent and the following general formula 3 (In the formula, R ₃ , R ₄ and R ₅ represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 1 to 8 carbon atoms, which may be substituted with a hydroxyl group, an alkoxy group, or an ester group.
R ₃ , R ₄ and R ₅ may be the same or different from each other. ) A tertiary amine compound (1
-B) A quaternary ammonium salt-containing photosensitive resin obtained by reacting an equivalent amount. 3. An alicyclic epoxy resin having a structure represented by the above general formula 1 (molecular weight 500 to 300,000).
And a compound having at least two or more isocyanate groups in a range of (isocyanate equivalent) / (hydroxyl equivalent of alicyclic epoxy resin) of 1.0 or less The photosensitive resin according to claim 1 or 2. 4. An alicyclic epoxy resin having a structure represented by the general formula 1 (molecular weight 500 to 300,000).
And a compound having at least two or more silanol groups or alkoxysilyl groups, with the value of (silanol group or alkoxysilyl group equivalent) / (hydroxyl group equivalent of alicyclic epoxy resin) being 1.0 or less. The photosensitive resin according to claim 1 or 2, which is synthesized from an epoxy resin obtained by the above. 5. A photosensitive resin composition comprising (A) at least one photosensitive resin according to any one of claims 1 to 4 and (B) a photopolymerization initiator as an essential component.