JP3180979B2 - Resin composition, solder resist resin composition and cured product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition useful as a solder resist for a printed wiring board and a cured product thereof, and more particularly to a resin composition which is selectively exposed to actinic rays through a film on which a pattern is formed. In developing the solder resist pattern by developing the exposed part, it has excellent developability and has resistance to the developing solution of the exposed part, photosensitivity, adhesion, electrical insulation, electric contact resistance, solder heat resistance, solvent resistance The present invention relates to a solder resist resin composition which gives a cured product having excellent resistance, alkali resistance, acid resistance and plating resistance, and a cured product thereof.

[0002]

2. Description of the Related Art Solder resist is intended to prevent the adhesion of solder to unnecessary parts and to protect circuits when soldering components to a printed wiring board. Various properties such as resistance, solvent resistance, alkali resistance, acid resistance and plating resistance are required. As the initial solder resist, epoxy melamine-based thermosetting type was used, but there were problems such as solder heat resistance, chemical resistance and plating resistance, and for industrial printed wiring boards, For example, Japanese Patent Publication No. 51-140
No. 44 discloses an epoxy-based thermosetting type in which these are improved, and has become mainstream. For commercial printed wiring boards, since the productivity is emphasized, for example, a fast-curing ultraviolet-curing type as disclosed in Japanese Patent Publication No. 61-48800 has become mainstream. I have. However, the ultraviolet curable type has a problem in the internal curability of a thick film and has poor soldering heat resistance, so that it cannot be used for industrial printed wiring boards. These methods use screen printing as a method of forming solder resist patterns. Solder resists have been used to increase the density of printed wiring boards and the surface mounting of components due to recent downsizing of electronic devices. To form a pattern,
There is a problem in bleeding and the embedding property between circuits, and the function as a solder resist film cannot be achieved.
In order to solve such a problem, a dry film type photo solder resist and a liquid photo solder resist have been developed.

[0003]

However, in the case of a dry film type photo solder resist, when used for a high density printed wiring board, the solder heat resistance and adhesion are not sufficient. On the other hand, currently available liquid photo solder resists include those using an organic solvent or a dilute alkaline aqueous solution as a developer, and when an organic solvent is used,
There are problems of air pollution, expensive solvents, and problems with solvent resistance and acid resistance. Further, those developed with a dilute aqueous alkaline solution have a problem that the developability is deteriorated depending on the combination of the photopolymerization initiator. Further, from the viewpoint of productivity, improvement in sensitivity is constantly required.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have good developability, high sensitivity, solder heat resistance, plating resistance, hardness, adhesion, and resistance. The present invention has succeeded in providing a resin composition which is excellent in chemical properties, electric insulation properties, and the like and can be developed with a dilute alkaline aqueous solution or water. That is, the present invention

A photosensitive prepolymer (A) having at least two ethylenically unsaturated bonds in one molecule, a diluent (B) comprising a photopolymerizable vinyl monomer and / or an organic solvent, represented by the formula (1) Compound (C) shown

[0006]

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(Wherein R ₁ is a hydrogen atom or a carbon number of 1 to 4)
Represents an alkyl group. ) And the compound (D) represented by the formula (2)

[0008]

Embedded image (Wherein, R _2, R ₃ is an alkyl group having 1 to 3 carbon atoms, R _{4
Is, -OR 5 -OCH 2 CH 2 OR} 5 hydrogen atom, an alkyl group of 1 to 13 carbon atoms, a phenyl group or

[0009]

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Wherein R ₅ is an alkyl group having 1 to 13 carbon atoms. ), A solder resist resin composition and a cured product thereof. Hereinafter, each component of the resin composition of the present invention will be described. Examples of the photosensitive prepolymer (A) having at least two ethylenically unsaturated bonds in one molecule used in the present invention include: (a) an esterified product of an epoxy group with a novolak type epoxy compound and an unsaturated monocarboxylic acid. Loads (a-1-1) and (a-1-1) of a secondary hydroxyl group generated by the esterification reaction of (a-1) and a saturated or unsaturated polybasic acid anhydride
Reaction product of 1-1) and (meth) acrylate having one hydroxyl group in one molecule via diisocyanate (a-1-2) (b) Epoxy by hydantoin epoxy resin and unsaturated monocarboxylic acid And esterified products of the group (b-1).

As the novolak type epoxy compound, for example, those obtained by reacting novolaks obtained by reacting phenol, cresol, halogenated phenols and alkylphenols with formaldehyde in the presence of an acidic catalyst and epichlorohydrin are suitable. , YDCN-701, YDCN-704, YD manufactured by Toto Kasei Co., Ltd.
PN-638, YDPN-602, manufactured by Dow Chemical Company
DEN-431, DEN-439, Ciba Geigy's EPN-1138, EPN-1235, EPN-12
99, Dainippon Ink and Chemicals N-730, N-7
70, N-865, N-665, N-673, VH-4
150, VH-4240, EOCN-12 manufactured by Nippon Kayaku
0, BRPN and the like. Further, a part or all of the novolak type epoxy compound is, for example, manufactured by Yuka Shell Co., Ltd. Epicoat 828, Epicoat 1007, Epicoat 80
7, Dainippon Ink and Chemicals, Inc. Epicron 840, Epicron 860, Epicron 3050, Dow Chemical's DER-330, DER-337, DER-36
1, Celloxide 2021, manufactured by Daicel Chemical Industries, Ltd., TETRAD-X, TETRAD-, manufactured by Mitsubishi Gas Chemical Company
C, Nippon Soda's EPB-13, EPB-27, Ciba-Geigy's GY-260, GY-255, XB-
Bisphenol A type such as 2615, bisphenol F
Type, hydrogenated bisphenol A type, brominated bisphenol A
Epoxy compounds such as glycidyl ether type such as type, amino group-containing, alicyclic, or polybutadiene modified can be used, but it is particularly preferable to use cresol or phenol novolak type epoxy compound.

The unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and saturated or unsaturated dibasic anhydrides and (meth) acrylates having one hydroxyl group in one molecule. Or a half ester of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound, for example, a saturated or unsaturated dibasic acid such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, etc. Anhydride and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Glycerin di (meth) acrylate, pentaerythritol triacrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, or the above-mentioned saturated or unsaturated dibasic acid and glycidyl (meth) acrylate are reacted in an equimolar ratio by a conventional method. The half-ester or the like obtained by the reaction is used alone or as a mixture, but acrylic acid is particularly preferred.

As the above-mentioned saturated or unsaturated polybasic acid anhydride, anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid and trimellitic acid are used. acid,
Phthalic anhydride or hexahydrophthalic anhydride is preferred.

The diisocyanates include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. Particularly, tolylene diisocyanate or isophorone diisocyanate is preferable. Next, as the (meth) acrylates having one hydroxyl group in one molecule, hydroxyethyl (meth) acrylate,
Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (hydroxyethyl)
For example, di (meth) acrylate of isocyanurate is used, and hydroxyethyl acrylate or pentaerythritol triacrylate is particularly preferable.

The hydantoin epoxy resin includes:
5,5-dimethylhydantoin diepoxide, 5,5-
Examples thereof include a condensation product of a diepoxide such as diethylhydantoin diepoxide and a hydantoin such as 5,5-dimethylhydantoin and 5,5-diethylhydantoin, or a reaction product of a condensation reaction product with epichlorohydrin. The novolak type epoxy compound or the esterified product (a-1) or (b-1) of the epoxy group with the hydantoin epoxy resin and the unsaturated monocarboxylic acid has an epoxy equivalent / carboxylic acid equivalent of preferably 0.8 to 3.3. Is reacted in a usual manner in the range of 0.9 to 1.1. When the equivalent ratio is 0.8 or less, the free acid remains, so that the solder heat resistance is reduced and the odor is large. When the value exceeds 3.3, the photosensitivity is lowered, which is not preferable. For example, dissolving the novolak type epoxy compound or the hydantoin epoxy resin in an organic solvent such as cellosolve acetate, carbitol acetate, ethyl methine ketone and the like, hydroquinone, a thermal polymerization inhibitor such as methoquinone, and benzyldimethylamine, benzyltrimethylammonium chloride, benzyltrimethylammonium The unsaturated monocarboxylic acid is mixed with the bromide or the like as a catalyst and reacted by heating and stirring at 70 to 140 ° C.

The ratio of the addition reaction between the secondary hydroxyl group of the esterified product of the novolak type epoxy compound (a-1) and the polybasic acid anhydride is based on the equivalent of the secondary hydroxyl group of (a-1). The equivalent is preferably 0.3 or more, and the acid value of the formed resin is usually 30 to 160 mgKOH / g, preferably 45 to 120 mgKOH / g. When the acid value is 30 or less, the solubility in an alkali developing solution is deteriorated. On the other hand, when the acid value is 160 or more, the cured film may be a factor for deteriorating various properties as a solder resist such as alkali resistance and electric characteristics. In this case, in the case of (a-1), if the residual epoxy group is large, it is easy to gel during the reaction with a saturated or unsaturated polybasic anhydride, so that the residual ratio of the epoxy group is preferably 20% or less,
Preferably it is 15% or less. Reaction temperature is 70-120
C is preferred.

The reaction product of the remaining secondary hydroxyl group of (a-1-1) and a (meth) acrylate having one hydroxyl group in one molecule via the diisocyanate (a-1-1)
1-2) is the presence of an organic solvent such as cellosolve acetate, carbitol acetate, ethyl methyl ketone, or the like, in an equimolar ratio of the diisocyanate and the (meth) acrylate having one hydroxyl group in one molecule. In the absence of the reaction, a half urethane acrylate is synthesized by reacting with an organotin compound such as tributyltin dilaurate as a catalyst at 30 to 100 ° C. for 2 to 12 hours by heating and stirring in a conventional manner. Next, after mixing such that the isocyanate equivalent of the half urethane acrylate has a reaction ratio of usually 0.1 or more, preferably 0.2 or more with respect to the secondary hydroxyl group equivalent of (a-1-1), usually 30 to 100 ° C. For 2 to 12 hours with heating and stirring. If the equivalent ratio in this case is 0.1 or less, there is a possibility that the effect of enhancing the curability by actinic light cannot be obtained.

Representative examples of the photopolymerizable vinyl monomer which is the diluent (B) used in the present invention include hydroxyalkyl such as 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate. Acrylates, mono- or di (meth) acrylates of glycols such as methoxytetraethylene glycol, polyethylene glycol, propylene glycol, etc., N, N-
(Meth) acrylamides such as dimethylacrylamide and N-methylolacrylamide, aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate, trimethylolpropane, pentaerythritol, dipentaerythritol, tris (hydroxy Polyhydric alcohols such as ethyl) isocyanurate or polyhydric (meth) acrylates of these ethylene oxide or propylene oxide adducts, glycidyl ethers such as glycerin triglycidyl ether, tritylolpropane triglycidyl ether, and triglycidyl isocyanurate (Meth) acrylates and melamine (meth) acrylate. Further, as the organic solvent, ethyl methyl ketone, ketones such as cyclohexane, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, Glycol ethers such as propylene glycol dimethyl ether, dipropylene glycol monoethyl ether, and triethylene glycol monoethyl ether;
Examples include petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. The purpose of use of the diluent (B) is that, in the case of a photopolymerizable vinyl monomer, the photosensitive raw prepolymer is diluted to make it easy to apply,
It serves to enhance photopolymerizability, and in the case of organic solvents, dissolves and dilutes the photosensitive prepolymer, thereby applying it as a liquid and then drying it to form a film. Therefore, depending on the diluent used, either a contact type or a non-contact type in which the photomask is brought into contact with the coating film is used.

Specific examples of the compound (C) represented by the formula (1) as a photopolymerization initiator used in the present invention include, for example,

[0020]

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(Quantacure BMS, manufactured by International Bio-Synthetics)

[0022]

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[0023]

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And the like. Specific examples of the compound (D) represented by the formula (2) as a photopolymerization accelerator used in the present invention include, for example, ethyl N, N-dimethylaminobenzoate, isoamyl N, N-dimethylaminobenzoate Ester, N, N-dimethylaminobenzoic acid amyl ester, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, N, N-dimethylaminobenzaldehyde, N, N
-Dimethylaminoacetophenone, 2-n-butoxyethyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethylbenzoate and the like.

The resin composition of the present invention can be obtained by mixing, dispersing, dissolving, kneading, etc. the components (A) to (D).
The resin composition thus obtained further includes, if necessary,
To improve the photosensitivity, a usual photopolymerization initiator, for example,
2-methyl-1- [4- (methylthio) phenyl] -2
-Morpholino-propan-1-one, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2-ethylanthraquinone, 2-methyl-1- (4-morpholinophenyl) -2-di (2-methoxyethyl) amino -Propane-1,2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butanone-1 or the like can be used alone or in combination of two or more.
Further, epoxy resins such as melamines, bisphenol A type epoxy resins, biphenyl type epoxy resins, bisphenol S type epoxy resins, triglycidyl isocyanurate, novolak type epoxy resins, and imidazoles, dicyandiamide, triazine as epoxy curing agents for these epoxy resins. , Guanamines, urea derivatives and the like can be used in combination. Also, the above epoxy resin (meta)
Acrylates or acrylates which are solid at room temperature and hardly soluble in the diluent (B) can be used.

The proportions of the components (A) to (D), which are the components of the resin composition of the present invention, are as follows.
It is preferably 84% by weight, particularly preferably 28 to 76% by weight, the component (B) is preferably 11 to 78% by weight, particularly preferably 16 to 66% by weight, and the component (C) is 0.5 to 25% by weight.
% By weight, particularly preferably 1 to 20% by weight
The component (D) is preferably from 0.05 to 25% by weight, particularly preferably from 0.2 to 20% by weight. Further, the resin composition of the present invention, if necessary for the purpose of improving properties such as adhesion, hardness, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay And conventional inorganic fillers such as magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder.
0% by weight, preferably 5 to 40% by weight. If necessary, conventional coloring agents such as phthalocyanine blue, phthalocyanine green, titanium oxide, carbon black, etc., thermal polymerization inhibitors such as hydroquinone, metokinoshi and phenothiazine, thickeners such as asbestos, olben, benton, montmorillonite, etc. , Silicone-based,
Known additives such as a fluorine-based or polymer-based antifoaming agent and / or an adhesion imparting agent such as a Leven rig agent, a thiazole-based, a triazole-based, or a silane coupling agent can be used.

The developer for forming a solder resist pattern after exposing the resin composition through a photomask varies depending on the selection of the photosensitive prepolymer (A), but may be selected from sodium hydroxide, sodium carbonate and potassium carbonate. An aqueous solution of alkali such as sodium phosphate, sodium silicate, ammonia, amine, etc. or water can be used. In order to obtain a cured product of the resin composition of the present invention, it can be irradiated with radiation such as ultraviolet rays. Specifically, curing is preferably performed by irradiating ultraviolet rays using a low-pressure, medium-pressure, high-pressure, ultra-high-pressure mercury lamp, xenon lamp, metal halide lamp, or the like.

[0028]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. Parts in Synthesis Examples and Examples are parts by weight. Synthesis Example 1 1090 parts of a cresol novolac type epoxy resin having an epoxy equivalent of 218 (EOCN-103 manufactured by Nippon Kayaku Co., Ltd.)
396 parts of acrylic acid, carbitol acetate
5 parts, 412.5 parts of ipsol @ 150 (a petroleum solvent mainly composed of tetramethylbenzene: manufactured by Idemitsu Petrochemical Co., Ltd.), 1.1 parts of hydroquinone, and 8.3 parts of triphenylphosphine were charged, and the mixture was heated at 100 to 110 ° C. for 15 hours. The reaction was conducted to obtain an esterified product (a-1) of a novolak-type epoxy compound having an acid value of 2.0 mgKOH / g with acrylic acid. Next, 700 parts of (a-1) and 120 parts of phthalic anhydride were mixed,
The temperature was raised to 95 to 100 ° C and the reaction was carried out for 8 hours.
5 mg KOH / g of a novolak type epoxy compound esterified with acrylic acid (a-1)
The organic solvent liquid of 1-1) was obtained.

Synthesis Example 2 87 parts of tolylene diisocyanate (2.4% 65%,
A mixture of 2.6% 35%), 50 parts of carbitol acetate and 50 parts of ipsol @ 150 were charged at 25 ° C.
While stirring and then 65 parts of 2-hydroxyethyl acrylate, 50 parts of carbitol acetate and 150 parts of ipsol @ 150, 0.05 parts of methoquinone
Part of a mixture of 0.2 part of dibutyltin dilaurate and 35 parts of
The solution is added dropwise over 2 hours while controlling so as not to exceed ° C.
Next, the temperature was raised to 50 ° C., and the mixture was stirred for 4 hours to carry out a reaction, thereby obtaining a semi-urethane compound having a terminal acrylic group. Next, 1640 parts of an organic solvent liquid of an acid anhydride adduct (a-1-1) of the esterified product (a-1) of the novolak type epoxy compound obtained by the acrylic acid of the novolak epoxy compound obtained in Synthesis Example 1 was mixed, and the mixture was heated to 80 ° C. After heating and reacting for 6 hours, the mixture was cooled and the urethane acrylate adduct (a-1) of the acid anhydride adduct (a-1-1) of the esterified product (a-1) of the novolak type epoxy compound with acrylic acid.
-2) The organic solvent liquid was obtained. Synthesis Example 3 Structural formula

[0030]

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2 moles and 5,5-dimethylhydantoin 1
And a hydantoin epoxy resin (epoxy equivalent: 304, softening point: 67 ° C.)
8 parts, acrylic acid 140 parts, methoquinone 0.4 part, triphenylphosphine 2.7 parts, carbitol acetate 160 parts and solvent naphtha 160 parts were charged, and 9
The reaction was performed at 5 ° C to obtain hydantoin epoxy acrylate (b-1).

Examples 1 to 4, Comparative Examples 1 and 2 After pre-mixing according to the composition shown in Table 1 (the numerical values are parts by weight), the mixture was kneaded three times with a three-roll mill to obtain a resin composition of the present invention. Next, when the particle size was measured with a grind meter manufactured by Toyo Seiki Co., Ltd., it was all 20 μm or less. This resin composition was applied to the entire surface of the copper through-hole printed wiring board by screen printing so as to have a thickness of 30 μm.
Then, it was placed in a hot-air circulation furnace, dried at 80 ° C. for 30 minutes, and then cooled to room temperature to obtain a dried coating film. Next, the patterned photomask is brought into contact with the coating film surface, and manufactured by Oak Manufacturing Co., Ltd.
Exposure was performed using an ultra-high pressure mercury lamp exposure apparatus, the photomask was peeled off from the coating surface, and then developed with a 1% aqueous solution of sodium carbonate as a developing solution at a spray pressure of 2.0 kg / m ² , washed with water and dried. Next, it was placed in a hot air circulating furnace heated to 150 ° C. for 60 minutes to form a post cure and a solder resist pattern. Table 2 shows the results of tests on various characteristics of the solder resist resin composition and the solder resist pattern obtained in Examples 1 to 4 and Comparative Examples 1 and 2. In addition, the test method and evaluation judgment of each performance of Table 2 are as follows.

(1) Photosensitivity test The irradiation light amount of the ultraviolet ray having a wavelength of 365 nm was measured using an integrated light amount manufactured by Oak Manufacturing Co., Ltd. at 200 mJ / cm ² , 300 mJ / cm ² and 50 mJ / cm ^2.
After irradiation with 0 mJ / cm ² and development with the respective developer at a spray pressure of ² kg / cm ² for 60 seconds, the state of the coating film was visually judged. : No change is observed at all △: Surface is changed ×: Coating film falls off

(2) Developability test The resin composition was applied to the entire surface of the copper through-hole printed wiring board for 30 days.
μm, and then placed in a hot-air circulating furnace and left at 80 ° C. for 30 minutes, 60 minutes, and 90 minutes, and passed through a photomask to measure the amount of ultraviolet light having a wavelength of 365 nm, manufactured by Oak Manufacturing Co., Ltd. 500mJ / cm ² using an integrated luminometer
The irradiated sample was used as a test piece, and after developing with a developing solution (1% aqueous solution of sodium carbonate) at a spray pressure of ² kg / cm ² for 60 seconds, a state where an unexposed portion was removed was visually determined. ◎: Complete development was completed. 薄 く: There was a part that was not developed thinly on the surface. ：: There was undeveloped part as a whole. X: Almost no development. (3) Adhesion test. Measure the light amount using an integrating light meter manufactured by Oak Manufacturing Co., Ltd. at 500 mJ / cm ²
The irradiated product was developed with each developing solution at a spray pressure of ² kg / cm ² for 60 seconds, post-cured into a test piece, cross-cut in a matrix shape according to the test method of JIS D0202, and then cellophane. The state of peeling after the peeling test was visually determined with a tape. ◎: 100/100 with no peeling at all ○: 100/100 cross cut part slightly peeled △: 50/100 to 90/100 ×: 0/100 to 50/100 (4) Pencil hardness test JIS K each test piece same as the test
The hardness was measured under a load of 1 kg according to the test method 5400.

(5) Acid Resistance Test The same test pieces as in the adhesion test were each 10% by volume.
After being immersed in an aqueous solution at 20 ° C. for 30 minutes in H ₂ SO _4, it was taken out, and the state and adhesion of the coating film were comprehensively evaluated. ：: No change is observed at all. △: Slight change. ×: Coating has swelling or swelling. (6) Alkali resistance test 10% by volume H ₂ SO ₄ aqueous solution is converted to 10% sodium hydroxide aqueous solution. The test and evaluation were performed in the same manner as in the acid resistance test except that the test was changed. (7) Solvent resistance test A test evaluation was performed in the same manner as in the acid resistance test, except that the 10% by volume aqueous sulfuric acid solution was changed to acetone.

(8) Plating Resistance Test Each of the same Tetos pieces as in the adhesion test was used for 10 minutes at a liquid temperature of 30 ° C. and a current density of 1 A / dm ² using “AUTORONEX CI” (gold plating solution manufactured by Celllex, USA). The state of the coating film after plating to deposit gold plating having a thickness of 1.5 μm was evaluated in the same manner as in the acid resistance test. (9) Solder resistance test JIS C
According to the test method of No. 6481, a solder bath at 260 ° C.
The state of the coating film after immersion for 1 second, 3 times and 5 times was evaluated in the same manner as in the acid resistance test. (10) Insulation Resistance Measurement Using the comb test pattern B of IPC-B-25, test pieces were prepared under the same conditions as in the adhesion test, and according to the test method of IPC-SM-840B (IPC class III), The moisture absorption after 7 days and the insulation resistance after contact were measured.

[0037]

Table 1 Example 1 Comparative Example * 10 12 3 4 12 2 (a-1-1) obtained in Synthesis Example 1 93 46.5 93 (a-1-2) obtained in Synthesis Example 2 100 100 Synthesis (B-1) obtained in Example 3 93 46.5 KAYARAD R-20591 * 1 20 20 20 20 20 20 KAYARAD DPHA * 2 5 5 5 5 5 5 Propylene glycol dimethyl ether 5.0 5.0 5.0 5.0 5.0 5.0 TEPIC-S * 3 10 5 10 10 5 KAYARAD SPGDA * 4 5 10 5 Quantacure BMS * 5 5 5 5 5 KAYACURE EPA * 6 5 5 5 5 15 Irgacure 907 * 7 9 KAYACURE DETX-S * 8 5 Barium sulfate 22 22 22 22 22 22 Oxidation Aluminum powder 5 5 5 5 5 5 Fine talc 5 5 5 5 5 5 Phthalocyanine green 1.5 1.5 1.5 1.5 1.5 1.5 Modaflow 1.5 1.5 1.5 1.5 1.5 1.5 Dicyandiamide 2 1 2 1 2 1 2P4MHZ * 9 1 0.5 1 0.5 1 0.5

Note * 1 KAYARAD R-20
58: Nippon Kayaku Co., Ltd. Phenol novolak type epoxy acrylate butyl cellosolve acetate 30% by weight * 2 KAYARAD DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol polyacrylate * 3 TEPIC-S: Nissan Chemical Co., Ltd. Tris ( 2,3-epoxypropyl) isocyanurate Melting point 95-125 ° C * 4 KAYARAD SPGDA: Nippon Kayaku Co., Ltd.
3,9-bis (1,1-dimethyl-2-hydroxyethyl) 2,4,8,10-tetraoxaspiro [5,5] undecane diacrylate (mp 117
~ 120 ° C), powder, poorly soluble acrylate. * 5 Quabtacure BMS: manufactured by International Biosynthetics Inc., 4-Benzoyl-
4'-methyldiphenyl sulfide.

* 6 KAYACURE EPA: N, N-dimethylaminobenzoic acid ethyl ester manufactured by Nippon Kayaku Co., Ltd. * 7 Irgacure 907: manufactured by Ciba Geigy
Photopolymerization initiator * 8 KAYACURE DETX-S: 2,4-diethylthioxanthone manufactured by Nippon Kayaku Co., Ltd. * 9 "2P4MHZ": Epoxy curing agent manufactured by Shikoku Chemicals Co., Ltd. * 10 Water is used as a developer in Example 3. did.

[0040]

[Table 2] Table 2 Example Comparative Example 1 2 3 4 1 2 Photosensitivity 100mJ / cm ² ○ ○ ○ ○ × △ 300mJ / cm ² ○ ○ ○ ○ ○ △ △ 500mJ / cm ² ○ ○ ○ ○ ○ ○ 30 minutes ◎ ◎ ◎ ◎ ◎ ◎ 60 minutes ◎ ◎ ◎ ◎ ○ △ 90 minutes ○ ◎ ○ ◎ △ × Adhesion ◎ ○ ◎ ◎ ◎ ○ Pencil hardness 9H 8H 7H 8H 9H 8H Acid resistance ○ ○ ○ ○ ○ ○ Alkali resistance ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ △ ○ Plating resistance ○ ○ ○ ○ △ △ Solder resistance 1 time ○ ○ ○ ○ ○ ○ 3 times ○ ○ ○ ○ ○ ○ 5 times ○ ○ ○ ○ △ △ Insulation resistance (Ω) Initial value (× 10 ¹³ ) 2.7 4.5 2.3 2.5 2.6 4.4 Value after test (× 10 ¹² ) 6.5 7.3 4.2 4.9 4.8 6.9

As is clear from the evaluation results in Table 2, the resin composition of the present invention is excellent in photosensitivity and developability, and the cured film has high hardness, heat resistance, acid resistance, alkali resistance,
Excellent solvent resistance, gold plating resistance, and electrolytic corrosion resistance.

[0042]

The resin composition of the present invention has excellent photosensitivity and developability, and the cured product has good adhesion, solder heat resistance, chemical resistance,
It has excellent gold plating resistance, electrolytic corrosion resistance, and electrical insulation properties, and is particularly suitable as a solder resist resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI H05K 3/28 H05K 3/28 D (56) References JP-A-3-237115 (JP, A) JP-A-4-7321 ( JP, A) JP-A-4-355450 (JP, A) JP-A-5-331240 (JP, A) JP-A-61-48800 (JP, A) JP-B-51-14044 (JP, B2) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 2/46-2/50 C08F 299/00-299/08 G03F 7/027 G03F 7/028 H05K 3/28

Claims (2)

(57) [Claims] 1. A photosensitive prepolymer (A) having at least two ethylenically unsaturated bonds in one molecule, a diluent (B) comprising a photopolymerizable vinyl monomer and / or an organic solvent, a compound represented by the formula (1) Compound (C) represented by the formula: (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) And a compound (D) represented by the formula (2): (Wherein, R _2, R ₃ is an alkyl group having 1 to 3 carbon atoms, R ₄
Represents —OR ₅ , —OCH ₂ CH ₂ OR ₅ , a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, a phenyl group or Wherein R ₅ is an alkyl group having 1 to 13 carbon atoms. )
A resin composition comprising: 2. A diluent (B) comprising a photosensitive prepolymer (A) having at least two ethylenically unsaturated bonds in one molecule, a photopolymerizable vinyl monomer and / or an organic solvent, and a compound represented by the formula (1) Compound (C) represented by the formula: (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) And a compound (D) represented by the formula (2): (Wherein, R _2, R ₃ is an alkyl group having 1 to 3 carbon atoms, R ₄
Represents —OR ₅ , —OCH ₂ CH ₂ OR ₅ , a hydrogen atom, an alkyl group having 1 to 13 carbon atoms, a phenyl group or Wherein R ₅ is an alkyl group having 1 to 13 carbon atoms. )
A solder resist resin composition comprising: