JPH06329971A - Resin composition, solder resist resin composition, and its cured article - Google Patents

Abstract

PURPOSE:To improve developability, photosensitivity, adhesive properties, electrical insulating properties, resistance to electrolytic corrosion, etc., by compounding a specific photosensitive prepolymer, a diluent, a photopolymn. initiator, and a photopolymn. accelerator. CONSTITUTION:21-84wt.% photosensitive prepolymer having at least two ethylenically unsatd. bonds in the molecule, 11-78wt.% diluent comprising a photopolymerizable vinyl monomer and/or an org. solvent, 0.5-25wt.% compd. of formula I (where R1, R2, and R3 are each H, Cl, Br, F, 1-5C alkyl, or 1-5C alkoxy excluding when they all are H) as the photopolymn, initiator, and 0.05-25wt.% compd. of formula II (wherein R4 an R5 are each 1-3C alkyl; R6 is -OR7,-OCH2CH2CH2OR7, H, 1-13C alkyl, phenyl, or a group of formula III; and R7 is 1-13C alkyl) as the photopolymn. accelerator are compounded.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition particularly useful as a solder resist for printed wiring boards and a cured product thereof. More specifically, the present invention relates to a resin composition which is not exposed to an active ray selectively through a patterned film. In forming the solder resist pattern by developing the exposed part, it has excellent developability and resistance to the developer in the exposed part, and it has photosensitivity, adhesiveness, electrical insulation, electric contact resistance, solder heat resistance, resistance The present invention relates to a solder resist resin composition that gives a cured product excellent in solvent 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 adhesion of solder to parts other than necessary when soldering parts to a printed wiring board and to protect circuits, and therefore, adhesion, electrical insulation, and solder heat resistance. Various properties such as resistance, solvent resistance, alkali resistance, acid resistance and plating resistance are required. The initial one as a solder resist, thermosetting epoxy melamine type was used, but there are problems such as solder heat resistance, chemical resistance and plating resistance, for industrial printed wiring boards, For example, Japanese Patent Publication 51-140
Japanese Patent Laid-Open No. 44-44 discloses an epoxy-based thermosetting type that is an improvement of these and has become the mainstream. Further, since productivity is important for a consumer printed wiring board, a fast-curing UV-curing type as disclosed in, for example, Japanese Patent Publication No. 61-48800, has become the mainstream. There is. However, the ultraviolet curable type has a problem of internal curability in a thick film, and also has poor solder heat resistance, and cannot be used for an industrial printed wiring board. In addition, these use screen printing as a method for forming a solder resist pattern, but the solder resist is suitable for higher density of printed wiring boards and surface mounting of components due to lighter, thinner, shorter, and smaller electronic devices. For pattern formation,
There is a problem in bleeding and embedding between circuits, and it is no longer possible to function as a solder resist film.
In order to solve such a problem, a dry film type photo solder resist or a liquid photo solder resist has been developed.

[0003]

However, in the case of a dry film type photo solder resist, when it is used for a high density printed wiring board, solder heat resistance and adhesion are not sufficient. On the other hand, liquid photosolder resists currently on the market include those that use 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 solvent resistance and acid resistance. Further, those developed with a dilute aqueous alkali solution have a problem that the developability deteriorates depending on the combination of photopolymerization initiators. Further, from the viewpoint of productivity, improvement in sensitivity is constantly required.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that the developability is good and the sensitivity is high, and the solder heat resistance, plating resistance, hardness, adhesion and resistance We have succeeded in providing a resin composition which is excellent in chemical resistance and electric insulation and can be developed with a dilute aqueous alkali solution or water. That is, the present invention is

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

[0006]

[Chemical 4]

(In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom and C _{1 to} C ₅
Is an alkyl group or a C ₁ -C ₅ alkoxy group. However, the case where R ₁ , R ₂ and R ₃ are simultaneously hydrogen atoms is excluded. ) And a compound (D) represented by formula (2),

[0008]

[Chemical 5]

(In the formula, R ₄ and R ₅ are C _{1 to} C ₃ alkyl groups, R ₆ is —OR ₇ , —OCH ₂ CH ₂ OR ₇ , hydrogen atom, C _{1 to} C ₁₃ alkyl group, and phenyl. Group or

[0010]

[Chemical 6]

Wherein R ₇ is a C ₁ -C ₁₃ alkyl group. The present invention relates to a resin composition, a solder resist resin composition and a cured product thereof. Hereinafter, each component of the resin composition of the present invention will be described. As the photosensitive prepolymer (A) having at least two ethylenically unsaturated bonds in one molecule used in the present invention,
For example, (a) a load of a secondary hydroxyl group and a saturated or unsaturated polybasic acid anhydride formed by the esterification reaction of an epoxy group esterified product (a-1) with a novolac type epoxy compound and an unsaturated monocarboxylic acid ( a-1-1) and (a-
1-1) and a reaction product of (meth) acrylate having one hydroxyl group in one molecule via diisocyanate (a-1-2) (b) Hydantoin epoxy resin and epoxy with unsaturated monocarboxylic acid Examples thereof include esterified products (b-1) of the group.

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

As the unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and saturated or unsaturated dibasic acid anhydrides and (meth) acrylates having one hydroxyl group in one molecule. , Or half-esters of a saturated or unsaturated dibasic acid and an unsaturated monoglycidyl compound, for example, a saturated or saturated dibasic acid such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, etc. Anhydrous and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate,
Glycerin di (meth) acrylate, pentaerythritol triacrylate, tris (hydroxyethyl) isocyanurate di (meth) acrylate, or the saturated or unsaturated dibasic acid and glycidyl (meth) acrylate are reacted in an equimolar ratio by a conventional method. The half-ester and the like obtained in this way may be used alone or in combination, and acrylic acid is particularly preferable.

As the saturated or unsaturated polybasic acid anhydride, anhydrides such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, succinic acid, trimellitic acid and the like are used, but especially tetrahydrophthalic anhydride. acid,
Phthalic anhydride or hexahydrophthalic anhydride are preferred.

As the diisocyanates, tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like are used. 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)
Di (meth) acrylate of isocyanurate is used, and hydroxyethyl acrylate or pentaerythritol triacrylate is particularly preferable.

As the hydantoin epoxy resin,
5,5-Dimethylhydantoin diepoxide, 5,5-
Examples thereof include a condensation reaction 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 the condensation reaction product and epichlorohydrin. The ester equivalent (a-1) or (b-1) of the epoxy group by the novolac type epoxy compound or hydantoin epoxy resin and unsaturated monocarboxylic acid is usually 0.8 to 3.3 epoxy equivalent / carboxylic acid equivalent. Is in the range of 0.9 to 1.1, and the reaction is carried out by a conventional method. If the equivalent ratio is 0.8 or less, the free acid remains, so that the solder heat resistance is lowered and the odor is large. When it exceeds 3.3, the photosensitivity is lowered, which is not preferable. For example, the novolac type epoxy compound or hydantoin epoxy resin is dissolved in an organic solvent such as cellosolve acetate, carbitol acetate, ethyl methine ketone, etc., and hydroquinone, a thermal polymerization inhibitor such as methoquinone and benzyldimethylamine, benzyltrimethylammonium chloride, benzyltrimethylammonium. The unsaturated monocarboxylic acid is mixed by using bromide or the like as a catalyst, and the mixture can be reacted by heating and stirring at 70 to 140 ° C.

The ratio of the addition reaction of the secondary hydroxyl group of the esterified product (a-1) of the novolac type epoxy compound and the polybasic acid anhydride is such that the acid anhydride is equivalent to the secondary hydroxyl group equivalent of (a-1). The equivalent weight is preferably 0.3 or more, and the acid value range of the produced resin is usually 30 to 160 mg / KOH / g, preferably 45 to 120 mg / KOH / g. If the acid value is 30 or less, the solubility in an alkali developing solution will be poor, and conversely, if it is 160 or more, it may be a factor that deteriorates various properties as a solder resist such as alkali resistance and electrical properties of the cured film. In this case, (a-1) easily gels during the reaction with a saturated or unsaturated polybasic acid anhydride when a large amount of residual epoxy groups are present, so the residual rate of epoxy groups is preferably 20% or less,
It is preferably 15% or less. Reaction temperature is 70-120
C is preferred.

Reaction product (a-) of the residual secondary hydroxyl group of (a-1-1) and (meth) acrylate having one hydroxyl group in one molecule through the diisocyanate.
1-2) is, for example, the presence of an organic solvent such as cellosolve acetate, carbitol acetate, ethyl methyl ketone or the like, in the equimolar ratio of the diisocyanates and the (meth) acrylates having one hydroxyl group in one molecule. In the absence of the catalyst, an organic tin compound such as tributyltin dilaurate is used as a catalyst to react for 2 to 12 hours by heating and stirring at 30 to 100 ° C. by a conventional method to synthesize a semi-urethane acrylate. Next, after mixing so that the isocyanate equivalent of the semi-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. It is obtained by reacting by heating and stirring for 2 to 12 hours. In this case, if the equivalent ratio is 0.1 or less, the effect of enhancing the curability by actinic rays may not be obtained.

Typical examples of the photopolymerizable vinyl-based 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, 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) Ethyl) polyhydric alcohols such as isocyanurate or polyhydric (meth) acrylates of adducts of ethylene oxide or propylene oxide, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, glycidyl ethers such as triglycidyl isocyanurate (Meth) acrylates, melamine (meth) acrylates and the like. Also, as the organic solvent, ethyl methyl ketone, ketones such as cyclohexane, toluene, xylene, aromatic hydrocarbons such as 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, triethylene glycol monoethyl ether,
Examples thereof include petroleum-based solvents such as petroleum ether, petroleum naphtha, and solvent naphtha. The purpose of use of the diluent (B) is to dilute the photosensitive prepolymer in the case of a photopolymerizable vinyl-based monomer to make it easy to apply and
It serves to enhance the photopolymerizability, and in the case of an organic solvent, it serves to dissolve and dilute the photosensitive prepolymer, thereby applying it as a liquid and then drying it to form a film. Therefore, either a contact method or a non-contact exposure method in which the photomask is brought into contact with the coating film is used depending on the diluent used.

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

[0021]

[Chemical 7]

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

[Chemical 14]

[0029]

[Chemical 15]

[0030]

[Chemical 16]

And the like. Preferred examples include the compounds of the above formulas (4), (5) and (7).

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

The resin composition of the present invention can be obtained by subjecting the components (A) to (D) to treatments such as mixing, dispersing, dissolving and kneading. The resin composition thus obtained may further contain a usual photopolymerization initiator such as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino, if necessary, for improving the photosensitivity. -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 and the like can be used alone or in combination of two or more kinds. Further, melamines, bisphenol A type epoxy resins, biphenyl type epoxy resins, bisphenol S type epoxy resins, triglycidyl isocyanurate, novolac type epoxy resins and other epoxy resins, and imidazoles, dicyandiamide, triazine as epoxy curing agents for these epoxy resins. , Guanamines,
A urea derivative or the like can be used in combination. Further, a (meth) acrylic acid esterified product of the above epoxy resin, or an acrylate which is solid at room temperature and hardly soluble in the diluent (B) can be used.

The proportions of the components (A) to (D) used as the constituents of the resin composition of the present invention are 21 to 21 for the component (A).
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 is preferred, particularly preferably 1 to 20% by weight
The component (D) is preferably 0.05 to 25% by weight, and particularly preferably 0.2 to 20% by weight. Further, in the resin composition of the present invention, barium sulfate, barium titanate, silicon oxide powder, finely divided silicon oxide, amorphous silica, talc, clay are added as necessary for the purpose of improving properties such as adhesion and hardness. , A conventional inorganic filler such as magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide or mica powder can be used, and the compounding ratio thereof is usually 0 to 6 of the resin composition.
It is 0% by weight, preferably 5 to 40% by weight. If necessary, conventional colorants such as phthalocyanine blue, phthalocyanine green, titanium oxide and carbon black, thermal polymerization inhibitors such as hydroquinone, metoquinone and phenothiazine, thickeners such as asbestos, olben, benton and montmorillonite. , Silicone type,
Known additives such as a fluorine-based or polymer-based defoaming agent and / or a leveling agent, an adhesion promoter such as a thiazole-based, a triazole-based, or a silane coupling agent can be used.

The developing solution for forming the solder resist pattern after exposing the resin composition through a photomask is different depending on the selection of the photosensitive prepolymer (A), but is sodium hydroxide, sodium carbonate, potassium carbonate. An aqueous alkaline solution 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, it is preferable to cure by irradiating with ultraviolet rays using a low pressure, medium pressure, high pressure and ultra high pressure mercury lamp, a xenon lamp, a metal halide lamp or the like.

[0036]

EXAMPLES The present invention will be described in more detail below with reference to examples. The parts in the synthesis examples are parts by weight. Synthesis Example 1 1090 parts of cresol novolac type epoxy resin having epoxy equivalent of 218 (EOCN-103 manufactured by Nippon Kayaku Co., Ltd.),
Acrylic acid 396 parts, carbitol acetate 412.
5 parts, Ipsol # 150 (petroleum solvent mainly composed of tetramethylbenzene: manufactured by Idemitsu Petrochemical Co., Ltd.) 412.5 parts, hydroquinone 1.1 parts, and triphenylphosphine 8.3 parts were charged, and the temperature was 100 to 110 ° C. for 15 hours. The reaction was carried out to obtain an esterified product (a-1) of acrylic acid of a novolac type epoxy compound having an acid value of 2.0 mg / KOH / g. Then, (a-1) 700 parts and 120 parts of phthalic anhydride are mixed,
The temperature is raised to 95 to 100 ° C and the reaction is carried out for 8 hours, and the acid value of the solid component is 8
5 mg / KOH / g novolak type epoxy compound esterified with acrylic acid (a-1) acid anhydride adduct (a-
An organic solvent solution of 1-1) was obtained.

Synthesis Example 2 87 parts of tolylene diisocyanate (2.4-position 65%,
(Mixture of 2.6% 35%), 50 parts of carbitol acetate and 50 parts of Ipsol # 150 were charged, and the temperature was 25 ° C.
65 parts of 2-hydroxyethyl acrylate, 50 parts of carbitol acetate and 50 parts of Ipsol # 150, metquinone 0.05
35 parts of a mixed solution of 0.2 parts of dibutyltin dilaurate and 35 parts of
Add dropwise over 2 hours while adjusting so that the temperature does not exceed ℃.
Next, the temperature was raised to 50 ° C. and the mixture was stirred for 4 hours to carry out a reaction to obtain a semi-urethane compound having a terminal acrylic group. Next, 1640 parts of an organic solvent solution of the acid anhydride adduct (a-1-1) of the esterified product (a-1) of acrylic acid with the novolac type epoxy compound obtained in Synthesis Example 1 was mixed, and the temperature was raised to 80 ° C. After warming and reacting for 6 hours, the mixture is cooled and the urethane acrylate adduct (a-1) of the acid anhydride adduct (a-1-1) of the esterification product (a-1) of the novolac type epoxy compound with acrylic acid is added.
An organic solvent solution of -2) was obtained. Synthesis example 3 Structural formula

[0038]

[Chemical 17]

Hydantoin epoxy resin (epoxy equivalent 304, softening point 67) obtained by condensing 2 mol of the compound of 1 and 5 mol of 5,5-dimethylhydantoin.
℃) 608 parts, acrylic acid 140 parts, metoquinone 0.4
Parts, 2.7 parts of triphenylphosphine, 160 parts of carbitol acetate and 160 parts of solvent naphtha were charged and reacted at 95 ° C. to obtain hydantoin epoxy acrylate (b-1).

Examples 1 to 4 and Comparative Examples 1 and 2 Premixing was carried out according to the blending composition shown in Table 1 (numerical values are parts by weight), followed by kneading 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., all were 20 μm or less. This resin composition was applied to the entire surface of a 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, a photomask with a pattern formed is brought into contact with the coating film surface, manufactured by Oak Manufacturing Co.,
The film was exposed using an ultrahigh pressure mercury lamp exposure device, the photomask was peeled off from the coating film surface, then developed with a 1% sodium carbonate aqueous solution 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 circulation furnace heated to 150 ° C. for 60 minutes to form a post cure and solder resist pattern. Table 2 shows the results of testing various properties 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 200 mJ / cm ² , 300 mJ / cm ² and 50 were used for the irradiation light quantity of ultraviolet rays having a wavelength of 365 nm using the integrated light quantity manufactured by Oak Manufacturing Co., Ltd.
The state of the coating film after irradiation with 0 mJ / cm ² and development with each developer at a spray pressure of ² kg / cm ² for 60 seconds was visually evaluated. ◯: No change was observed Δ: Surface was changed ×: Coating film fell off

(2) Developability test The resin composition was applied to the entire surface of the copper through-hole printed wiring board for 30 minutes.
It was applied to a thickness of μm, then placed in a hot air circulation furnace and left at 80 ° C. for 30, 60, and 90 minutes, respectively, and the amount of ultraviolet light having a wavelength of 365 nm was passed through a photomask and manufactured by Oak Manufacturing Co., Ltd. 500 mJ / cm ² using the integrated photometer
The irradiated piece was used as a test piece, and the state in which the unexposed portion was removed after the development was performed for 60 seconds with a developing solution (1% sodium carbonate aqueous solution) at a spray pressure of ² kg / cm ² was visually judged. ◎: Completely developed ○: There is a thin undeveloped area on the surface △: Overall undeveloped residue ×: Almost no development (3) Adhesion test Each photomask is irradiated with UV light having a wavelength of 365 nm The amount of light is 500 mJ / cm ² using an integrating photometer manufactured by Oak Manufacturing Co., Ltd.
The irradiated material is developed with a spraying pressure of ² kg / cm ² for 60 seconds with each developing solution, then post-cured into a test piece, and a cross-cut is made 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 judged by the tape. ◎: 100/100 with no peeling ○: 100/100 Cross-cut part was slightly peeled △: 50/100 to 90/100 ×: 0/100 to 50/100 (4) Pencil hardness test Adhesion Each test piece same as the test is JIS K
The hardness was measured according to the test method of 5400 under a load of 1 kg.

(5) Acid resistance test Each of the same test pieces as in the adhesion test was used at 10% by volume.
Immerse in H ₂ SO ₄ aqueous solution at 20 ° C. for 30 minutes and take out,
The state of the coating film and the adhesiveness were comprehensively evaluated. ◯: No change was observed Δ: Slightly changed ×: Blistering or swelling / shedding in the coating film (6) Alkali resistance test 10% by volume H ₂ SO ₄ aqueous solution into 10% sodium hydroxide aqueous solution Test evaluation was performed in the same manner as the acid resistance test except that the acid resistance was changed. (7) Solvent resistance test A test evaluation was performed in the same manner as the acid resistance test except that the 10% by volume sulfuric acid aqueous solution was changed to acetone.

(8) Plating resistance test Each of the same test pieces as in the adhesion test was subjected to 10 A current density of 1 A / dm ² at a liquid temperature of 30 ° C. by using "Autoronex Cl" (gold plating liquid manufactured by Cellex, USA). The state of the coating film after plating for 1.5 minutes to deposit a 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
10 in a solder bath at 260 ° C according to the test method of 6481.
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-shaped test pattern B of IPC-B-25, test pieces were produced under the same conditions as the adhesion test, and according to the test method (IPC class III) of IPC-SM-840B, Moisture absorption after 7 days and insulation resistance after contact with electricity were measured.

[0045]

Table 1 Table 1 Examples Comparative Examples * 12 1 2 3 4 1 2 Obtained in Synthesis Example 1 (a-1-1) 93 93 93 Obtained in Synthesis Example 2 (a-1-2) 100 100 Synthesis (B-1) 93 KAYARAD R-2058 * 1 20 20 20 20 20 20 KAYARAD DPHA * 2 5 5 5 5 5 5 5 propylene glycol dimethyl ether 5 5 5 5 5 5 TEPIC-S * 3 10 10 10 obtained in Example 3 5 10 5 KAYARAD SPGDA * 4 5 5 Compound (C) represented by formula (1) * 5 5 * 6 5 * 7 5 5 Compound (D) represented by formula (2) KAYACURE EPA * 8 5 5 5 5 1 5 Irgacure 907 * 9 9 KAYACURE DETX-S * 10 5 Barium sulfate 22 22 22 22 22 22 Aluminum oxide powder 5 5 5 5 5 5 Fine talc 5 5 5 5 5 5 Phthalosine anine 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 2 2 1 2 1 "2P4MHZ" * 11 1 1 1 0.5 1 0.5

Note * 1 KAYARAD R-205
8: Nippon Kayaku Co., Ltd. phenol novolac 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.
Manufactured 3,9-bis (1,1-dimethyl-2-hydroxyethyl) 2,4,8,10-tetraoxaspiro [5,
5] Undecane diacrylate (m.P. 117-12
0 ° C), powder, poorly soluble acrylate.

* 5: Compound of the above formula (5) * 6: Compound of the above formula (4) * 7: Compound of the above formula (7) * 8 KAYACURE EPA: Nippon Kayaku Co., Ltd.
Manufactured by N, N-dimethylaminobenzoic acid ethyl ester * 9 Irgacure 907: manufactured by Ciba Geigy
Photopolymerization initiator * 10 KAYACURE DETX-S: Nippon Kayaku Co., Ltd., 2,4-diethylthioxanthone * 11 "2P4MHZ": Epoxy curing agent manufactured by Shikoku Chemicals Co., Ltd. * 12 The developer of Example 3 was water. used.

[0048]

[Table 2] Table 2 Examples Comparative Examples 1 2 3 4 1 2 Photosensitivity 100 mJ / cm ² ○ ○ ○ ○ × △ 300 mJ / cm ² ○ ○ ○ ○ △ △ 500 mJ / cm ² ○ ○ ○ ○ ○ ○ Developability 30 minutes ◎ ◎ ◎ ◎ ◎ ◎ ◎ 60 minutes ◎ ◎ ◎ ◎ ○ △ 90 minutes ○ ◎ ○ ◎ △ × Adhesion ◎ ○ ◎ ◎ ◎ ◎ ○ Pencil hardness 9H 8H 7H 8H 9H 8H Acid resistance ○ ○ ○ ○ ○ ○ Alkali resistance ○ ○ ○ ○ ○ ○ Solvent resistance ○ ○ ○ ○ △ △ ○ Plating resistance ○ ○ ○ ○ △ △ Soldering 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 a large hardness, heat resistance, acid resistance, alkali resistance,
It has excellent solvent resistance, gold plating resistance, and electrolytic corrosion resistance.

[0050]

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

Claims (3)

[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, and a formula (1) ) Compound (C) represented by (In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a C _{1 to} C ₅ alkyl group or a C _{1 to} C ₅ alkoxy group. , R ₁ , R ₂ and R ₃ are simultaneously hydrogen atoms) and a compound (D) represented by the formula (2): (In the formula, R ₄ and R ₅ are C _{1 to} C ₃ alkyl groups, R ₆ is OR ₇ , —OCH ₂ CH ₂ CH ₂ OR ₇ , hydrogen atom, C
_{1 to} C ₁₃ alkyl group, phenyl group or And R ₇ is a C ₁ -C ₁₃ alkyl group. ) Is contained. 2. A photosensitive prepolymer (A) having at least two ethylenically unsaturated groups in one molecule, a diluent (B) comprising a photopolymerizable vinyl-based monomer and / or an organic solvent, the above-mentioned. A solder resist resin composition comprising a compound (C) represented by formula (1) according to item 1 and a compound (D) represented by formula (2) according to claim 1. 3. A cured product of the resin composition according to claim 1 or 2.