JP3319621B2 - Epoxy (meth) acrylate, polymerizable 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 an epoxy (meth) acrylate and an electric component casting material, an adhesive, an ink material, an optical material, a coating material, a solder resist material for a printed wiring board and the like containing the same. The present invention relates to a polymerizable resin composition suitable for use and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, epoxy acrylate has been used as a polymerizable resin such as an electric component casting material, an adhesive, an ink material, an optical material, a coating material, and a solder resist material for a printed wiring board. In recent years, components used in the electric and electronic fields have been required to have high performance, small size, light weight, etc., and accordingly, high heat resistance, high strength, etc. of polymerizable resins to be used. Is getting tougher. The conventional bisphenol A-based epoxy acrylate has low heat resistance and low mechanical strength, and thus has a defect such as cracking when used for casting electric parts or as a coating material.

[0003]

SUMMARY OF THE INVENTION The present invention provides an epoxy (meth) acrylate polymerizable resin which solves the above-mentioned drawbacks of the conventional epoxy acrylate resin and which gives a cured product having particularly excellent heat resistance and mechanical strength. It is an object of the present invention to provide a heat and photopolymerizable resin composition using the same polymerizable resin, and to provide a cured product thereof.

[0004]

Means for Solving the Problems In order to solve the above-mentioned drawbacks, the present inventors have made intensive studies and have developed a novel epoxy (meth) acrylate, and by using it, the storage stability has been improved. Good, can be heat-cured at relatively low temperature, suitable for casting materials, coating materials, especially solder resist inks that give cured products with excellent adhesion to various substrates, chemical resistance, electrical insulation properties and hardness. The present invention was completed by successfully providing a resin composition. That is,
The present invention relates to 1) Formula (1)

[0005]

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(In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 0 to 30 and G represents a glycidyl group. 2) an epoxy (meth) acrylate which is a reaction product of a polyepoxy compound represented by the formula (1) and (meth) acrylic acid; 2) an epoxy (meth) acrylate (A) described in 1) above and a radical polymerization initiator (B). 3) A photopolymerizable resin composition comprising the epoxy (meth) acrylate (A) described in the above item 1) and a photopolymerization initiator (C). 4) a cured product of the polymerizable resin composition according to the above item 1) or 2).

The epoxy (meth) acrylate (A) of the present invention can be obtained by reacting a polyepoxy compound represented by the formula (1) with (meth) acrylic acid. Here, (meth) acrylic acid means acrylic acid or methacrylic acid or a mixture thereof. As described above, the polymerizable resin composition of the present invention can be used for a casting material, a coating material, and a solder resist ink. In addition, it can be used for an adhesive, a general ink, and a paint field. Useful as Hereinafter, each of the components constituting the polymerizable resin composition of the present invention will be described in detail. A typical reactant obtained by reacting the polyepoxy compound represented by the formula (1) with (meth) acrylic acid is represented by the formula (2)

[0008]

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(In the formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n represents 0 to 30. A represents an acryloyl group,
Or a methacryloyl group. ). The polyepoxy compound represented by the above formula (1) used in the present invention is, for example, a compound represented by the formula (3) as described in Synthesis Example 1.

[0010]

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In the formula (3), R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a naphthol represented by the formula (4):

[0012]

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(In the formula (4), R ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom.) A halogen-containing phenol represented by the formula: And further reacting with epihalohydrin in the presence of an alkali metal hydroxide. The reaction between the compound represented by the formula (1) and the (meth) acrylic acid is performed by converting (meth) acrylic acid to about 0.1 to 1 chemical equivalent of the epoxy group of the compound represented by the formula (1). The reaction is carried out at a ratio of 1.0 chemical equivalent, and at the time of the reaction, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexane, esters such as ethyl acetate and butyl acetate, ethers such as 1,4-dioxane and tetrahydrofuran, and ethyl cellosolve , Glycol derivatives such as butyl cellosolve acetate, solvents such as aromatic hydrocarbons such as toluene, or alkylene oxide addition of carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, acryloylmorpholine, bisphenol A or hydrogenated bisphenol A Diacrylates, trimethylol Polymerizable unsaturated compounds such as (meth) acrylic compounds such as lopantri (meth) acrylate and dipentaerythritol poly (meth) acrylate, allyl compounds such as diallyl phthalate and diethylene glycol bisallyl carbonate, and vinyl compounds such as styrene and N-vinylpyrrolidone. It is preferable to use a monomer as a diluent, and to further promote the reaction, it is preferable to use a catalyst such as triethylamine, benzyldimethylamine, methyltriethylammonium chloride, and triphenylstibine. It is preferably 0.1 to 10% by weight, particularly preferably 1 to 5% by weight, based on the raw material mixture. In order to prevent polymerization during the reaction, it is preferable to use a thermal polymerization inhibitor such as methoquinone, hydroquinone, and phenothiazine, and the amount of the thermal polymerization inhibitor is preferably 0.01 to 1 based on the raw material mixture.
%, Particularly preferably 0.05 to 0.5% by weight. The reaction temperature is preferably from 60 to 150 ° C, particularly preferably from 80 to 120 ° C.

In the polymerizable resin composition of the present invention, the amount of the epoxy (meth) acrylate (A) used is preferably 5 to 99.9 with respect to the thermopolymerizable resin composition. %, Particularly preferably 10 to 97% by weight, and in the case of a photopolymerizable resin composition, preferably 5 to 99% by weight, more preferably 10 to 9% by weight, based on the composition.
5% by weight. As the radical polymerization initiator (B), any known radical polymerization initiator can be used, and examples thereof include benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, P-chlorobenzoyl peroxide, cyclohexanone peroxide, and dihexyl peroxide. Organic peroxides such as t-butyl peroxide and acetylacetone peroxide; and azo compounds such as azoisobutyronitrile are exemplified. The amount of the radical polymerization initiator used is preferably from 0.01 to 5% by weight, particularly preferably from 0.1 to 3% by weight, based on the thermopolymerizable resin composition of the present invention. An accelerator can be used in combination with the organic peroxide, and various known accelerators can be used, for example, dimethylaniline,
Cobalt naphthenate and the like. The accelerator is preferably used in a proportion of 5 to 300% by weight based on the organic peroxide.

Photopolymerization initiator (C) used in the present invention
Specific examples of benzoin, benzoin methyl ether, benzoin ethyl ether, benzoins such as benzoin isopropyl ether, acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
Acetophenones such as diethoxy-2-phenylacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, anthraquinones such as 1-chloroanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone and hydroxybenzophenone or xanthones, 1-hydroxycyclohexyl phenyl ketone (Irgacure 184, manufactured by Ciba-Geigy KK), 1- (4-isopropylphenyl) ) -2-Hydroxy-2-methyl-propan-1-one (Darocur 1116, manufactured by Merck & Co., Ltd.), 2-hydroxy-2-methyl-1-phenyl-propane Reaction products of photopolymerization initiators such as 1-one (Derocure 1173, Merck Co., Ltd.) and photopolymerization initiators having a hydroxyl group with isocyanate compounds having a (meth) acryloyl group, and halides having a (meth) acryloyl group And the like. The amount of the photopolymerization initiator to be used is preferably 0.5 to 10% by weight, particularly preferably 1 to 5% by weight, based on the photopolymerizable resin composition of the present invention. The speed tends to be low, and if it exceeds 10% by weight, the cured product tends to be brittle.

In the polymerizable resin composition of the present invention, in addition to the above essential components, if necessary, other reactive compounds (for example, the polymerizable unsaturated monomer used as the diluent), and thermal crosslinking Agents, polymerization inhibitors, tackifiers, thickeners, leveling agents,
A fluidity improver, a matting agent, a solubilizer, a solvent, a filler, a coloring agent such as a pigment or a dye, and other auxiliaries can be used in combination. Further, the polymerizable resin composition of the present invention can be used after being emulsified. The polymerizable resin composition of the present invention is obtained by uniformly mixing the respective components, using a dispenser, a deep coater, a roll coater, a knife coater, a spray coater, screen printing, offset printing, and other ordinary coating and printing devices. Painted or printed. The epoxy (meth) acrylate of the present invention can be cured by electron beam irradiation. or,
A composition using a radical polymerization initiator can be cured by heating to preferably 50 to 200 ° C. with an infrared lamp, hot air or the like, and a composition using a photopolymerization initiator can be a high-pressure mercury lamp, a metal halide lamp or a xenon lamp. And the like, and can be cured by an ordinary method by ultraviolet irradiation. The polymerizable resin composition of the present invention is excellent in storage stability and gives a cured product excellent in heat resistance, strength, adhesion, chemical resistance, electrical insulation properties and hardness.

[0017]

The synthesis examples, examples and comparative examples are shown below.
The present invention will be described more specifically, but the present invention is not limited to only these examples. The evaluation of various properties of the composition and the cured product thereof was performed by the following methods. (Glass transition temperature) Viscoelasticity analyzer (Seiko Electronics, D
MS-100, 10 cycles). (Heat resistance) The heat deformation temperature was measured by a heat deformation test apparatus according to ASTM-D-648. (Strength) Flexural strength and elastic modulus were measured according to JIS K-6911. (Surface hardness) The pencil hardness according to JIS K56651-1966 was measured. (Adhesion) Cross-cut cellophane tape peel test for crosslinked cured film. That is, 11 cut lines are vertically and horizontally inserted into the coating to reach the substrate at 1 mm intervals, and 1 mm
^Two hundred stitches were made, a cellophane tape was stuck thereon, and they were rapidly peeled off, and the peeled state was measured.・: No peeling ・: partial peeling ×: all peeling (storage stability) The resin composition was left at 30 ° C., and the number of days until thickening or gelation was measured. (Solubility) Ultraviolet light was irradiated using a 5 kw ultra-high pressure mercury lamp, and then the non-irradiated portion was dissolved and removed with 25 ° C. trichloroethane to determine the solubility.・: The dissolution rate is fast. ×: not dissolved or extremely slow. (Solder Resistance) The state of the coating film after immersion in molten solder at 260 ° C. for 2 minutes was determined. ○ ・ ・ ・ ・ ・ ・ No abnormal appearance of the coating film. ×: Blistering, melting, peeling. (Insulation Resistance) The coating film was left standing in an atmosphere of 80 ° C. and 95% RH for 240 hours, and the insulation resistance of the coating film was measured.

Synthesis Example 1 (Synthesis of polyepoxy compound) 1 L equipped with a thermometer, a cooling pipe, a liquid separating device, and a stirrer
In a reaction flask, 288 parts by weight of 1 naphthol (2 mol) and 126 parts by weight of 2,4-dibromophenol (0.
5 mol) was dissolved at 150 ° C. Next, 41 parts by weight (1.0 mol) of flaky sodium hydroxide (pure content: 99% by weight) was added at once, and then reacted at 170 ° C. for 2 hours. The reaction temperature rose temporarily to 210 ° C. During the reaction, generated water and phenol were distilled off, but after cooling, water was removed and oil was returned to the reaction system. After the completion of the reaction, the mixture was cooled to 120 ° C., and 400 parts by weight of methyl isobutyl ketone and 300 parts by weight of water were added under stirring, and the mixture was allowed to stand, and the aqueous layer was removed. After neutralization with a 20% aqueous solution of sodium dihydrogen phosphate, washing with water was repeated. Thereafter, methyl isobutyl ketone, unreacted 1-naphthol, and the like were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 179 parts by weight of a pale yellow, transparent, and solid polyphenol resin at room temperature. The softening point of the obtained polyphenol resin is IC at 121 ° C. and 150 ° C.
The I viscosity was 15 poise and the hydroxyl equivalent was 143. Next, 172 parts by weight of the obtained polyphenol resin (1.2 hydroxyl equivalents), 666 parts by weight of epichlorohydrin (6 mol), and 167 parts by weight of DMSO were charged, and after the resin component was dissolved, the temperature was raised to 40 ° C. Next, 51 parts by weight of flaky sodium hydroxide (99% pure content) was added to the system under stirring over 100 minutes. After the addition is complete,
The reaction was carried out at 50 ° C. for 1 hour and at 70 ° C. for 1 hour. After the completion of the reaction, water washing was repeated, the aqueous layer was separated and removed, excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 500 parts by weight of methyl isobutyl ketone was added to the residue,
The residue was dissolved. Further, the solution of methyl isobutyl ketone was heated to 70 ° C., 16 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was reacted for 1 hour. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to obtain 225 parts by weight of a pale yellow, transparent, solid polyphenol epoxy resin (polyepoxy compound) at room temperature.

Example 1 (Synthesis of Epoxy Acrylate) The polyepoxy compound 160 obtained in Synthesis Example 1 was placed in a 1 L reaction flask equipped with a thermometer, a cooling tube, and a stirrer.
g, 320 g of methyl isobutyl ketone, 0.11 g of hydroquinone monomethyl ether, 52 g of acrylic acid, and 1.1 g of triphenyl phosphate. After stirring and dissolving, the temperature was raised to 90 ° C. and maintained at the same temperature for 13 hours. And reacted. After the completion of the reaction, methyl isobutyl ketone was distilled off with an evaporator to obtain an epoxy acrylate 10
6 g were obtained. This epoxy acrylate is represented by the formula (2) (R ₁ = R ₂ = H, n = 0.8) and has a viscosity of 23.
1PS / 60 ° C. The obtained epoxy acrylate was subjected to ¹ H-NMR (300 MH) using a CDCl ₃ solvent.
z) When analyzed, 6.8-8.5 ppm, 5.6-
A peak was observed at 6.6 ppm, 3.5 to 4.7 ppm, and IR analysis using a KBr plate revealed that the peak was 172.
Since a peak was observed at 5 cm ^-1 , this resin was converted to an epoxy acrylate represented by the formula (2) (R ₁ = H,
R ₂ = H). Example 2 Epoxy acrylate 100 obtained according to Example 1
1 part of benzoyl peroxide was added to the mixture, and the mixture was heated to 60 ° C., uniformly stirred and mixed, degassed under reduced pressure, poured into a mold, and kept at 90 ° C. for 5 hours and at 120 ° C. for 5 hours to carry out polymerization.
Cured. When the cured product was taken out of the mold and evaluated for physical properties, the results shown in Table 1 were obtained.

Example 3 To 100 parts of the epoxy acrylate obtained in Example 1, 3 parts of 1-hydroxycyclohexylphenyl ketone (Irg-184, manufactured by Ciba Geigy) was added, and the mixture was heated to 60 ° C. and uniformly stirred and mixed. After defoaming under reduced pressure, this liquid was applied to a test piece with a thickness of 200 μm, and irradiated with 500 mj / cm ^{2 from} a high-pressure mercury lamp of 80 W / cm to be cured. When the physical properties of this cured product were evaluated, the results shown in Table 1 were obtained. Comparative Example 1 An epoxy acrylate was obtained in the same manner as in Example 1, except that a bisphenol A-based polyepoxy compound (Epicoat 828, manufactured by Yuka Shell Epoxy) was used instead of the polyepoxy compound used in Synthesis Example 1. Was. One part of benzoyl peroxide was added to 100 parts of the epoxy acrylate, and cured in the same manner as in Example 2. The physical properties of the cured product were evaluated. The results shown in Table 1 were obtained.

Example 4 A solder resist resin composition was blended according to the blending composition shown in Table 2, mixed uniformly at 50 to 80 ° C., and then sufficiently kneaded with three rolls to obtain a copper foil for a printed wiring board. After applying to the foil about 30μ thickness by screen printing method,
The composition was cured by ultraviolet rays, and the physical properties of the cured coating film were evaluated. The results shown in Table 2 were obtained. Example 5 A solder resist resin composition was blended according to the blending composition shown in Table 2, mixed uniformly at 50 to 80 ° C., and then thoroughly kneaded with three rolls onto a copper foil of a printed wiring board. The coating was applied to a thickness of about 60 μm by screen printing, the solvent was removed by heating, and the coating was cured with ultraviolet rays. The physical properties of the cured coating film were evaluated. The results shown in Table 2 were obtained.

[0022]

Table 1 Example 1 Example 2 Example 3 Comparative Example 1 Glass transition temperature (° C.) 185 150 100 Heat distortion temperature (° C.) 200 180 120 Flexural strength (Kg / cm ² ) 12 119 Modulus of elasticity (Kg / cm) ² ) 390 340 230 Surface hardness 3H 3H HB Adhesion Glass plate ○ ○ ○ Aluminum ○ ○ ○ Copper plate ○ ○ ○

[0023]

Table 2 Example 4 Example 5 Epoxy acrylate obtained in Example 1 1334.0 TMPTA 38 1.1 2-HEMA 15 Talc 27 16.3 Modaflow 1 Aerosil # 300 3 EOCN-104 10.9 SP-170 0.1 2-EAQ 3 DETX 2.2 EPA 2.2 Butyl cellosolve acetate 33.2 Storage stability 30 days or more 30 days or more Solubility-○ Solder resistance ○ ○ Adhesion Insulation resistance (Ω) 3. 0 × 10 ¹³ 5.6 × 10 ¹³ Surface hardness 3H 4H In Table 2, the numerical values of each component indicate parts by weight.

TMPTA: trimethylolpropane triacrylate (manufactured by Nippon Kayaku Co., Ltd.) 2-HEMA: 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Aerosil # 300: thixotropic agent EOCN-104: cresol novolac type Epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) SP-170: Cationic photopolymerization catalyst (manufactured by Asahi Denka Co., Ltd.) 2-EAQ: 2-ethylanthraquinone, rust polymerization initiator (manufactured by Nippon Kayaku Co., Ltd.) DETX: 2,4-diethylthioxanthone, photopolymerization initiator (manufactured by Nippon Kayaku Co., Ltd.) EPA: P-dimethylaminobenzoic acid ethyl ester,
Photopolymerization accelerator (Nippon Kayaku Co., Ltd.)

[0025]

The polymerizable resin composition containing the compound of the present invention can provide a cured product excellent in heat resistance, mechanical strength, hardness, etc., and can be used for coating agents, inks, adhesives, etc., especially solder resists. Suitable for ink.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁷ , DB name) C08G 59/17 C08F 220/30 C08F 299/02-299/08

Claims (4)

(57) [Claims] (1) Formula (1) (In the formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0
~ 30. G represents a glycidyl group. Epoxy (meth) acrylate which is a reaction product of the polyepoxy compound represented by the formula (1) and (meth) acrylic acid. 2. A thermopolymerizable resin composition comprising the epoxy (meth) acrylate (A) according to claim 1 and a radical polymerization initiator (B). 3. A photopolymerizable resin composition comprising the epoxy (meth) acrylate (A) according to claim 1 and a photopolymerization initiator (C). 4. A cured product of the polymerizable resin composition according to claim 2 or 3.