JPH047320A - Curable resin and curable resin composition containing the same - Google Patents

Abstract

PURPOSE:To prepare the title resin giving a cured article excellent in heat resistance, mechanical strength, hardness, etc., by reacting a specific polyepoxy compd. with (meth)acrylic acid. CONSTITUTION:A polyepoxy compd. of the formula (wherein R is 1-18C alkyl or methoxy; (n) is 0-4; X is H or halogen; Z is H or 1-10C alkyl; and (m) is a mean value and 0-3) is allowed to react with (meth)acrylic acid to give the title resin.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a heat-resistant material suitable for use in electrical component casting materials, sealing materials, adhesives, ink materials, laminated materials, optical materials, coating materials, etc. The present invention relates to a curable resin that provides a cured product with excellent properties, strength, hardness, and adhesiveness, and a curable resin composition using the curable resin.

(Prior art) In recent years, there has been a strong demand for higher performance, smaller size, lighter weight, etc. in the electrical and electronic fields, and accordingly, the thermosetting resins used have also been required to have high heat resistance, high strength, etc. The required properties of materials are becoming increasingly strict, and heat resistance has become the most stringent requirement for each material. Epoxy acrylate resins are known as thermosetting resins that meet these demands. This type of epoxy acrylate resin can be produced, for example, by adding acrylic acid to a bisphenol A epoxy resin (Japanese Patent Laid-Open No.
The cured product obtained by curing this using a radical initiator (see Publication No. 28599) has excellent electrical insulation and adhesive properties, but has poor heat resistance and mechanical strength. Because of its low viscosity, it has drawbacks such as cracking when used in the fields of electrical component casting materials and coating materials.

(Problem of the Invention) The present invention provides an epoxy acrylate curable resin that solves the above-mentioned drawbacks of conventional epoxy acrylate resins and provides a cured product with particularly excellent heat resistance and mechanical strength. The object of the present invention is to provide a method for producing a resin, a thermosetting resin composition using the curable resin, and a photocurable resin composition using the curable resin. It is.

The curable resin of the present invention has the general formula (wherein R is an alkyl group having 1 to 18 carbon atoms or a methoxy group, n is an integer of 0 to 4, and X is a hydrogen atom or a halogen atom. , Z is a hydrogen atom or has 1-1 carbon atoms
There are 0 alkyl groups, and m is a number of O to 3 on average. ) A curable resin obtained by reacting (meth)acrylic acid represented by the general formula % (in the formula, R'' represents a hydrogen atom or a methyl group) with a polyepoxy compound represented by It is.

Furthermore, the method for producing the curable resin of the present invention can be carried out using the general formula (
For one chemical equivalent of epoxy group of the polyepoxy compound represented by I),
This is a method of reacting 0.5 to 4 chemical equivalents of meth)acrylic acid in a charged amount.

Further, the thermosetting resin composition of the present invention is a composition obtained by blending a radical initiator with the above-mentioned curable resin.

Further, the photocurable resin composition of the present invention is a composition obtained by blending the above-mentioned curable resin with a photosensitizer.

The polyepoxy compound represented by the general formula (I) as a raw material used in the present invention is a polyfunctional novolac resin obtained by condensing phenols and aromatic aldehydes having a phenolic hydroxyl group under an acidic catalyst. , can be easily synthesized by reacting epihalohydrin.

Further, the (meth)acrylic acid represented by the general formula (I[) used in the present invention may be acrylic acid,
It may be methacrylic acid or a mixture of acrylic acid and methacrylic acid in any proportion.

In the present invention, the reaction between the polyepoxy compound represented by the general formula (I) and the (meth)acrylic acid represented by the general formula (II) can be carried out using a known method for producing an -i unsaturated epoxy ester. It can be easily done. That is, with respect to the chemical equivalent of 1 epoxy group of the polyepoxy compound represented by the general formula (I), the chemical equivalent of the general formula (I
The (meth)acrylic acid represented by I) is usually used in a charging ratio of 0.5 to 4 chemical equivalents, preferably 0.8 to 2 chemical equivalents, and heated at 0 to 200°C, preferably 2.
0-150°C for 1-20 hours, preferably 1-1O
Allow time to react. Examples of reaction catalysts used in this case include triethylamine, benzyldimethylamine, 1,8-
Tertiary amines such as diazabicyclo[5,4,0)undecene-7, quaternary ammonium salts such as cetyl ammonium bromide and tetramethylammonium bromide, 2-methylimidazole, 2-ethyl-4-methylimidazole, etc. Examples include imidazoles, phosphine derivatives such as triphenylphosphine, and tricyclophosphine. The amount of these reaction catalysts used is 0.01 to 100 parts by weight of the polyepoxy compound.
It is within the range of 10 parts by weight.

The reaction for producing the thermosetting resin of the present invention is preferably carried out in the presence of a radical polymerization inhibitor in order to suppress polymerization of the resulting resin. Examples of the radical polymerization inhibitor include quinones such as henzoquinone and naphthoquinone, hydroquinone, toluhydroquinone,
Examples include polyhydric phenols such as catechol, and alkyl ethers of these polyhydric phenols. The amount of these radical polymerization inhibitors used is usually determined based on reaction mixture 1.
The amount is 0.01 to 5 parts by weight per 00 parts by weight.

The reaction for producing the thermosetting resin of the present invention can be carried out in an organic solvent and/or a polymerizable unsaturated monomer that acts as a viscosity reducing agent under the reaction conditions.

Examples of the organic solvent include methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and cyclohexane, esters such as ethyl acetate and butyl acetate, 1.4
-Ethers such as dioxane and tetrahydrofuran,
Examples include glycol derivatives such as cellosolve and butyl cellosolve, and aromatic hydrocarbons such as toluene and xylene.

Examples of the polymerizable unsaturated monomer include vinyl compounds such as styrene and divinylbenzene, and methyl (
meth)acrylate, benzyl(meth)acrylate,
Examples include (meth)acrylic compounds such as 1,6-hexanethiol di(meth)acrylate and trimethylolpropane tri(meth)acrylate, and allyl compounds such as diallyl phthalate and diethylene glycol bisallyl carbonate.

The curable resin of the present invention obtained by reacting in the above organic solvent or polymerizable unsaturated monomer can be cured by removing the organic solvent or monomer before curing, or In the case of a monomer, it can be used as it is as long as the properties such as heat resistance and mechanical strength of the cured resin are not deteriorated.

The curable resin of the present invention obtained as described above can be easily cured by radical polymerization means. In particular, by blending a radical initiator such as an organic peroxide or an azo compound with this curable resin and heating the composition, or by blending a photosensitizer with the composition, it is exposed to ultraviolet rays, electron beams, etc. It can be easily hardened by irradiating with radiation or the like.

Various radical initiators can be used, including organic peroxides such as hendyl peroxide, diisopropyl peroxide and lauryl peroxide; and ab compounds such as azoisobutyronitrile. In addition, examples of the photosensitizer include benzophenone, hendiine ethyl ether, acetophenone,
Examples include anthraquinone. The amount of these radical polymerization initiators or photosensitizers used is usually 0.0 parts by weight per 100 parts by weight of the thermosetting resin obtained by the production method of the present invention.
It ranges from 1 to 20 parts by weight, preferably from 0.1 to 10 parts by weight.

(Examples etc.) Below, polyepoxy compound production examples, examples, and comparative examples are given and explained in detail. In these examples, "parts" and "%" are based on weight.

The physical properties of the cured thermosetting resins obtained in Examples and Comparative Examples were measured by the following test methods.

■ Glass transition point It was measured with a differential scanning calorimeter (DSC).

(2) Heat resistance Measured using a heat deformation tester according to ASTM-D-648.

(2) Strength Bending strength and elastic modulus were measured according to JIS K-6911.

■ Hardness Measured using a pencil hardness tester according to JIS K-6911.

(2) Adhesion Measured by a cross-cut peel test according to JIS K-5400.

Polyepoxy compound production example 1 Capacity 1 equipped with thermometer, stirrer, and cooler! 210g of phenol and 60g of salicylaldehyde in a three-bottle flask.
g5p-) Prepare 2 g of luenesulfonic acid and heat at 100°C.
After reacting for 4 hours, unreacted phenol was removed. Next, 750 g of epichlorohydrin and 1 g of tetraethylammonium chloride were added, and the reaction was carried out under reflux at 117°C for 2 hours, then cooled to 60°C, a water separator was attached, 842 g of Na was added, and 40 to 110 g of Na was added.
The produced water was removed from the system while controlling the temperature to 50 to 70°C under a reduced pressure of 0InInH, and the reaction was allowed to proceed for about 2 hours.

After adding 2.51 g of methyl isobutyl ketone to the obtained reaction solution and washing off the salt and NaOH in the solution with a large amount of water, epichlorohydrin and methyl isobutyl ketone were added using an evaporator to 100 to 0.1 g of methyl isobutyl ketone. m
Removed at 60-150 °C under reduced pressure of mHg, yield 17
8 g of a pale yellow transparent solid polyepoxy compound having a softening point of 65° C. and an epoxy equivalent of 197 was obtained. This polyepoxy compound has a value of m in the general formula (I) of 0.3.
Met.

Polyepoxy compound production example 2 O-cresol 2 was used instead of phenol in production example 1 above.
Using 40 g, the reaction was otherwise carried out in accordance with the method of Production Example 1, followed by post-treatment to obtain a pale yellow, transparent solid polyepoxy compound with a yield of 201 g, a softening point of 72° C., and an epoxy equivalent of 210. This polyepoxy compound has the general formula (I
) The average value of m was 0.3.

Example 1 Capacity 1 with thermometer, stirrer, water separator, nitrogen inlet tube
In the fourth flask of No. 1, 197 g of the polyepoxy compound obtained in Production Example 1, 100 g of methyl isobutyl ketone, and 1 portion of hydroquinone monomethyl ether.
After stirring and dissolving 4 g of triphenylphosphine, the temperature was raised to 90°C and 80 g of acrylic acid was mixed with 30 g of triphenylphosphine.
The solution was added dropwise over a period of minutes, and after the completion of the addition, the temperature was kept at the same temperature for 4 hours to allow the reaction to occur.

After the reaction is completed, it is cooled, the excess acid is neutralized with an aqueous solution of sodium carbonate, and the organic layer is washed three times with pure water, and the methyl isobutyl ketone is distilled off using an evaporator to form a thermosetting resin. 230 g were obtained as a pale yellow viscous liquid.

1 part of benzoyl peroxide was added to 100 parts of this thermosetting resin, heated to 60°C, stirred and mixed uniformly, degassed under a reduced pressure of 0.1 mnHg, and then molded. injected at 80°C for 6 hours, then at 120°C.
It was held at °C for 4 hours to polymerize and harden.

The cured product was removed from the mold and the various physical properties were evaluated.
It is shown in Experiment No. 1 of Example 1 in Table 1.

Further, 3 parts of hendiyl ethyl ether was added to this thermosetting resin 100, heated to 60°C, stirred and mixed uniformly, defoamed in the same manner as above, and this liquid was
After applying it to a test piece using an applicator, it was cured by irradiating it with ultraviolet rays for 1 minute using a high-pressure mercury lamp with an output of 80 W/cm.

The evaluation results of this cured product are shown in Experiment Nα2 of Example 1 in Table 1.

Example 2 Instead of the polyepoxy compound obtained in Production Example 1, 210 g of the polyepoxy compound obtained in Production Example 2 was used, otherwise the reaction was carried out in the same manner as in Example 1, and treated in the same manner. 250 g of thermosetting resin was obtained as a pale yellow viscous liquid.

Table 1 shows the evaluation results of various physical properties of the cured product obtained by curing this thermosetting resin in the same manner as in the experiment No. 1 of Example 1.

Comparison Example Instead of the polyepoxy compound used in Example 1, 190 g of a bisphenol A-based polyepoxy compound (trade name Epicoat 82B, manufactured by Yuka Shell Epoxy Co., Ltd.) was used.
Other than that, the reaction was carried out in the same manner as in Example 1, and the same treatment was carried out to obtain a colorless, transparent and viscous liquid polyepoxy compound 23.
5g was obtained.

1 part of benzoyl peroxide was added to 100 parts of this polyepoxy compound and cured in the same manner as in the experiment No. 1 of Example 1. The evaluation results of the cured product are shown in Table 1.

(Effects of the Invention) The thermosetting resin of the present invention can provide a cured product with excellent heat resistance, mechanical strength, hardness, and the like.

Claims (1)

[Claims] (I) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R is an alkyl group or methoxy group having 1 to 18 carbon atoms, and n is 0 to 4 is an integer, X is a hydrogen atom or a halogen atom, and Z is a hydrogen atom or a carbon number of 1 to 1
There are 0 alkyl groups, and m is a number from 0 to 3 on average. ) Polyepoxy compounds represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R' represents a hydrogen atom or a methyl group) are reacted with (meth)acrylic acid represented by curable resin obtained by (2) The charged amount of (meth)acrylic acid represented by general formula (II) is 0.5 per chemical equivalent of epoxy group of the polyepoxy compound represented by general formula (I) according to claim 1. 2. The method for producing a curable resin according to claim 1, wherein the reaction is performed in an amount of 4 to 4 chemical equivalents. (3) A thermosetting resin composition obtained by blending a radical initiator with the curable resin according to claim 1. (4) A photocurable resin composition obtained by blending the curable resin according to claim 1 with a photosensitizer.