JPH09272722A - Resin composition for electrical insulation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for electrical insulation which has an excellent curability/dryability and a low viscosity, and gives a coating film having a satisfactory appearance. SOLUTION: The composition comprises as essential components 5-70 pts.wt. epoxy acrylate resin (A) obtained through esterification using a quaternary phosphonium as a catalyst, 95-30 pts.wt. unsaturated polyester resin (B) modified with 5-30wt.% thermoplastic polyester resin, and a reactive monomer (C). The amount of the catalyst in the component (A) is 0.1-1.0 pt.wt. based on the epoxy acrylate resin, and that of the monomer (C) is 40-300 pts.wt. per 100 pts.wt. the sum of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition for electrical insulation, which has a low viscosity, a good coating film appearance, and an excellent curing and drying property.

[0002]

2. Description of the Related Art Resin compositions containing epoxy acrylate resins have excellent mechanical, electrical, thermal characteristics, chemical characteristics, curing characteristics, etc., and are therefore used in various fields. It is used for business.

[0003]

However, since 2,4,6-trisdimethylaminomethylphenol (TAP) is mainly used as a reaction catalyst when producing an epoxy acrylate resin, there is a limit to the curing and drying property. there were. The reason is that TAP is involved in the termination reaction of radical polymerization using organic peroxide as a reaction initiator, so that the curing and drying reaction is delayed.

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a resin composition for electrical insulation which is excellent in curing and drying properties, has a low viscosity, and has a good coating film appearance.

[0005]

DISCLOSURE OF THE INVENTION As a result of intensive studies to achieve the above object, the present inventor has found that the composition described below containing an epoxy acrylate resin can achieve the above object. The present invention has been completed.

That is, according to the present invention, (A) 5 to 70 parts by weight of an epoxy acrylate resin esterified with a quaternary phosphonium as a catalyst, and (B) a modified polyester modified with 5 to 30% by weight of a thermoplastic polyester resin. Saturated polyester resin
95 to 30 parts by weight and (C) a reactive monomer as an essential component, 0.1 to 1.0 part by weight of the quaternary phosphonium catalyst in (A) with respect to the epoxy acrylate resin, and (C) a reactive monomer. Resin component [(A) + (B)]
The resin composition for electrical insulation is characterized by being mixed in a ratio of 40 to 300 parts by weight with respect to 100 parts by weight.

Hereinafter, the present invention will be described in detail.

The (A) epoxy acrylate resin used in the present invention is, for example, one or more epoxy resins such as bisphenol A type, bisphenol F type, polyphenol type, halogenated bisphenol type, polyvalent glycidyl ester type and the like. It is obtained by the esterification reaction of the epoxy group with one or more of acrylic acid or methacrylic acid or a derivative thereof while suppressing the polymerization of the acrylic group. Further, if necessary, ester modification with phthalic anhydride, tetrahydrophthalic anhydride, or the like can be performed.

The epoxy resin for synthesizing the epoxy acrylate resin preferably has an epoxy equivalent of 1000 or less, preferably 500 or less. Epoxy equivalent is 1
If it exceeds 000, the solubility in the reactive monomer is significantly lowered, which is not preferable. The mixing ratio of the epoxy acrylate resin is preferably 5 to 70 parts by weight. The amount
If it is less than 5 parts by weight, sufficient mechanical, electrical and thermal characteristics cannot be obtained, and if it exceeds 70 parts by weight, the viscosity does not decrease,
It is not preferable because air-drying property and sufficient flexibility cannot be obtained.

The quaternary phosphonium used in the present invention is used as a reaction catalyst for reacting an epoxy resin with acrylic acid. The compounding ratio of this quaternary phosphonium is the above-mentioned (A) epoxy acrylate resin 10
It is desirable to add 0.1 to 1.0 part by weight to 0 part by weight. If this proportion is less than 0.1 parts by weight, the reaction time becomes short, and if it exceeds 1.0 parts by weight, the stock life becomes short, which is not preferable.

The (B) modified unsaturated polyester resin used in the present invention is an unsaturated polyester resin modified with a thermoplastic polyester resin. Examples of the thermoplastic resin used for modification include polyethylene terephthalate, polybutylene terephthalate, and the like. One or more of these are used to modify the unsaturated polyester resin by transesterification or the like. The modification ratio of the modified unsaturated polyester resin is preferably such that the thermoplastic polyester resin is contained in an amount of 5 to 30% by weight based on the modified unsaturated polyester resin. If the content of the thermoplastic polyester resin is less than 5% by weight, the mechanical properties are insufficient, and if it exceeds 30% by weight, the air-drying property is deteriorated, which is not preferable.

The unsaturated polyester resin is obtained by reacting an acid component and an alcohol component. As the acidic component used here, maleic acid, maleic anhydride, unsaturated acids such as fumaric acid and phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, Examples thereof include saturated acids such as hexahydrophthalic anhydride and adipic acid, and these can be used alone or in combination of two or more kinds. As the alcohol component, propylene glycol,
Examples thereof include ethylene glycol, dipropylene glycol, diethylene glycol, 1,3-butanediol, neopentyl glycol, glycerin, pentaerythritol, and polyether polyalcohol, which may be used alone or
Two or more kinds can be mixed and used. Further, the unsaturated polyester resin can be modified by adding a modifying component other than the thermoplastic polyester resin, if necessary.
Examples of the modifying component other than the thermoplastic polyester resin include linseed oil, soybean oil, tall oil, petroleum resin, dicyclopentadiene, etc. These may be used alone or in combination of two or more.

The content of the modified unsaturated polyester resin is preferably 95 to 30 parts by weight. If the amount is less than 30 parts by weight, sufficient flexibility cannot be obtained, and if it exceeds 95 parts by weight, sufficient mechanical, electrical and thermal characteristics cannot be obtained, which is not preferable.

Examples of the (C) reactive monomer used in the present invention include styrene, styrene derivatives, acrylic acid esters,
Methacrylic acid ester, various allyl esters and the like can be mentioned, and these can be used alone or in combination of two or more kinds. The proportion of the reactive monomer is preferably 40 to 300 parts by weight based on 100 parts by weight of the total amount of the above-mentioned (A) epoxy acrylate resin and (B) modified unsaturated polyester resin. If the blending ratio is less than 40 parts by weight, the viscosity is high and the workability is impaired, and if it exceeds 300 parts by weight, sufficient mechanical and thermal properties cannot be obtained, which is not preferable.

The resin composition for electrical insulation of the present invention contains an epoxy acrylate resin using quaternary phosphonium as a reaction catalyst, a modified unsaturated polyester resin and a reactive monomer as essential components. Other components such as a curing agent, a curing accelerator, a polymerization inhibitor, a colorant, a defoaming agent, and a leveling agent may be added and compounded as long as they do not conflict with each other. Examples of the curing agent include organic peroxides such as benzoyl peroxide, tertiary butyl peroxide, acetyl peroxide and other acyl peroxides, cumene hydroxide peroxide, and the like. These may be used alone or in combination of two or more. can do. The amount of curing agent added is 100
It is desirable to add 0.5 to 3.0 parts by weight to parts by weight. Examples of the curing accelerator include metal salts of naphthenic acid or octenoic acid (metal salts of cobalt, manganese, zinc, zirconium, etc.), and these can be used alone or in combination of two or more. Examples of the polymerization inhibitor include quinones such as hydroquinone, paratertiary butyl catechol, and pyrogallol, which may be used alone or in combination of two or more.

The resin composition for electrical insulation of the present invention is produced by mixing an epoxy acrylate resin, a modified unsaturated polyester resin, a reactive monomer, a quaternary phosphonium and other components, and uniformly stirring and mixing them. can do. The resin composition for electrical insulation thus produced can be widely used in the field of electrical insulation.

[0017]

Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”. A. [Production of Epoxy Acrylate Resin] A-1 Epoxy resin Epicoat # 828 (trade name of Shell Co., epoxy equivalent 180-200) 160 parts, Epicoat # 1001 of epoxy resin (trade name of Shell Co., epoxy equivalent 450-525) ) 100 parts, 169 parts of methacrylic acid, 1 part of triphenylbenzylphosphonium bromide and 0.08 part of hydroquinone are reacted at 90 to 100 ° C to give an acid value of 25
Resin was obtained. Hydroquinone (0.02 parts) and styrene (55 parts) were added to the resin (45 parts) and dissolved by stirring to produce an epoxy acrylate resin.

A-2 2-hydroxyethyl methacrylate 120 parts, tetrahydrophthalic anhydride 140 parts, triphenylbenzylphosphonium bromide 0.65 parts and hydroquinone 0.09 parts were reacted at 90 to 100 ° C. for 2 hours,
Next, Epoxy Coat # 828 (supra) 183
Parts were added and reacted at 90 to 100 ° C. to obtain a resin having an acid value of 10. 45 parts of this resin are mixed with 0.02 parts of hydroquinone and styrene.
55 parts were added and dissolved by stirring to produce an epoxy acrylate resin.

A-3 120 parts of 2-hydroxyethyl methacrylate, 140 parts of tetrahydrophthalic anhydride, 0.65 parts of 2,4,6-trisdimethylaminomethylphenol and 0.09 parts of hydroquinone were reacted at 90 to 100 ° C. for 2 hours,
Next, Epoxy Coat # 828 (supra) 183
Parts were added and reacted at 90 to 100 ° C. to obtain a resin having an acid value of 10. 45 parts of this resin are mixed with 0.02 parts of hydroquinone and styrene.
55 parts were added and dissolved by stirring to produce an epoxy acrylate resin. B. [Production of modified unsaturated polyester resin] B-1 160 parts of polyethylene terephthalate, 190 parts of neopentyl glycol and tetrabutyl titanate
After 0.1 part was reacted at 210 to 230 ° C. for 2 hours and cooled, 150 parts of maleic anhydride and 0.02 part of hydroquinone were added and reacted at 180 to 190 ° C. to obtain a resin having an acid value of 25.
Hydroquinone (0.01 part), styrene (45 parts) and 2-hydroxyethyl methacrylate (10 parts) were added to the resin (45 parts) and dissolved by stirring to produce a modified unsaturated polyester resin.

B-2 polyethylene terephthalate 160
Part, diethylene glycol 200 parts and tetrabutyl titanate 0.1 part were reacted at 210 to 230 ° C. for 2 hours and then cooled, then maleic anhydride 150 parts and hydroquinone were added.
A resin having an acid value of 20 was obtained by adding 0.02 part and reacting at 180 to 190 ° C. Hydroquinone 0.01 parts, styrene 45 parts and 2-hydroxyethyl methacrylate 10 parts
Parts were added and dissolved by stirring to produce a modified unsaturated polyester resin.

Example 1 100 parts of A-1 epoxy acrylate resin, 160 parts of B-2 modified unsaturated polyester resin, 6 parts as a curing accelerator
% Cobalt naphthenate 0.05 part and 1,1-as hardener
Bis (tert-butylperoxy) 3,3,5-trimethylcyclohexane (2 parts) was added and uniformly mixed and stirred to produce a resin composition for electrical insulation.

Example 2 A resin composition for electrical insulation was produced in the same manner as in Example 1 with the composition shown in Table 1.

Comparative Examples 1 and 2 An electrical insulating resin composition was produced in the same manner as in Example 1 except that the composition shown in Table 1 was used.

The resin compositions for electrical insulation produced in Examples 1 and 2 and Comparative Examples 1 and 2 were flow-coated on a tin plate plate to form a coating film, and then a curing and drying test was conducted. The results are shown in Table 1. The present invention was excellent, and its effects could be confirmed.

[0025]

[Table 1] * 1: A tin plate coated with a resin composition for electrical insulation was vertically hung in a 120 ° C thermostat, and after 10 minutes, it was taken out and the dried state of the coating film surface was confirmed by touch. ○: Good, ×: Adhesive remains.

[0026]

As is apparent from the above description and Table 1, the electrical insulating resin composition of the present invention has excellent curing and drying properties without adversely affecting the curing and drying properties, has a low viscosity, and has a good coating appearance. It is good and suitable for the field of electrical insulation.

Claims (1)

[Claims] 1. A modified unsaturated polyester resin 95 modified with (A) 5 to 70 parts by weight of an epoxy acrylate resin esterified with a quaternary phosphonium as a catalyst and (B) 5 to 30% by weight of a thermoplastic polyester resin. To 30 parts by weight and (C) a reactive monomer as essential components, the quaternary phosphonium catalyst in (A) above is 0.1 to 1.0 parts by weight with respect to the epoxy acrylate resin, and the reactive unit amount of (C) above Body to 100 parts by weight of resin component [(A) + (B)]
A resin composition for electrical insulation, characterized by being mixed in a proportion of 40 to 300 parts by weight.