JPH1139948A - Injection resin composition for electric apparatus insulation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition in which viscosity is adjusted into a proper amount, and workability is improved by mixing a main agent formed by mixing bisphenol epoxy resin with alicyclic epoxy resin and a curing agent in an equivalent ratio of a specific amount, and filling a filler. SOLUTION: A main agent and a curing agent are mixed in an equivalent ratio of 1:(0.95 to 0.9), and a filler is filled so as to form an electrical apparatus insulating injection resin composition. Preferably, the filler is aluminum oxide. As to the mixing of an epoxy resin, for example, bisphenol epoxy resin of 250 epoxy equivalent, bisphenol epoxy resin of 400 epoxy equivalent, and alicyclic epoxy resin of 138 equivalent are mixed in a range of 40:40:20 so as to form the main agent. As to the curing agent, acid anhydride can be cited, but not limited to the same. As to the filler, aluminum oxide of an average particle size of 12 μm is cited. Since a pot life is long, it can cope with mass-production.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cast resin composition for insulating electrical equipment and an epoxy resin cast product.

[0002]

2. Description of the Related Art Hitherto, as an insulating material and a structural material for high-voltage equipment, a polymer composite cured product using an epoxy resin as a matrix, that is, a so-called molded product has been widely used.

Also, with the recent sophistication and concentration of society, there is a strong demand for large capacity, small size, and high reliability of equipment, and a mold for a gas circuit breaker (GIS) using an SF ₆ insulating medium is required. For cast products, the maximum operating temperature of stationary equipment is 10
There is an increasing tendency to use heat-resistant epoxy cast products having a glass transition temperature (hereinafter referred to as “Tg”) of 125 ° C. or higher, in which the physical properties of the material are stable even at 5 ° C. or higher.

[0004]

However, the heat-resistant epoxy resin having Tg ≧ 125 ° C. or higher according to the prior art is
Since it is hard and brittle, there is a problem that the obtained cast product is easily broken. As a result, in order to maintain the crack resistance test result using iron conductor at -20 ° C or less and the crack resistance test result using aluminum conductor at -80 ° C or less, a solid epoxy resin with poor workability was used. Or a large amount of filler needs to be filled. As a result, the viscosity is remarkably increased, and the operable time (pot life) is shorter than 60 minutes.

[0005]

The electric insulating resin composition of the present invention for solving the above-mentioned problems is an electric insulating resin composition comprising a main agent comprising an epoxy resin and a curing agent, wherein the main agent is bisphenol. A mixture of a type epoxy resin and an alicyclic epoxy resin, the equivalent ratio of the above-mentioned base agent and the curing agent being 1: 0.95-0.9, and filling with a filler. Features.

[0006] In the above resin composition for electrical insulation, the filler is aluminum oxide.

An epoxy resin cast product of the present invention is characterized by using the above-mentioned resin composition for electrical insulation.

[0008]

Embodiments of the present invention will be described below.

[0009] The resin composition for electrical insulation of the present invention comprises a bisphenol type epoxy resin and an alicyclic epoxy resin as main ingredients, and the equivalent ratio of the main ingredient to the curing agent is 1: 0.9.
They are mixed in the range of 5-0.9 and filled with a filler. Here, the bisphenol-type epoxy resin is, for example, “Epicoat 834” (trade name, manufactured by Yuka Shell Co., Ltd.) with an epoxy equivalent of 250, and “YL-” with an epoxy equivalent of 400.
6425B "(trade name; manufactured by Yuka Shell Co., Ltd.)," CT-200 "(trade name; manufactured by Ciba Geigy) having an epoxy equivalent of 400, and glycidyl ester type epoxy resin having an epoxy equivalent of 170 (e.g.," CY-184 "trade name) , Manufactured by Ciba-Geigy), but the present invention is not limited thereto. Examples of the alicyclic epoxy resin include "CY-179" (trade name; manufactured by Ciba Geigy), epoxy equivalent = 400), but the present invention is not limited thereto.

The epoxy resin is mixed, for example, with a bisphenol-type epoxy resin having an epoxy equivalent of 250, a bisphenol-type epoxy resin having an epoxy equivalent of 400, and an alicyclic epoxy resin having an equivalent of 138;
It is preferable to use a mixture in a ratio of 40:20 as the main agent. As other compounding of the epoxy resin, for example, a bisphenol type epoxy resin having an epoxy equivalent of 250, a bisphenol type epoxy resin having an epoxy equivalent of 475, and an alicyclic epoxy resin having an equivalent of 138 are 40:
It is preferable to use a mixture in a ratio of 40:20 as the main agent. As another compounding of the epoxy resin, for example, a bisphenol type epoxy resin having an epoxy equivalent of 330 and an alicyclic epoxy resin having an equivalent of 138 are mixed at 80:20.
It is preferable to use a mixture obtained in the range of the above as the main agent. As other compounding of the epoxy resin, for example, a bisphenol type epoxy resin having an epoxy equivalent of 250, a bisphenol type epoxy resin having an epoxy equivalent of 475, and a glycidyl ester type epoxy resin having an equivalent of 170 are used.
It is preferable to use a mixture in the range of 0:40:20 as the main agent.

[0011] Examples of the curing agent include acid anhydrides, but the present invention is not limited thereto.

As the curing accelerator, a tertiary amine can be exemplified, but the present invention is not limited to this.

The epoxy resin cast product of the present invention is obtained by adding a filler to the above-mentioned resin composition for electrical insulation and heat-curing it in a predetermined shape.

Examples of the filler include aluminum oxide having an average particle size of 12 μm.
A curing accelerator is mixed in an equivalent ratio of 1: 0.95-0.9, and 42-46% by volume of the above filler is added and mixed until uniform, for example, at 100 ° C. for 16 hours and at 150 ° C. By performing heat curing for 8 hours, a resin cast product is obtained.

[0015]

Embodiments of the present invention will be described below.

(Example 1) a) Preparation of main agent Epoxy equivalent 2 having general properties as base resin
50 bisphenol A type epoxy resin (for example, “Epicoat 834” trade name, manufactured by Yuka Shell Co., Ltd.) and a bisphenol A type epoxy resin having an epoxy equivalent of 400 (for example, “YL-6425B” trade name, manufactured by Yuka Shell Co., Ltd.) Is blended in a fixed ratio of 50:50, and an alicyclic epoxy resin having an epoxy equivalent of 138 (for example, “CY-17
9 "(trade name, manufactured by Ciba Geigy). A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Adjustment of Curing Agent / Curing Accelerator The curing agent used was methylhexahydrophthalic anhydride (for example, “HN-5500” trade name, manufactured by Hitachi Chemical Co., Ltd., acid anhydride equivalent = 168), which is an acid anhydride. In order to start the reaction smoothly, a small amount of a tertiary amine (for example, “L-86” (trade name, manufactured by Meiden Chemical Co., Ltd.)) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 12 μm (for example, “F
X-4 "(trade name: manufactured by Tatsumori Co., Ltd.)
Are mixed at an equivalent ratio of 1: 0.95,
Mix until uniform, 100 ℃ -16hr + 150 ℃
Heat curing was performed at -8 hr. The amount of the filler is 4
One having 2% by volume (Example 1-1) and one having 46% by volume (Example 1-2) were used.

Comparative Example 1 As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 400 having general characteristics as a base resin (for example, “YL-642”)
The operation was performed in the same manner as in Example 1-1, except that “5B” (trade name, manufactured by Yuka Shell Co.) was changed to 100.

(Example 2) a) Epoxy equivalent 2 having general properties as a base resin
50 bisphenol A type epoxy resin (for example, "Epicoat 834" trade name, manufactured by Yuka Shell Co., Ltd.) and an epoxy equivalent of 475 bisphenol A type epoxy resin (for example, "Epicoat 1001" trade name, manufactured by Yuka Shell Co., Ltd.)
Is blended at a fixed ratio of 50:50 with an alicyclic epoxy resin having an epoxy equivalent of 138 (for example, “CY-1
79 "(trade name, manufactured by Ciba Geigy). A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Curing Agent / Curing Accelerator The curing agent used was methylhexahydrophthalic anhydride as an acid anhydride (for example, “HN-5500” (trade name, manufactured by Hitachi Chemical Co., Ltd., acid anhydride equivalent = 168)). To start smoothly, a small amount of a tertiary amine (for example, “L-86” (trade name, manufactured by Meiden Chemical Co., Ltd.)) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 14 μm (for example,
(FX-4) (trade name: manufactured by Tatsumori Co.), (a) and (b) were mixed at an equivalent ratio of 1: 0.95, and mixed until uniform.
Heat curing was performed at 100 ° C. for 16 hours + 150 ° C. for 8 hours. The amount of the filler added was 42% by volume (Example 2-1) and 44% by volume (Example 2-2).

Comparative Example 2 As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 475 having general characteristics as a base resin (for example, Epicoat 1
001 "(trade name, manufactured by Yuka Shell Co.) was changed to 100, and the same operation as in Example 2-1 was performed.

Example 3 a) Epoxy equivalent 3 having general properties as a base resin
30 bisphenol A type epoxy resins (for example, “Z
X1289 "(trade name, manufactured by Toto Kasei Co., Ltd.) and an alicyclic epoxy resin having an epoxy equivalent of 138 (for example," CY-17 ").
9 "(trade name, manufactured by Ciba Geigy). A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Curing Agent / Curing Accelerator The curing agent used was methylhexahydrophthalic anhydride as an acid anhydride (for example, “HN-5500” (trade name, manufactured by Hitachi Chemical Co., Ltd., acid anhydride equivalent = 168)). To start smoothly, a small amount of a tertiary amine (for example, “L-86” (trade name, manufactured by Meiden Chemical Co., Ltd.)) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 14 μm (for example,
(FX-4) (trade name: manufactured by Tatsumori Co.), (a) and (b) were mixed at an equivalent ratio of 1: 0.95, and mixed until uniform.
Heat curing was performed at 100 ° C. for 16 hours + 150 ° C. for 8 hours. The amount of the filler added was 42% by volume (Example 3-1) and 44% by volume (Example 3-2).

Comparative Example 3 As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 330 having a general property as a base resin (for example, “ZX128”)
The same operation was performed as in Example 3-1 except that “9” trade name, manufactured by Toto Kasei Co., Ltd.) was changed to 100.

Example 4 a) Epoxy equivalent weight 2 having general properties as a base resin
50 bisphenol A type epoxy resin (for example, “Epicoat 834” trade name, manufactured by Yuka Shell Co., Ltd.) and a bisphenol A type epoxy resin having an epoxy equivalent of 400 (for example, “YL-6425B trade name, manufactured by Yuka Shell Co., Ltd.) 5
An alicyclic epoxy resin having an epoxy equivalent of 138 (for example, “CY-17
9 "(trade name, manufactured by Ciba Geigy). A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Curing Agent / Curing Accelerator The curing agent is hexahydrophthalic anhydride (for example, “Ricacid HH” (trade name, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent = 154)) which is an acid anhydride, and the reaction is smoothly performed. To start, a small amount of a tertiary amine (for example, “L-86” trade name, manufactured by Meiden Chemical Co., Ltd.) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 14 μm (for example, “F
X-4 "(trade name: manufactured by Tatsumori Co.), (a) and (b) were mixed at an equivalent ratio of 1: 0.9, and mixed until uniform.
Heat curing was carried out at a temperature of -16 ° C for 16 hours and 150 ° C for 8 hours.
The amount of the filler was 42% by volume (Example 4-
1) and 46% by volume (Example 4-2).

(Comparative Example 4) As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 400 having general characteristics as a base resin (for example, “YL-642”)
5B trade name, manufactured by Yuka Shell Co.)
The same operation as in Example 4-1 was performed.

(Example 5) a) Epoxy equivalent weight 2 having general properties as a base resin
50 bisphenol A type epoxy resin (for example, "Epicoat 834" trade name, manufactured by Yuka Shell Co., Ltd.) and an epoxy equivalent of 475 bisphenol A type epoxy resin (for example, "Epicoat 1001" trade name, manufactured by Yuka Shell Co., Ltd.)
Is blended at a fixed ratio of 50:50 with an alicyclic epoxy resin having an epoxy equivalent of 138 (for example, “CY-1
79 "(trade name, manufactured by Ciba Geigy). A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Curing Agent / Curing Accelerator The curing agent is hexahydrophthalic anhydride (for example, “Ricacid HH” (trade name, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent = 154)) which is an acid anhydride, and the reaction is smoothly performed. To start, a small amount of a tertiary amine (for example, “L-86” trade name, manufactured by Meiden Chemical Co., Ltd.) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 14 μm (for example,
(FX-4) (trade name, manufactured by Tatsumori Co.), (a) and (b) were mixed at an equivalent ratio of 1: 0.9, and mixed until uniform.
Heat curing was performed at 00 ° C.-16 hr + 150 ° C.-8 hr. The amount of the filler was 42% by volume (Example 4).
-1) and 44% by volume (Example 4-2).

Comparative Example 5 As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 475 having general properties as a base resin (for example, “Epicoat 1”)
The same operation as in Example 5-1 was performed except that “001” (trade name, manufactured by Yuka Shell Co.) was changed to 100.

(Example 6) a) Epoxy equivalent 3 having general properties as a base resin
30 bisphenol A type epoxy resins (for example, “Z
X1289 "(trade name, manufactured by Toto Kasei Co., Ltd.) and an alicyclic epoxy resin having an epoxy equivalent of 138 (for example," CY-17 ").
9 "(trade name, manufactured by Ciba Geigy). A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Curing Agent / Curing Accelerator The curing agent is hexahydrophthalic anhydride (for example, “Ricacid HH” (trade name, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent = 154)) which is an acid anhydride, and the reaction is smoothly performed. To start, a small amount of a tertiary amine (for example, “L-86” trade name, manufactured by Meiden Chemical Co., Ltd.) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 14 μm (for example, F
X-4: Tatsumori), (a) and (b) in an equivalent ratio of 1: 0.9
And mixed until uniform, 100 ° C. for 16 hours
Heat curing was performed at + 150 ° C.-8 hr. The amount of the filler added was 42% by volume (Example 6-1) and 46% by volume (Example 6-2).

Comparative Example 6 As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 330 having general properties as a base resin (for example, “ZX128”)
The same operation as in Example 6-1 was performed, except that “9” trade name, manufactured by Toto Kasei Co., Ltd.) was changed to 100.

(Example 7) a) Epoxy equivalent 2 having general properties as a base resin
50 bisphenol A type epoxy resin (for example, “Epicoat 834” trade name, manufactured by Yuka Shell Co., Ltd.) and a bisphenol A type epoxy resin having an epoxy equivalent of 400 (for example, “YL-6425B” trade name, manufactured by Yuka Shell Co., Ltd.) Was blended at a fixed ratio of 50:50, and a glycidyl ester type epoxy resin having an epoxy equivalent of 170 (for example, “CY-184” (trade name, manufactured by Ciba Geigy)) was used. A predetermined amount of this resin was placed in a stainless beaker and stirred while heating at 100 ° C. until uniform. b) Curing Agent / Curing Accelerator The curing agent used was methylhexahydrophthalic anhydride as an acid anhydride (for example, “Ricacid MH” (trade name, manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent = 168)). To start smoothly, a small amount of a tertiary amine (for example, “L-86” (trade name, manufactured by Meiden Chemical Co., Ltd.)) was added as a curing accelerator, and the mixture was stirred until it became uniform. c) Filler Alumina having an average particle size of 14 μm (for example, “F
X-4 "(trade name: manufactured by Tatsumori Co.), (a) and (b) were mixed at an equivalent ratio of 1: 0.9 until uniform, and then mixed at 100 ° C.-16.
Heat curing was performed at hr + 150 ° C.-8 hr. The amount of the filler was 42% by volume (Example 7-1),
It was 6% by volume (Example 7-2).

Comparative Example 7 As a comparative example, a bisphenol A type epoxy resin having an epoxy equivalent of 400 having general properties as a base resin (for example, “YL-642”)
The same operation was performed as in Example 6-1 except that “5B” (trade name, manufactured by Yuka Shell Co.) was changed to 100.

Table 1 below shows the test items and their conditions.
"Table 2" to "Table 8" show the results.

[0031]

[Table 1]

[0032]

[Table 2]

[0033]

[Table 3]

[0034]

[Table 4]

[0035]

[Table 5]

[0036]

[Table 6]

[0037]

[Table 7]

[0038]

[Table 8]

As shown in Tables 2 to 8, the resin having the composition of this example has excellent properties as a casting resin, and has a high heat resistance at a Tg of 125 ° C. or higher. In addition, crack resistance was excellent at ≦ −20 ° C. for iron bolt nuts and ≦ −80 ° C. for aluminum bolt nuts. Also, the pot life was as long as ≧ 60 minutes.

[0040]

As described above, the resin having these compositions is excellent in various properties as a casting resin, and has a high heat resistance at a Tg of 125 ° C. or more, and has a crack resistance of an iron bolt and nut. ≤-20 ℃, -8 with aluminum bolt and nut
Since it has an excellent ability to clear 0 ° C, it can respond to the downsizing of electrical equipment and the high heat resistance of insulating materials accompanying the increase in output. In addition, since the pot life is industrially long as ≧ 60 minutes, it can be used for mass production.

Claims (3)

[Claims] 1. A resin composition for electrical insulation comprising a main agent comprising an epoxy resin and a curing agent, wherein the main agent comprises a bisphenol type epoxy resin and an alicyclic epoxy resin, A resin composition for electrical insulation characterized by being mixed with an agent at an equivalent ratio of 1: 0.95 to 0.9 and filled with a filler. 2. The resin composition for electrical insulation according to claim 1, wherein the filler is aluminum oxide. 3. An epoxy resin cast product comprising the resin composition for electrical insulation according to claim 1 or 2.