JPS6011525A - Production of low-viscosity impregnating epoxy resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin having excellent machanical and electrical properties and a long pot life, by adding butylphenyl glycidyl ether, a phenoxy resin, zinc caprylate, and a cyclic acid anhydride successively to a cycloaliphatic epoxy compound. CONSTITUTION:5-50pts.wt. p-t-butylphenyl glycidyl ether of formula I is added to 100pts.wt. cycloaliphatic epoxy compound having 1,2-epoxy group. 0.1- 10pts.wt. phenolic resin of formula II (wherein n is 200-1,000) is added to 100pts.wt. resulting composition. 0.01-1.0pt.wt. zinc caprylate is added to 100pts.wt. resulting composition, and the mixture is heat-treated at 100-150 deg.C for 10-120min and, after cooling, it is mixed with a cyclic acid anhydride. Examples of the cycloaliphatic expoxy compounds include 3,4-epoxy cyclohexylmethyl 3',4'-epoxycyclohexane-carboxylate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing a low-viscosity epoxy-impregnated resin, and more specifically, the present invention relates to a method for producing a novel low-viscosity gas epoxy-impregnated resin. The present invention relates to a method for producing a low-viscosity epoxy resin that has excellent properties such as mechanical properties and electrical properties, and has a long pot life, by preheating the resin and then blending it with an acid anhydride.

Many patents have been filed for epoxy impregnated resins, and many epoxy impregnated resins are used in actual equipment.

However, many of these epoxy-impregnated resins have high viscosity at room temperature and often have short pot lives. Adding a diluent is a common method for lowering the viscosity, but the current situation is that the usual diluents are highly irritating to the skin and have a drastic drop in properties, making it difficult to obtain sufficient properties. be.

In view of these current circumstances, the present inventors have conducted extensive research on a method for producing an epoxy-impregnated resin that improves the above-mentioned drawbacks, and have arrived at the present invention.

That is, the present invention includes 3 to 0 parts of TI-t-butylphenyl glycidyl ether of the following formula (T) to 100 parts by weight (hereinafter referred to as "parts") of a cycloaliphatic epoxy compound having a /1.2-epoxy group. and the resulting composition (AJ to
The phenoxy resin represented by the general formula (n) in the o part (in the formula n
is 200 to tooO) 0 07%/0 parts, and the resulting composition (B)
0.00 parts of zinc octylate. A low viscosity epoxy-impregnated resin is produced by adding Q/~lO part to /θO~/, heat-treating at 5-θ°C for 10~/20 minutes, cooling, and then blending a liquid cyclic acid anhydride. It's a method.

One feature of the present invention is that the epoxy component is mainly a cyclic 2-oxy compound having a 12,2-epoxy group, and pt-butylphenyl glycidyl ether is used as a low-viscosity diluent. Although pt-butylphenyl glycidyl ether is a low-viscosity diluent, it has low skin irritation and little deterioration in properties.

A further feature of the present invention is that a specific metal salt catalyst called zinc octylate is used as the oxidation curing catalyst, and this catalyst is heated in advance at a certain temperature range for a predetermined period of time.

A cyclic epoxy compound having a 2-epoxy group and p-1-
The purpose is to obtain an impregnated resin with a long pot life by treating it in a mixture of butylphenyl glycidyl ether and a phenoxy resin.

That is, the present inventors used a zinc octylate catalyst as l.

A cyclic epoxy compound having a co-epoxy group and a p-t-
When butylphenyl glycidyl ether is mixed with Sara at a ratio of 0.0/~tO parts to too parts of the phenoxy resin mixture and treated in a temperature range of too-ts:o parts, the above epoxy compound is It has been found that the pot life is longer than that of a mixture containing a mixture and an acid anhydride.

In the present invention, a high molecular weight phenoxy resin is added to a low viscosity epoxy compound at a ratio of 0./% to 100 parts of the former.
By blending within the range of 70 parts, adhesiveness is improved and flexibility is imparted.

In the present invention, it is desirable to mainly use a cyclic epoxy compound having a 1,2-epoxy group (hereinafter referred to as a cyclo-epoxy compound) due to the characteristics of the impregnating resin, but bisphenol A-type epoxy compounds, glycidyl ester-type epoxy compounds, A novolac type epoxy compound or the like may be used in an amount not exceeding 30% by weight based on the cyclo-epoxy compound.

Examples of cycloepoxy compounds that can be used in the present invention include 3. ψ-epoxycyclohexylmethyl-31, F/-epoxycyclohexane carboxylate (Chisson Noxco, 2/ (trade name manufactured by Chisso Corporation), C
Y-/79 (product name manufactured by Ciba)), 3. 'l-epoxy-6-methylcyclohexylmethyl-J/, ql-
Examples include epoxy-6'-methylcyclohexane carboxylate, vinyl cyclohexene dioxide (Chissonox 206 (trade name, manufactured by Chisso Corporation)), dicyclopentadiene dioxide, and dipentene dioxide.

In the present invention, the above cycloepoxy compound i00
pt-butylphenyl glycidyl ether is used in a range of 3 to 50 parts. If the amount added is less than 5 parts, the viscosity will not be sufficiently lowered, and if it exceeds the SO part, the properties of the cured product will deteriorate.

Also, the amount of phenoxy resin represented by the general formula (rr) added to the epoxy compound is the same as that of the cyclo-epoxy compound and p
-t-butylphenyl glycidyl ether mixture 10
Q, / % / Q part is desirable for 0 part. If the amount added is less than 0.1 part, the effects of adding the phenoxy resin, such as improving adhesion and imparting flexibility, will not appear. or,
If the amount added exceeds 10 parts, the effect of adding the phenoxy resin can be obtained, but the viscosity of the impregnated resin will increase and the pot life will be shortened, which is not preferable.

Furthermore, the amount of zinc octylate added to the epoxy mixture blended with the phenoxy resin obtained here was 0.0
/~10 parts is desirable. If the amount added is less than 0.01 parts, the effect of extending the pot life due to the heat treatment effect is sufficient, and if it exceeds tr < 10 parts, the pot life will be shortened.

Here, the heat treatment temperature after addition of zinc octylate is 100
~1 left θ°C is desirable; if it is less than too°C, no significant effect will be obtained as shown in the figure, and if it exceeds iro°C, the pot life will be shortened. The cause of this effect due to heat treatment temperature is not clear, but it is thought that zinc octylate is added uniformly through heat treatment, which lengthens the pot life (7).

The liquid cyclic acid anhydride that can be used in the present invention includes HN- as methyltetrahydrophthalic anhydride.
x2oo (trade name manufactured by Hitachi Chemical).

QH-200 (trade name manufactured by Nippon Zeon Co., Ltd.), HN-rr00 (trade name manufactured by Hitachi Chemical Co., Ltd.) as methylhexahydrophthalic anhydride, methylhimic anhydride as methylendomethylenetetrahydrophthalic anhydride (trade name manufactured by Hitachi Chemical Co., Ltd.), hexahydrophthalic anhydride, etc.

The manufacturing method of the present invention will be explained below using Examples.

Example l CY-/7? mentioned above as a cyclo-epoxy compound?
Blend 0 parts of pt-butylphenyl glycidyl ether to t0 parts, add io parts of phenoxy resin/,
After heating at 10°C for 1 hour to dissolve, add 02 parts by weight of zinc octylate, heat-treating at 120°C for 30 minutes, and melting at 25°C.
After cooling until.

700 parts of HN-2200 described above as an acid anhydride was added to produce an epoxy-impregnated resin. This resin was left in a constant temperature and humidity bath at a humidity of 35% and tracked by measuring the viscosity. That is, in this measurement, the number of days until the viscosity at 23° C. reached 200 centipoise was defined as the pot life. The figure shows the change over time in the viscosity of the produced epoxy-impregnated resin at 25°C. The viscosity of the above impregnated resin is 30
It showed good properties with a pot life of 3 months or more until it reached 240 centipoise after a day and 500 centipoise (100 MA in the figure).

This resin was cured at tSO° C. for 14 hours to obtain a cured product. The bending strength of this cured product was /10 kp/- at 25°C, and the weight loss after heating at 200°C for 16 days was % Yuco, which showed good properties.

When measuring adhesive strength using the helical coil method, /'l
! showed an excellent value of 9 (both JIEIC21
03). Also, in a skin irritation test of this product, no changes were observed on the skin.

Example C An epoxy-impregnated resin was produced in the same manner as in Example 1 above, with the heat treatment conditions for zinc octylate being 100°C and 30 minutes. In a pot life test conducted in the same manner as in Example 1, the viscosity after 30 days at 2 parts °C was 2gθ centiboise, and the pot life at 2 parts °C was 3 months or more, showing good properties (in the figure). Curve B).

Further, the properties of the resin cured under the same curing conditions as in Example 1 also showed good properties almost equivalent to those of the resin in Example 1.

Example 3 An epoxy-impregnated resin was produced in the same manner as in Example 3 above, except that the heat treatment conditions for zinc octylate were changed to 10° C. for 30 minutes. In a pot life test of the produced resin in the same manner as in Example 1, the viscosity of 2 parts after 30 days at ℃ was 2.
50 centipoise.

2! The pot life at r°C was 3 months or more, indicating good properties (straight line C in the figure).

Further, the properties of the resin cured under the same curing conditions as in Example 1 also showed good properties almost equivalent to those of the resin in Example/.

Comparative Example l 20 parts of pt-butylphenylglycidyl ether was blended with 10 parts of CY-179 as a cyclo-based epoxy resin, 70 parts of phenoxy resin was added, heated at 730°C for an hour to dissolve, and then 2 parts After cooling to 100%, 100 parts of HN-2,200'fK was added as an acid anhydride to produce an epoxy-impregnated resin.

In a pot life test conducted in the same manner as in Example 1, this product had a viscosity of 1/2 after 3C days at 25°C.

Centipoise and Example 1~? It is clear that the viscosity increased significantly compared to the above, and the pot life was short (straight line D in the figure).

Comparative Example An epoxy-impregnated resin was produced in the same manner as in Example 1 above, with the heat treatment conditions for zinc octylate being 30 minutes at 00C.

In a pot life test conducted in the same manner as in Example, this product had a viscosity of zo at 23° C. and a 30-day bale.

centipoise and a larger viscosity (ll
) It is clear that the pot life is short (straight line E in the figure).

Example V CY-77970 parts as a cyclo-epoxy compound,
Blend 10 parts of GY-2 Tata and 20 parts of pt-butylphenyl glycidyl ether, add a part of phenoxy resin and dissolve at iqo℃ for 1 hour, then add 0 parts of zinc octylate.
．． 7 parts were added, heat treated at 130°C for 30 minutes, cooled to 23°C, and further converted to HN-! as an acid anhydride. rk00 no 9
An epoxy-impregnated resin was produced by adding a part. The initial viscosity of this resin was 90 centipoise at 23°C. In a pot life test conducted in the same manner as in Example 1, the pot life was 3 months or more before reaching SOO cell size, indicating good properties. This product was cured at 750° C. for 76 hours to obtain a cured product. The bending strength of this cured product was 2 parts 1/- at 200°C, and the weight loss after heating at 200°C was 2%, which was a good value. Furthermore, the adhesive strength measurement using the helical coil method was /9. It showed an excellent value of Okl (according to Tl5(12) C2103).

Also, in a skin irritation test of this product, no changes in the skin were observed.

Example ! As a cyclo-based epoxy compound, 9 parts of C'Y-/'19 were blended with 9 parts of T)-t-butylarhenylglycidyl ether, and 3 parts of phenoxy resin was added.

After dissolving at 130°C for 2 hours, zinc octylate 02
1 part of methylhimic acid anhydride was added, heated at 119°C for 30 minutes, cooled to 2 parts°C, and added 1 part of methylhimic acid anhydride as an acid anhydride.
00 parts were added to produce an epoxy-impregnated resin. The initial viscosity of this resin was 1 g at 1 g°C. In addition, in a pot life test conducted in the same manner as in Example 1, the pot life until reaching SOO cell size was 3 months or more, showing good properties.

This product was cured at tS-O°C for 16 hours to obtain a cured product. The bending strength of this cured product was 11 g-1 at 25 DEG C., and the weight loss after heating at 200 DEG C. was 2 t%, showing good properties. In addition, the adhesive strength by the helical coil method is
It showed an excellent value of tgkg (both JIS C2
103).

In the skin irritation test of this product, no changes in the skin were observed.

Comparative Example 3 An impregnated resin was produced in the same manner as in Example 3, except that talesyl glycidyl ether, a common diluent, was used instead of p-t-7' tylphenyl glycidyl ether. 2 of this resin! The initial viscosity at C was Q centipoise.

The pot life of this resin was measured in the same manner as in Example 1, and the number of days until it reached SOO centipoise was 2!
It showed only a short pot life in days. Furthermore, according to a skin irritation test of this resin, mild inflammation was observed on the skin.

This resin was cured at /jθ0C for 76 hours to obtain a cured product. The bending strength of this cured product is 2! The adhesive strength of the heated mold after 200°C/6 days was 75%, and the adhesive strength by helical coil method was tlOkg at 23°C, and the resin obtained by the method of Example 1. When compared, only those with poor properties were obtained (according to JIS C Co. 103)
.

Comparative Example An epoxy-impregnated resin was produced in the same manner as in Example 1 except that the gphenoxy resin was not used.

2 of this resin! The initial viscosity at °C was 12 tacentivoise. The pot life obtained by the same method as in Example 1 was approximately the same as that of the resin obtained in Example 1. In addition, the properties of the cured product cured at /jtO℃ for /2 hours were almost the same as the results of Example 1 in terms of bending strength and heating weight loss, but the adhesive strength was /! ! It showed a low value of rlq7.

As described above in the examples, according to the manufacturing method of the present invention,
A low-viscosity epoxy-impregnated resin having a long pot life and good curing properties is obtained.

[Brief explanation of drawings]

The figure is a diagram showing the change over time in the viscosity of the epoxy-impregnated resin produced in Examples or Comparative Examples in U-A-c. Agent Masuo Oiwa (/, 1) Date of elapsed & (days) (16) Inventor of the continuation of page 1 Takeshi Daiei Mitsubishi Electric Corporation Production Technology Laboratory, 8-1-1 Tsukaguchi Honmachi, Amagasaki City

Claims (3)

[Claims] (1) Parts by weight of pt-butylphenyl glycidyl ether CH30 t-go of the following formula (I) were added to 100 parts by weight of a cycloaliphatic epoxy compound having an l,2-epoxy group, and the resulting composition ( A) t
Composition (B) 1 obtained by adding 27-70 parts by weight of a phenoxy resin represented by general formula (II) to 00 parts by weight
00 parts by weight of zinc octylate, heat-treated at 700 to 150°C for 10 to 20 minutes, cooled, and then blended with a liquid cyclic acid anhydride. Method for producing low viscosity epoxy impregnated resin. (2) A cycloaliphatic epoxy resin having a t,S-epoxy group is 3. epoxy chlorohexylmethyl-sl,
tI/-epoxycyclohexane carboxylate,
3. Goo epoxy-6-methylcyclohexylmethyl-
3/, f-epoxy-61-methylcyclohexane carboxylate, vinylcyclohexe/dioxide, dicyclopentadiene dioxide, or dipentene dioxide. Law. (3) The liquid cyclic acid anhydride is hexahydrophthalic anhydride and methylhexahydrophthalic anhydride. 2. The method for producing a low-viscosity epoxy-impregnated resin according to claim 1, which is methyltetrahydrophthalic anhydride or methylendomethylenetetrahydrophthalic anhydride.