JP2003268075A - Insulating polymer material composition for indoor and outdoor use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polymer insulating material product having heat resistance and crack resistance even in a severe temperature change environment of outdoors, etc., in high productivity. <P>SOLUTION: A resin slurry obtained by mixing a low-equivalent resin (about 250 epoxy equivalents by a one-stage method) and a high-equivalent resin (about 390 epoxy equivalents) composed of bisphenol A epoxy resins in the ratio of the low-equivalent resin/the high-equivalent resin of 50 wt.%/50 wt.% to 90 wt.%/10 wt.% is used and mixed with a curing agent (e.g. phthalic anhydride in the ratio of the resin slurry/the curing agent of 1/0.8-1/1.2), a curing promoter (e.g. 0.05 wt.%-0.37 wt.% of a tertiary amine salt), an inorganic filler (e.g. 35 vol.%-50 vol.% of fused silica) and a silane coupling agent (e.g. 0.1 wt.%-0.6 wt.% of γ-glycidoxypropyltrimethoxysilane, heated and cured. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an indoor / outdoor insulating polymer material that can be used in molded articles that are directly exposed indoors or outdoors by high-voltage equipment. For example, insulators, insulators, spacers, bushings, cable heads. , VI case and other insulating polymer material compositions for indoor and outdoor use.

[0002]

2. Description of the Related Art As an insulating material and a structural material used indoors and outdoors (especially, directly exposed to the outdoors) of high-voltage equipment (eg switchgear), for example, an insulating polymer material containing epoxy resin as a main component ( Hereinafter, a polymer insulating material product (mold cast product; hereinafter referred to as a polymer material)
The term “polymer products” is widely known, but
With the sophistication and concentration of society, there has been a strong demand for higher capacity, higher reliability, and durability of high-voltage equipment. The glass transition point (hereinafter referred to as Tg) of an epoxy resin which has been widely used for general polymer materials is about 90 to 100 ° C.

Therefore, for example, by using a polymer material whose main component is a highly heat-resistant epoxy resin having a Tg of 115 ° C. or more (hereinafter referred to as a high temperature resistant resin), in an atmosphere of the maximum temperature of stationary equipment (105 ° C.). 2) has been researched and developed a polymer product that is physically stable and has crack resistance even in an environment where the temperature changes drastically such as outdoors.

[0004]

However, as described above, the high temperature resistant resin having Tg of 115 ° C. or higher is relatively expensive and has a high degree of cross-linking, and a polymer product using the high temperature resistant resin has a high production cost. In addition to being high in hardness, it is hard and fragile, so cracks are likely to occur when used in an environment where the temperature changes drastically.

On the other hand, Tg is low (for example, Tg is 90 ° C.
In the following epoxy resin (hereinafter referred to as low temperature resistant resin), the low temperature resistant resin is solid at room temperature and the resin viscosity (initial viscosity during the mixing operation) is relatively large.

Therefore, for example, when a filler made of an inorganic material (hereinafter referred to as an inorganic filler) is added to the low temperature resistant resin for the purpose of reducing the expansion coefficient (for example, linear expansion coefficient) of a polymer product. However, it is necessary to hold the mixed slurry at a high temperature to uniformly disperse the inorganic filler and then perform the casting operation, which requires a long time in the mixing operation and the casting operation. Further, a large amount of inorganic filler is required to sufficiently reduce the expansion coefficient of the polymer product, but the viscosity of the mixed slurry further increases as the amount of the inorganic filler added increases. Further, for the purpose of shortening the heat curing in casting and improving the productivity of polymer products, a method of adding a curing accelerator or the like to the low temperature resistant resin is generally adopted. In the mixed slurry of 3, the reaction time of the curing accelerator becomes too fast, and it becomes impossible to secure sufficient pot life (minimum time required for industrial work; for example, 20 minutes) in casting work, for example. There is a fear.

That is, in the case of sufficiently reducing the expansion coefficient of the polymer product using the low temperature resistant resin, it is necessary to perform the mixing operation of the mixed slurry at a high temperature and for a long time. Productivity cannot be improved due to (it is not possible to achieve both productivity and crack resistance).

As a main component of the polymer material, the bisphenol A type epoxy resin (hereinafter referred to as bisphenol resin) having an epoxy equivalent of about 390 which is relatively inexpensive and widely used worldwide has the following problems. is there.

(Problems of crack resistance, workability and Tg) When a bisphenol resin having an epoxy equivalent of about 390 is used, the bisphenol resin has a solid and a melting point of about 52 ° C. at room temperature, and a resin viscosity (and an initial value). Since the viscosity) is relatively large, even if the mixed slurry is kept at a temperature higher than the melting point, a long time is spent in the mixing work. Therefore, it is extremely difficult to achieve both high productivity and sufficient crack resistance as with the low temperature resistant resin.

Since the Tg of the bisphenol resin is low, a method of securing heat resistance by using a novolac type epoxy resin or a cycloaliphatic epoxy resin, which is relatively expensive, is used. Tg of resin
Is too high (Tg is about 150 to 180 ° C.), the polymer product becomes hard and brittle, crack resistance is reduced and production cost is increased.

When polyglycol, polyglycol type epoxy resin, dimer acid epoxy compound, thiochol, etc. are added to the bisphenol resin, productivity is improved (productivity is improved due to the low viscosity of the additive) and crack resistance. Is known to be improved, but it is not practical because the Tg of the polymer material is significantly reduced.

The present invention has been made based on the above-mentioned problems, and it is possible to improve productivity in polymer products such as high-voltage equipment while having sufficient heat resistance and crack resistance. Another object of the present invention is to provide an indoor / outdoor insulating polymer material composition.

[0013]

In order to solve the above-mentioned problems, the present invention provides a low-equivalent resin comprising a bisphenol A type epoxy resin (for example, a resin having an epoxy equivalent of about 250). ) And a high equivalent weight resin (eg,
Epoxy equivalent is about 390) and low equivalent resin / high equivalent resin = 50 wt% / 50 wt% to 90 wt% / 10
A resin slurry mixed within a range of wt% is used, and a curing agent, a curing accelerator, an inorganic filler, and a silane coupling agent are added to the resin slurry (added and cured by heating).

The invention according to claim 2 is characterized in that the low equivalent resin is produced by a one-step method.

In the invention of claim 3, as the curing agent, methyl tetrahydrophthalic anhydride or hexahydrophthalic anhydride is used as resin slurry / curing agent = 1/0.
It is characterized by being added within the range of 8 to 1 / 1.2.

In the invention according to claim 4, a tertiary amine salt is contained in an amount of 0.05 wt% to 0.37 as the curing accelerator.
It is characterized by being added within the range of wt%.

In the invention according to claim 5, 35 vol% to 50 vol% of fused silica is used as the inorganic filler.
Is added within the range of.

The invention according to claim 6 is characterized in that γ-glycidoxypropyltrimethoxysilane is added as the silane coupling agent within the range of 0.1 wt% to 0.6 wt%.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an indoor / outdoor insulating polymer material composition according to an embodiment of the present invention will be described in detail with reference to the drawings.

In this embodiment, two kinds of bisphenol resins having different epoxy equivalents are mixed as a main component of the polymer material, that is, a bisphenol resin having a small epoxy equivalent (for example, an epoxy equivalent of about 250; hereinafter, a low equivalent resin). And a bisphenol resin having a large epoxy equivalent (for example, an epoxy equivalent of about 390;
Hereinafter, it is referred to as a high equivalent resin) by heating (in the present embodiment, 1).
(00 ° C.) while mixing and uniformly dispersing to obtain a slurry (hereinafter referred to as resin slurry).

Further, a curing agent and a curing accelerator are added to the above-mentioned resin slurry, and a predetermined temperature (60 in this embodiment) is added.
(° C) while mixing and uniformly dispersing, then an inorganic filler and a silane coupling agent are further added, and vacuum mixing is performed at a predetermined temperature (100 ° C in this embodiment) to uniformly disperse the mixture. Obtain molecular material. Then, the above-mentioned polymer material is cast (heat-cured) at a predetermined temperature to produce an indoor / outdoor insulating polymer material composition for switchgear and the like.

The mixing ratio of the low equivalent resin and the high equivalent resin in the resin slurry (hereinafter referred to as low equivalent resin / high equivalent resin) is low equivalent resin / high equivalent resin = 50.
Within the range of wt% / 50 wt% to 90 wt% / 10 wt% (preferably 80 wt% / 20 wt%). The equivalent ratio of the resin slurry to the curing agent (hereinafter referred to as resin slurry / curing agent) is within the range of resin slurry / curing agent = 1 / 0.8 to 1 / 1.2. Further, the amount of the curing accelerator added is 0.05 wt% to 0.37 wt.
% (Preferably 0.17 wt%), the addition amount of the inorganic filler is in the range of 35 vol% to 50 vol% (preferably 45 vol%), and the addition amount of the silane coupling agent is 0.1 wt%. Each of them is used within a range of preferably 0.6 wt% (preferably 0.4 wt%).

(Examples) Next, according to the present embodiment, samples of polymer products were prepared using various polymer materials, and various observations were performed on these samples.

First, at various mixing ratios (Table 2 below),
A low-equivalent resin having an average epoxy equivalent of about 250 (Epicoat 834 manufactured by Yuka Shell Co., Ltd.) having a general characteristic and a high-equivalent resin having an average epoxy equivalent of about 390 (an oil equivalent in this example) Epicoat 17 made of synthetic shell
00) was added and mixed while heating at a temperature of 100 ° C. and uniformly dispersed to obtain a plurality of resin slurries.

Thereafter, an acid anhydride (methyltetrahydrophthalic anhydride (HN2200R, acid anhydride equivalent 166) manufactured by Hitachi Chemical Co., Ltd. in the present embodiment) was added as a curing agent to each of the resin slurries described above. = 1 / 0.9
Of the tertiary amine salt (K61B manufactured by ACI Japan in this example) as a curing accelerator, and mixed while heating to a temperature of 60 ° C. By uniformly dispersing, mixed slurries were obtained.

To each of the above-mentioned mixed slurries, 40 vol% of fused silica having an average particle size of 11 μm (MCF-4 manufactured by Tatsumori in this example) was added as an inorganic filler, and a silane coupling agent was added. 1.5 p of γ-glycidoxypropyltrimethoxysilane (KBM-403 (molecular weight 236) manufactured by Shin-Etsu Silicone in this example) was used.
Polymer materials A to H were respectively obtained by adding hr and vacuum mixing at a temperature of 100 ° C. and rapidly and uniformly dispersing.

Then, about 10 kg of each of the above-mentioned polymer materials A to H was used and poured into a desired mold at a temperature of 120.degree.
Samples of a plurality of polymer products (VI case with a total length of about 500 mm; details will be described later based on FIG. 1) by heating for 2 hours at 150 ° C. for 15 hours. Was produced. The polymer material A
In the sample using, the pot life was too short as shown in Table 2 below, and therefore the sample was prepared without adding the curing accelerator. The low-equivalent resin used for each of the polymeric materials B to H is prepared by the one-step method.

1A (partial cross-sectional view), B (right side view)
Shows a schematic configuration diagram of a sample of a polymer product in this example, and after the vacuum interrupter 1 and the conductors 2 and 3 are bonded to each other, surface treatment thereof (for example, surface treatment using silicone rubber) is performed. It was performed and then molded with the polymer material 4. The vacuum interrupter 1
The insulating container was composed of a ceramic container 1a, and copper (or aluminum) was used for the conductors 2 and 3.

In each of the polymer products produced as described above, the pot life, viscosity, and Tg of the polymer materials A to H were measured under the conditions and the equipment shown in Table 1 below, and at the same time, each polymer material A was measured. The linear expansion coefficient, the crack resistance, the castability, the moldability, and the gel time of a polymer product sample obtained by casting ~ H are measured.
It was shown to. The Tg and the coefficient of linear expansion are average values in the measurement results of “N” samples as shown in Table 1 below.

[0030]

[Table 1]

[0031]

[Table 2]

As shown in Table 2 above, low equivalent resin / high equivalent resin = 50 wt% / 50 wt% to 90 wt% / 10
Unlike the polymeric materials A, B, and H, the polymeric materials C to G produced within the range of wt% have a low viscosity and can secure a sufficient pot life (20 minutes or more) and a high Tg, and
In each sample in which the respective polymeric materials C to G are cast,
It was confirmed that the gel time was relatively short with a relatively low coefficient of linear expansion, and that the crack resistance, castability, and moldability were all good. Especially low equivalent resin / high equivalent resin = 80w
In the case where the polymer material F of t% / 20 wt% was used, the best overall result was obtained.

Here, a polymer material Fs having the same composition as the polymer material F was obtained by using a low-equivalent resin prepared by the two-step method, and the molecular weight distributions of the polymer materials F and Fs were analyzed by gas-liquid chromatography. The pot life, the viscosity, the Tg, the linear expansion coefficient, the crack resistance, the castability, and the moldability were measured in the same manner as in Table 2 above, and the measurement results are shown in FIGS. Indicated.

[0034]

[Table 3]

As shown in Table 3 above, the polymer material F,
Fs had good castability and moldability, respectively, but the polymer material F had better pot life, viscosity, Tg, coefficient of linear expansion, and crack resistance than the polymer material Fs. Can be read. The reason for this is considered that, in the case of the polymer material Fs by the two-step method, terminal modification occurs at n = 0 as shown in FIG. 3, which affects each characteristic. Such terminal modification was not observed in the case of the polymer material F by the one-step method of FIG.

Next, with the same composition as the polymer material F,
Polymer materials F11 to F15 were prepared by changing the addition amount of the inorganic filler as shown in Table 4 below, and pot life, viscosity, Tg, linear expansion coefficient, crack resistance,
The castability and moldability were measured, and the measurement results are shown in Table 4.

[0037]

[Table 4]

From the results shown in Table 4 above, the polymeric materials F and F11 to F15 each had the same Tg and good castability and moldability, but among them, the polymeric materials F and F12 to F14 had high It was confirmed that, unlike the molecular materials F11 and F15, the pot life, viscosity, linear expansion coefficient, and crack resistance were all good. In particular, in the case of the polymer material F13 in which the amount of the inorganic filler added was 45 vol%, the best overall results were obtained.

Next, as shown in Table 5 below, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, 4 having the same composition as the polymer material F13 as a curing agent was used.
-Methyltetrahydrophthalic anhydride and hexahydrophthalic anhydride were used to prepare polymer materials F21 to F24,
The pot life, viscosity, Tg, coefficient of linear expansion, crack resistance, castability, and moldability were measured in the same manner as in Table 2, and the measurement results are shown in Table 5.

[0040]

[Table 5]

As shown in Table 5, each of the polymer materials F21 to F24 had good Tg, linear expansion coefficient and moldability. Among them, methyltetrahydrophthalic anhydride or hexahydrophthalic anhydride was selected. It was confirmed that the used polymeric materials F22 to F24 were good in all of pot life, viscosity, crack resistance, and castability. Especially, in the case of the polymer material F23 using 4-methyltetrahydrophthalic anhydride, the best overall results were obtained.

Next, with the same composition as the polymer material F13, the resin slurry / hardener was changed as shown in Table 6 below to prepare polymer materials F31 to F35, and pots were prepared in the same manner as in Table 2 above. Life, viscosity, Tg, linear expansion coefficient, crack resistance, castability, and moldability were measured, and the measurement results are shown in Table 6.
It was shown to.

[0043]

[Table 6]

As shown in Table 6 above, the polymeric material F13
And F31 to F35 have good viscosities, linear expansion coefficients, castability and moldability, respectively, of which resin slurry / hardener = 1 / 0.8 to 1 / 1.2 polymeric material F1
3 and F31 to F34 were confirmed to have good pot life, Tg, and crack resistance. In particular, polymer slurry F with resin slurry / hardener = 1 / 0.9
In the case of 13, the best overall results were obtained.

Next, with the same composition as the polymer material F,
Polymer materials 41 to 48 were prepared by changing the addition amount of the curing accelerator as shown in Table 7 below, and pot life, viscosity, Tg, linear expansion coefficient, crack resistance, casting were performed in the same manner as in Table 2 above. The moldability and moldability were measured, and the measurement results are shown in Table 6.

[0046]

[Table 7]

As shown in Table 7, polymer material F41
.About.F48, good linear expansion coefficient and moldability were obtained, but the addition amount of the curing accelerator was 0.05 to 0.37.
It was confirmed that the wt% polymer materials F42 to F47 were good in all of pot life, viscosity, Tg, crack resistance, and castability. Particularly, in the case of the polymer material F45 in which the addition amount of the curing accelerator is 0.17 wt%,
Overall, the best results were obtained.

Next, polymer materials F51 to F56 having the same composition as that of the polymer material F13 were prepared by changing the addition amount of the silane coupling agent as shown in Table 8 below. The initial bending strength of F51 to F56, the initial bending strength after 16 hours of boiling and the strength retention were measured, and the measurement results are shown in Table 8 below.

[0049]

[Table 8]

From the results shown in Table 8 above, the polymer material F containing 0.1 to 0.6 wt% of the silane coupling agent was added.
It was confirmed that 52 to F56 had higher strength and better moisture resistance than the polymeric material F51. Particularly, the polymer material F containing 0.4 wt% of the silane coupling agent
In the case of 54, the best result was obtained.

As in the present embodiment shown above, low-equivalent resin and high-equivalent resin obtained by the one-step method are low-equivalent resin / high-equivalent resin = 50 wt% / 50 wt% to 90 wt% / 10 wt.
% Resin tetramethyl phthalic anhydride or hexahydrophthalic anhydride as a curing agent resin slurry / curing agent = 1 / 0.8 to 1
/1.2, the tertiary amine salt as a curing accelerator in the range of 0.05 wt% to 0.37 wt%, and the fused silica as the inorganic filler in the range of 35 vol% to 50%.
It is used within the range of vol% and γ-glycidoxypropyltrimethoxysilane is used as a silane coupling agent.
By using the polymer material in the range of 1 wt% to 0.6 wt%, it is possible to secure a sufficient pot life (20 minutes or more) and Tg with low viscosity in the polymer material. In addition, even in polymer insulating material products, etc. in which the above polymer material is cast, the gel time becomes short with a relatively low linear expansion coefficient, and crack resistance (and moisture resistance), castability, molding The property can be improved.

In the above, the present invention has been described in detail only with respect to the specific examples described, but it is obvious to those skilled in the art that various variations and modifications are possible within the scope of the technical idea of the present invention. Of course, such variations and modifications are within the scope of the claims.

[0053]

As described above, according to the present invention, a low viscosity and sufficient pot life of a polymer material can be obtained without using a relatively expensive material such as a novolac type epoxy resin or a cycloaliphatic epoxy resin. (20 minutes or more) and a good Tg (115 ° C. or more) can be secured, and the gel time can be shortened with a relatively low linear expansion coefficient even in a polymer insulating material product or the like in which the polymer material is cast. It is possible to provide high-productivity polymer insulating material products with heat resistance and crack resistance even in environments with severe temperature changes, such as outdoors, in response to the increasing capacity and miniaturization of high-voltage equipment. Become.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a sample of a polymer product in this example.

FIG. 2 is a molecular weight distribution diagram of a polymer material using a low equivalent weight resin by a one-step method.

FIG. 3 is a molecular weight distribution diagram of a polymer material using a low-equivalent resin by a two-step method.

[Explanation of symbols]

1 ... Vacuum interrupter 1a ... Ceramic container 2, 3 ... conductor 4 ... Resin

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] April 11, 2002 (2002.4.1)
1)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Title of invention

[Correction method] Change

[Correction content]

Title: Insulating polymer material composition for indoor and outdoor use

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 63/02 H01B 3/40 C H01B 3/40 F H J C08K 5/54 F term (reference) 4J002 CD051 CD052 DJ018 EF126 EL136 EN027 EX069 FD018 FD146 FD157 GQ01 4J036 AA05 AD08 DB21 DC05 FA01 FA05 FA13 JA05 5G305 AA14 AB24 AB27 AB36 AB40 BA09 CA16 CB13 CB16 CB26 CC02 CD01 CD06 CD08

Claims (6)

[Claims] 1. A resin slurry prepared by mixing a low-equivalent resin composed of a bisphenol A type epoxy resin and a high-equivalent resin within a range of low-equivalent resin / high-equivalent resin = 50 wt% / 50 wt% to 90 wt% / 10 wt%. A polymeric material composition for indoor and outdoor use, wherein a curing agent, a curing accelerator, an inorganic filler, and a silane coupling agent are added to the resin slurry. 2. The indoor / outdoor insulating polymer material composition according to claim 1, wherein the low-equivalent resin is produced by a one-step method. 3. The curing agent according to claim 1, wherein methyltetrahydrophthalic anhydride or hexahydrophthalic anhydride is added within the range of resin slurry / curing agent = 1 / 0.8 to 1 / 1.2. Item 3. The indoor / outdoor insulating polymer material composition according to Item 1 or 2. 4. The indoor / outdoor insulating polymer material composition according to claim 1, wherein a tertiary amine salt is added in the range of 0.05 wt% to 0.37 wt% as the curing accelerator. object. 5. A fused silica is used as the inorganic filler in an amount of 3
The indoor / outdoor insulating polymer material composition according to any one of claims 1 to 4, which is added within a range of 5 vol% to 50 vol%. 6. The silane coupling agent is γ-
0.1 wt of glycidoxypropyltrimethoxysilane
% -0.6 wt% added in the range of 1 to 5, the indoor / outdoor insulating polymer material composition according to claim 1.