JPH01318062A - Epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain an epoxy resin composition which can give a cured product excellent in SF6 resistance, improved in mechanical strengths and useful as a material for molding a high-voltage apparatus by adding fused alumina surface-treated with an epoxysilane coupling agent to an epoxy resin. CONSTITUTION:This epoxy resin composition is obtained by adding 50-80wt.%, based on the total solid matter, fused alumina surface-treated with an epoxysilane coupling agent (e.g., A-187, a product of Nippon Unicar) and/or a reactive silicone oil (e.g., FZ-3704, a product of Nippon Unicar) to an epoxy resin, e.g., a bisphenol A epoxy resin containing diaminodiphenylmethane as a curing agent. It is also possible to add a combination of untreated fused alumina with the surface-treating agent to the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an epoxy resin composition used as a molding material for high voltage equipment.

[Conventional technology]

Sulfur hexafluoride (SF) is a synthetic gas that currently has the most practical value and is widely used as a gas insulating material used in high-voltage equipment.It is compressed to 1 to 6 atmospheres and used in gas-insulated switchgear. (gas switches), gas circuit breakers, gas insulated transformers, X-ray equipment power sources, waveguides, etc.

The resins used as molding materials for such devices include:
Therefore, resistance to SF, cracked gas, etc. (high sulfur fluoride resistance) is required. Therefore, hydrated alumina or alumina has conventionally been blended into epoxy resin molding materials used for gas switch arms and the like as a filler with excellent SF resistance and properties.

[Problem to be solved by the invention]

However, the above-mentioned hydrated alumina and epoxy resin containing alumina have low tJ3j mechanical strength, especially bending strength, and are not sufficient for use in gas switch arms and the like.

In view of the above circumstances, it is an object of the present invention to provide an epoxy resin composition that can provide a cured product that is highly resistant to large sulfur fluorides and has excellent mechanical strength.

[Means to solve the problem]

Among the aluminas used as fillers that provide SF resistance and properties, fused alumina is most suitable in terms of increasing mechanical strength, but this fused alumina has the disadvantage of poor affinity with resins. have. Therefore, we focused our attention on applying surface treatment to molten alumina to change its surface condition, and completed this invention.

That is, in order to solve the above problems, the epoxy resin composition according to the present invention has a content of 5% based on the total solid content of the composition.
Contains 0 to 80% by weight of fused alumina, and the fused alumina has been surface-treated in advance with an epoxy silane-based carboxylic agent and/or reactive silicone oil as a surface treatment agent, or the surface treatment agent has not been treated. of the molten alumina.

[Function] Fused alumina as a filler is contained in an amount of 50 to 80% by weight in the total solid content of the composition.

If the blending amount is too small, the effect of the present invention, that is, the improvement in mechanical strength, will not be sufficiently achieved. On the other hand, if the amount is too high, various problems will occur, such as difficulty in kneading, poor appearance of the molded product, or excessively high hydrophilicity, which may reduce the water resistance of the resin.

The surface treatment of the molten alumina improves the affinity or compatibility (compatibility) with the epoxy resin, and as a result, the mechanical strength of the cured epoxy resin is improved.

〔Example〕

The epoxy resin in this invention includes, for example,
Examples include bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, brominated epoxy resin, alicyclic epoxy resin, and heterocyclic epoxy resin, but are not particularly limited. These may be used alone or in combination.

The type of curing agent is not particularly limited, and common curing agents such as various amines, acid anhydrides, imidazoles, and phenol novolak resins can be used alone or in combination. Further, there is no limit to the usage amount, and the necessary amount may be set as appropriate.

The epoxysilane-based carboxylic agent used as a surface treatment agent is a silane carboxylic acid containing one or more glycidoxyalkyl groups (or epoxy groups) in the molecule, and has the following general formula; [wherein, R is an alkylene group] , X is hydrogen, hydroxyl group,
Alkyl group, alkenyl group, phenyl group.

An alkoxyl group, an aminoalkyl group, a carboxyalkyl group, a glycidoxyalkyl group, an epoxy group, etc.] Those represented by the following can be used. For example, as a commercially available product, Nippon Unicar ■! ! Examples include A-187 and KBM403 manufactured by Shin% Silicone tJ@.

For example, the reactive silicone oil has the following general formula (1)
~(■); ・・・ (r) ・・・
(II)... (III)
... (IV) [wherein, X is the same as above, m, n
indicates any positive integer. ] Those represented by these can be used, but are not limited to these.

Each of the above two types of surface treatment agents may be used alone, or both may be used in combination. The amount used is not particularly limited, but it is preferable to use about 0.1 to 10 parts by weight of each of them per 100 parts by weight of the filler. If the amount of the surface treatment agent is too small, a sufficient treatment effect cannot be obtained, whereas if the amount is too large, the water resistance of the filler tends to decrease.

The surface treatment method is not particularly limited; for example, the surface of the molten alumina may be modified in advance with the above-mentioned surface treatment agent by performing the 130-b treatment in the presence of water (pretreatment method), Alternatively, untreated molten alumina and the surface treatment agent may be mixed together with other components at the stage of preparing the composition (integral blend method). Furthermore, it is also possible to use a combination of three materials: fused alumina that has been surface-treated in advance, untreated alumina, and a surface treatment agent.

The epoxy resin composition according to the present invention may contain fillers other than those mentioned above, such as talc, calcium silicate, magnesium silicate, etc., and may also be diluted with a solvent such as lower alcohol or acetone. You can. Furthermore, the same composition may contain, if necessary, - a curing accelerator (tertiary amine, imidazole, etc.), a mold release agent (wax, stearic acid, stearate, etc.), a coloring agent (carbon Other additives such as pigments such as black, metal oxides, etc.) may also be included.

An epoxy resin composition as a molding material can be obtained by mixing the above components using, for example, a mixer, a blender, or the like, and kneading them using a kneader, roll, or the like. After kneading, the mixture may be cooled and solidified, and pulverized into granules, if necessary.

It goes without saying that the epoxy resin composition according to the present invention is widely used in addition to various molding materials, such as coating materials, dip materials, casting materials, paints, and the like.

Next, examples of the present invention will be described together with comparative examples.

Examples 1 to 4 - “As the epoxy resin component, a bisphenol A type epoxy resin containing diaminodiphenylmethane as a hardening agent (Epicoat 1001 manufactured by Yuka Shell Epoxy FL), fused alumina as a filler, and an epoxy silane system as a surface treatment agent. Coupling agent (Nippon Unicar A-187) and/or reactive silicone oil (Nippon Unicar@
! IFZ-3704) were blended in the proportions shown in Table 1, mixed in a mixer, and then kneaded in a kneader to obtain an epoxy resin composition molding material. In Example 3, the surface treatment of the filler was carried out at 130-b in the presence of water.

- Comparative Examples 1 and 2 - Epoxy resin compositions were obtained in the same manner as in the above examples, except that hydrated alumina or calcined alumina was used as the filler instead of fused alumina.

Comparative Examples 3 and 4 - An epoxy resin composition was obtained in the same manner as in the above example except that no surface treatment agent was used.

After curing the epoxy resin compositions of the above Examples and Comparative Examples, the bending strength and Charpy impact strength of the cured products were measured.

The above results are also shown in Table 1.

As shown in Table 1, the cured epoxy resins of Examples containing surface-treated molten alumina have higher bending strength and Charpy impact strength than those of Comparative Examples. Further, in Example 3, in which the surface treatment of the filler was performed by a pretreatment method, excellent strength was achieved.

Furthermore, as a result of exposing the cured product of the example to SF and gas for 100 hours or more, no change was observed, and it was found that the cured product had good SF resistance and properties.

〔Effect of the invention〕

The epoxy resin composition according to the present invention has excellent resistance to large sulfur fluorides and can provide a cured product with significantly improved mechanical strength compared to conventional products. Therefore, the epoxy resin composition is expected to have a wide range of uses, including as a molding material for high voltage equipment such as gas switch arms.

Agent: Takehiko Matsumoto, Patent Attorney (Masari Ichi) (Volunteer 1, Relation to the indicated case Patent applicant address: 1048 Kadoma, Kadoma City, Osaka Prefecture Name (583) Matsushita Electric Works Co., Ltd. Company representative ((Toshio Miyoshi as Jomi ffi 4, no agent 6, subject of amendment yJ + plate 6, specification subject to amendment 7, content of amendment■ Full text of the scope of claims column of the specification amended as follows.

[1] 50 to 80% by weight of molten alumina is contained based on the total solid content of the composition, and the molten alumina is treated with an epoxy silane-based coating agent and/or a reactive silicone oil as a surface treatment agent. An epoxy resin composition characterized in that it has been surface-treated in advance, or that the same surface-treating agent is added together with the untreated molten alumina. ” ■ A total of 5 locations: page 3, line 12 of the specification, page 5, lines 4 to 5, page 5, lines 6 to 7, page 8, line 18, and page 10, table 1, extra notes ☆ ``Kaburisoge agent'' is written in ``
``Campling agent'' is corrected.

Claims (1)

[Claims] 1 Contains 50 to 80% by weight of molten alumina based on the total solid content of the composition, and the molten alumina has been surface-treated in advance with an epoxysilane cupric agent and/or reactive silicone oil as a surface treatment agent. An epoxy resin composition characterized in that the same surface treatment agent is added to the untreated molten alumina.