JPH11293094A - Epoxy resin composition for SF6 gas insulated equipment and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which is excellent in durability, mechanical strength and crack resistance to decomposition products of SF ₆ gas (HF gas) in a well-balanced manner and can provide an insulating molded article having a low dielectric constant. Getting things. SOLUTION: The epoxy resin composition for SF ₆ gas insulation equipment, which is obtained by adding a silicate compound powder to an epoxy resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the opening and closing device of SF ₆ gas-insulated equipment to encapsulate the SF ₆ gas, such as an insulating spacer between Kanroki in the power transmission device, or an insulating support or electrical members of other electrical equipment The present invention relates to an epoxy resin composition that can be suitably used for an insulating member and the like.

[0002]

2. Description of the Related Art In recent years, SF ₆ gas, which has excellent electrical insulation properties, has been used as an insulating medium for insulating equipment such as substation equipment and circuit breakers. Although this SF ₆ gas is chemically stable, it is decomposed by corona discharge or arc discharge generated inside the insulating device, and SF ₂ , SF ₄ , S ₂ F ₂ , SO ₃ , SO ₃
It produces F ₄ , SO ₂ F _4, etc. Among them, SF ₄ gas reacts with water present in insulating equipment and decomposes according to the following reaction formulas (1) and (2) to generate HF gas: SF ₄ + H ₂ O → SOF ₂ + 2HF ( 1) SOF ₂ + H ₂ O → SO ₂ + 2HF (2)

In addition, parts such as an opening / closing device of an insulating device using SF ₆ gas as an insulating medium, an airborne power transmission device, or an insulating member such as an insulating support of an electric device or an insulating spacer between electric members are included. , Excellent insulation properties,
Conventionally, an insulating molded article made of an epoxy resin composition has been used from the viewpoint of mechanical properties and moldability. However, silica (SiO 2) is used as a filler for the filler because of its low dielectric constant and high mechanical strength. ₂ ) A powder is used, and the silica powder is decomposed and deteriorated according to the reaction formula (3): SiO ₂ + 4HF → SiF ₄ + 2H ₂ O. As a result, there is a problem that the surface resistance of the insulating molded article is reduced to cause dielectric breakdown, and further corrosion leads to a reduction in mechanical properties.

Therefore, for example, Japanese Patent Application Laid-Open No. 1-247449
JP, JP-A-4-130126, JP-A-4-3126
No. 41711, SF is used as the filler.
_A technique using aluminum oxide (alumina) powder having durability against decomposition products of ₆ gases (HF gas) (hereinafter, also referred to as “SF ₆ gas resistance”) is disclosed.

However, the dielectric constant of alumina powder is usually 9 to
Since it is relatively high at 11, the dielectric constant of the insulating molded article containing such alumina powder also becomes high. In recent years, in particular, with the increase in voltage and miniaturization of electrical devices including insulating equipment, insulating molded products that can withstand more severe conditions have been demanded.
It is not desirable to increase the dielectric constant because the reduction of the corona discharge starting voltage in view of the shape is a problem.
Although it is conceivable to reduce the filling amount of the alumina powder, there is a problem that the mechanical strength and the crack resistance of the insulating molded product are reduced.

Other fillers having a dielectric constant lower than that of alumina powder and having an SF ₆ gas resistance include, for example, dolomite, sodium fluoride, aluminum fluoride, and magnesium fluoride. An insulating molded article made of an epoxy resin composition containing the same has a problem that mechanical strength, crack resistance, and moldability are poor. Further, Japanese Patent Publication No. 49-38718 discloses a technique in which cordierite is used in combination with magnesium fluoride or the like as a filler, but the above problem has not been solved yet.

That is, the decomposition product of SF ₆ gas (HF
It has been desired to develop an epoxy resin composition which is excellent in durability against gas, mechanical strength and crack resistance in a well-balanced manner and can provide an insulating molded article having a low dielectric constant.

[0008]

SUMMARY OF THE INVENTION In view of the above facts, an object of the present invention is to provide an insulating molded article having a good balance of SF ₆ gas resistance, mechanical strength and crack resistance, and a low dielectric constant. The object of the present invention is to obtain an epoxy resin composition.

[0009]

SUMMARY OF THE INVENTION The present invention relates to an epoxy resin composition for SF ₆ gas insulated equipment obtained by adding a silicate compound powder to an epoxy resin.

[0010] Further, the present invention provides an SF ₆ powder obtained by adding a silicate compound powder, or a silicate compound powder and an inorganic powder other than the silicate compound to an epoxy resin.
The present invention relates to an epoxy resin composition for gas insulation equipment.

In these cases, the silicate compound is preferably an independent silicate.

The silicate compound is preferably a cyclic silicate.

The silicate compound is preferably a chain silicate.

Further, the independent silicate is preferably forsterite, fayalite, tephrite, knevelite or montecelite having an olivine structure.

The independent silicate is preferably zircon.

The cyclic silicate is preferably cordierite.

The chain silicate is preferably wollastonite belonging to the pyroxene group.

The silicate compound powder is preferably composed of fine particles having an average particle diameter of 100 μm or less or needle-like substances having an average fiber diameter of 100 μm or less.

Further, the epoxy resin composition for an SF ₆ gas insulating device has a glass transition temperature of 140 ° C. or higher and a linear expansion coefficient of 40 ° C. or lower at a temperature lower than the glass transition temperature.
It is preferable that an organic powder or fiber having a ppm / ° C. or lower is further added.

Further, the present invention provides an epoxy resin comprising an inorganic powder other than a silicate compound and an organic substance having a glass transition temperature of 140 ° C. or higher and a linear expansion coefficient of 40 ppm / ° C. or lower at a glass transition temperature or lower. The present invention also relates to an epoxy resin composition for SF ₆ gas insulation equipment, which is obtained by adding powder or fiber of the formula (1).

In these cases, the composition is mainly MgO and Si
It is preferably a silicate compound consisting of O ₂ .

In this case, the content of the MgO component is 16 to
Preferably it is 94% by weight.

It is preferable that the composition is a silicate compound mainly composed of CaO and SiO ₂ .

In this case, the CaO component is 20 to 20% of all components.
Preferably it is 90% by weight.

It is preferable that the composition is a silicate compound mainly composed of CaO, MgO and SiO ₂ .

In this case, the total of the MgO component and the CaO component in the composition is preferably 20 to 90% by weight of the total components.

A silicate compound mainly composed of MgO and SiO ₂ , a silicate compound mainly composed of CaO and SiO _2, and a silicate compound mainly composed of CaO and Mg 2
One or a mixture of two or more silicate compounds composed of O and SiO ₂ can also be used.

Further, the present invention also relates to moldings and SF ₆ gas insulated apparatus using the same comprising the SF ₆ gas insulation apparatus epoxy resin composition.

[0029]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an epoxy resin composition for an SF ₆ gas insulating device, which is obtained by adding a silicate compound powder to an epoxy resin.

The epoxy resin used in the present invention has at least two epoxy groups and has an epoxy equivalent of 10
There is no particular limitation as long as the softening point is 0 to 5000 and the softening point is 200 ° C. or less. For example, bisphenol type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, Glycidylamine type epoxy resin, linear aliphatic epoxy resin,
Examples include alicyclic epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, biphenyl type epoxy resins, cyclopentadiene type epoxy resins, and naphthalene type epoxy resins, but are not particularly limited. Further, the present invention can be applied not only to epoxy resins but also to thermosetting resins such as phenol resins and unsaturated polyester resins.

The epoxy resins can be used alone or in any combination. Above all, it is preferable to use a bisphenol-type epoxy resin or an alicyclic epoxy resin from the viewpoints of viscosity, heat resistance of the obtained molded article, and mechanical strength.

Examples of the bisphenol type epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol D type epoxy resin, brominated bisphenol A type epoxy resin, and bisphenol A modified with isocyanate. It is preferable to use a bisphenol-type epoxy resin having an epoxy equivalent of 100 to 2,000 and a softening point of 150 ° C. or less from the viewpoint of the resin viscosity during molding and the heat resistance and mechanical strength of the obtained cured product.

Examples of the alicyclic epoxy resin include cyclohexene oxide epoxy resins synthesized by a peroxide method such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and 3,4-epoxy-cyclohexyl-3 ', 4'. -Epoxy cyclohexane carboxylate and polyglycidyl ester-based epoxy resins such as hexahydrophthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester, etc., because of their excellent balance of heat resistance and mechanical strength. It is preferable to use an alicyclic epoxy resin having an epoxy equivalent of 100 to 2000 and a softening point of 150 ° C. or less.

Next, the silicate compound powder according to the present invention will be described. The silicate compound powder in the present invention serves as a filler in order to impart mechanical strength to the obtained molded article, and is more SF ₆ than silica which has been conventionally used. It has excellent durability against gas decomposition products (HF gas) and has a lower induction ratio than alumina. The most significant feature of the present invention is that the powder of the silicate compound having such advantages is used as a filler for the epoxy resin composition for SF ₆ gas insulating equipment.

The silicate compound may be an epoxy resin
There is no particular limitation as long as it can be dispersed in fats.
For example, the following can be mentioned.
Can be used in any combination. (I) Forsteri, a lankanite family
te: 2MgO ・ SiO_Two), Fayalite (2)
FeO / SiO_Two), Tephrite (Tephroite: 2MnO)
・ SiO_Two), Knebelite (Knebelite: FeO.Mn)
O ・ SiO_Two) And Montecelite (C)
aO ・ 2MgO ・ SiO_Two), Zircon (Zircon: ZrO)
_Two・ SiO_Two), A garnet tribe of Almandin
ndine: Fe_Three ²⁺Al_TwoSi_ThreeO₁₂), Andradite (And
radite: Ca_Three(Fe³⁺, Ti)_TwoSi_ThreeO₁₂), Gross
Lahr (Grossular: Ca_ThreeAl_TwoSi_ThreeO₁₂), Spessa
Rutin (Spessartine: Mn_ThreeAl_TwoSi_ThreeO₁₂)and
Chrome garnet (Uvarovite: Ca_ThreeCr_TwoSi_ThreeO₁₂),
Fenasite (Be)_TwoSiO_Four)
And silica sphalerite (Zn_TwoSiO_Four), Aluminum silicate
Sillimanite (Al)_TwoO (Si
O_Four)), Andalusite: Al_TwoO (S
iO_Four)), Topaz (Topaz: Al_TwoO (SiO_Four) (O
H, F)_Two) And Kyanite (Al)_TwoO (S
iO_Four)) And other independent silicates. (Ii) Cordierite (Al)_ThreeMg
_Two(Si_FiveAlO₁₈)), Beryl (Beryl: Be)_ThreeAl_Two(S
i₆O₁₈)) And other cyclic silicates. (Iii) Enstarite which is a pyroxene group
gSi_TwoO_Five), Steatite (Meat Si)
_TwoO_Five), Diopside (Diopside: CAMgSi)_TwoO₆), Sports
Jumen (Spodumene: LiAlSi_TwoO₆), Jade (Ja
deite: NaAlSi_TwoO₆), Wollastonite (silica ash)
(Wollastonite: CaSiO)_Three) And rose pyroxene (M
nSiO_Three), Tremolite: C, an amphibolite family
a_TwoMg_Five(OH)_Two(Si_FourO₁₁)_Two) And anthrite (Ant)
hophylite: (Mg, Fe)₇(OH)_Two(Si_FourO₁₁)_Two)
Such as chain silicates. (Iv) Others, sodium melilla, a member of the melilite family
(Sodium melilite: NaCaAlSi_TwoO₇), Game
Gehlenite: Ca_TwoAl_TwoSi_TwoO₇) And Ake
Lumanite (Akermanite: Ca_TwoMgSi_TwoO₇)
Muscovite: K_TwoAl_TwoM
g_Two(OH)_Four[(Si_FourO_Ten)_Two]), Muscovite (K_TwoAl_Four
(OH)_Four[(Si_FourAlO_Ten)_Two]) And Paragonai
(Pallagonite: NaAl_TwoMg_Two(OH)_Four[(Si_FourO
_Ten)_Two]), Wax stone (Pyroohyllite: Al_Four(OH)
_Four[(Si_FourO_Ten)_Two]), Talc (Talc: Mg₆(OH)
_Four[(Si_FourO _Ten)_Two]), Kaori, a Kaolinite tribe
Knight (Al_Four(OH)₈(Si_FourO_Ten)), Montmorillo
Montmorillonite, a Knight tribe
(Na)_{0. 7}(Al_3.3Mg_0.7) (OH)_Four[(Si_FourO
_Ten)_Two]), Layered silicates, feldspar family soda length
Stone (Sodium feldspar: NaAlSi_ThreeO₈), Feldspar (Fe
ldspar: KAlSi_ThreeO₈), Barium feldspar (Celsian: B
aAl_TwoSi_TwoO₈), Anorthite (Anorthite: CaAl)_TwoSi
_TwoO₈) And potassium feldspar (Sanidine: KAlSi)_ThreeO₈),
Nepheline, a member of the nepheline family (NaAlS)
iO_FourAnd Na_ThreeK (Al_FourSi_FourO₁₆)) And Carnegie
Stone (Carnegieite: KAlSiO)_Four), Zeolite
Borozite (Analcite: NaAlSi_TwoO₆・ H_TwoO) and
Soda zeolite (Na_TwoAl_TwoSi_ThreeO_Ten・ 2H_TwoO), soda
Sodalite: Na₈[Al₆
Si₆O_{twenty four}] · Cl_Two) And Nozelite (Nosean: N)
a₈[Al₆Si₆O_{twenty four}] · SO_Four3D reticulated silicic acid such as
salt. And so on.

The silicate having the lowest dielectric constant is a three-dimensional network silicate quartz (silica; SiO ₂ ). The three-dimensional network silicate has a structure in which each Si-O tetrahedron has an adjacent Si-O tetrahedron.
It shares a tetrahedron and all four vertices, creating a three-dimensional network. For this reason, it is dense, has high hardness and excellent mechanical strength, but is easily eroded by hydrofluoric acid. Focusing on silicate compounds that have a low dielectric constant next to quartz (silica; SiO ₂ ) and are also industrially produced, evaluate the SF ₆ gas resistance and electrical and mechanical properties of the silicate compounds. did.

The feldspar group and the quasi-feldspar group, which are three-dimensional network silicates, have a structure similar to that of quartz (silica; SiO ₂ ). Are dissolved in alkali metals K, Na, and Ca, which may decrease the content, and the zeolite group further has water of crystallization in the composition, so that it is inferior in hydrofluoric acid resistance.

Further, mica and talc, which are typical natural ores, belong to the layered silicate. In a layered silicate, a Si-O tetrahedron shares three corners to form a flat plate-like structure (two-dimensional network structure). Although this layered silicate is excellent in electrical properties, it is cleaved remarkably because the layers are bonded by a weak van der Waals force, and the layers are susceptible to chemical attack by hydrofluoric acid. For this reason, layered silicates such as mica are inferior in SF ₆ gas resistance as already reported (National Institute of Electrical Engineers of Japan, S.4-3; 1989).

Accordingly, three types of independent silicates, cyclic silicates and chain silicates are particularly useful.

[0040] those independent silicate and is present as standalone that SiO tetrahedra are separated, i.e. SiO tetrahedra not also share how vertices are independent one by one, the (SiO ₄ ) A structure in which cations enter between Si-O tetrahedrons and bond to each other in a form that neutralizes ^4- ions. In particular, in the olivine group, (SiO ₄ ) ^4- ions are the oxygen atoms Structure chemically bonded via divalent cations (R ₂ ²⁺ [SiO ₄ ], R ²⁺ = Mg, Fe ²⁺ , Ca)
With. Naturally produced olivine, which is a solid solution of forsterite and fayalite ((Mg,
Fe ₂ ²⁺ ) SiO ₄ ). Forsterite, an end component of solid solution, is considered to be a typical compound of the Earth's mantle. (SiO ₄ ) ^4- M
g ²⁺ is coordinated. Oxygen is in a hexagonal close-packed state, and the structure has a structure in which silicon is contained in four coordination positions and magnesium is contained in six coordination positions.

Cyclic silicate refers to Si having a tetrahedral structure.
O ₄ is bonded in a ring, the cation is 2 Si—O tetrahedron,
Connects two corners to form a continuous ring (Si ₂ O ₇ )
^{_{6-, (Si 3 O 9)}} 6-, (Si 4 O 12) 8-, (Si 6 O 18)
^A silicate compound having a structure that exists in a form that neutralizes ^12- ions.

In the chain silicate, a Si—O tetrahedron is connected in a chain with two corners in common, and a cation forms a (Si ₂ O ₆ ) _∞ ^4- ion formed by the chain. A silicate compound having a structure that exists in a neutralizing form.

Among the above-mentioned independent silicates, SF ₆ gas resistance is excellent (because it does not contain an alkali metal which may degrade the electrical insulation due to ion dissociation due to erosion by hydrofluoric acid), It is preferable to use forsterite, fayalite, tephrite, knevelite or montecelite having an olivine structure in terms of excellent strength. Further, it is preferable to use zircon in terms of low thermal expansion, high electrical insulation, and excellent arc resistance.

Among the cyclic silicates, cordierite is preferably used because it is excellent in SF ₆ gas resistance, has excellent mechanical strength, and does not contain toxic Be.

Among chain silicates, wollastonite belonging to the pyroxene group is preferred because it is excellent in SF ₆ gas resistance, mechanical strength and crack resistance.

Of these, the compositions are mainly MgO and Si
O_TwoAs silicate compounds consisting of olivine (Oli
vine: (Mg, Fe)_TwoSiO_Four), Forsterite (F
orsterite: 2MgO ・ SiO_Two), Clino Enstati
(Clinoenstatite: MgO / SiO_Two), Enstatai
(Enstatite: MgO / SiO_Two), Steatite (Ste
atite: MgO ・ SiO_Two), Warm asbestos (Chrysotile: 3Mg)
O.2SiO_Two・ 2H _TwoO), talc (Talc: 3MgO.4)
SiO_Two・ H_TwoO), Cordirite (2M)
gO ・ 2Al_TwoO_Three・ 5SiO_Two), Red garnet (Pyrope: 3
MgO / Al_TwoO _Three・ 3SiO_Two), Sapphline (Sapph
irine: 4MgO ・ 5Al_TwoO_Three・ 2SiO_Two)
Can be

As silicate compounds mainly composed of CaO and SiO _2, Wollastonites
te: CaO.SiO ₂ ), Larnite (Larnite: 2CaO)
・ SiO ₂ ), Rankinite (Rankinite: 3CaO ・ 2)
SiO ₂ ), anorthite (Anorthite: CaO.Al ₂ O ₃ .2)
SiO _2), gehlenite (Gehlenite: 2CaO · Al ₂
O ₃・ SiO ₂ ), Grossuralite (Garnet):
3CaO.Al ₂ O ₃ .3SiO ₂ ), Danburite (Danbu)
rite: CaO.B ₂ O ₃ .2SiO ₂ ), gray iron pyroxene (Hedenb
_{ergite: CaO · FeO · 2SiO 2} ), Nagel hobby tight _{(Nagelschmidtite: 7CaO · P 2 O} 5 · 2SiO
₂ ), Silicocarnotite: 5CaO
・ P ₂ O ₅ .SiO ₂ ), titanite (Titanite: CaO
TiO ₂ · SiO ₂ ).

Further, as the silicate compounds mainly composed of CaO, MgO and SiO ₂ , Montecellite (Monticellite: CaO.MgO.SiO ₂ ) and Okermanite (Akermanite2CaO.MgO.2Si)
O ₂ ), diopside (Diopside: CaO.MgO.2Si)
O ₂ ), Merwinite (MgO.3CaO)
.2SiO ₂ ).

Among the silicate compounds, SF ₆ resistant
It is preferable to use forsterite, montecelite, wollastonite, or steatite from the viewpoint of excellent gas properties and mechanical strength and low dielectric constant.

In the silicate compound mainly composed of MgO and SiO ₂ , the content of MgO in the composition is 1% in view of the excellent SF ₆ gas resistance and the excellent mechanical strength.
It is preferably from 6 to 94% by weight. In particular, the content of MgO is preferably 20 to 80% by weight of the composition in view of excellent SF ₆ gas resistance, excellent mechanical strength, and low dielectric constant.

In the silicate compound mainly composed of CaO and SiO ₂ , the content of CaO is 2% in the composition in view of excellent SF ₆ gas resistance and mechanical strength.
It is preferably from 0 to 90% by weight. In particular, the content of CaO is preferably 30 to 70% by weight in the composition in view of excellent SF ₆ gas resistance, excellent mechanical strength and low dielectric constant.

Further, in the silicate compound mainly composed of CaO, MgO and SiO ₂ , the sum of the MgO component and the CaO component in all components is high in terms of excellent SF ₆ gas resistance and mechanical strength. It is preferably 20 to 90% by weight. Particularly excellent in SF ₆ gas resistance and mechanical strength,
In view of the low dielectric constant, the total of the MgO component and the CaO component is preferably 25 to 70% by weight of all the components.

Examples of the shape of the powder of the silicate compound in the present invention include fine particles, needles, plates, balloons, beads, etc., but they are characterized by moldability, mechanical strength and crack resistance. Therefore, it is preferably in the form of fine particles or needles.

In the case of fine particles, the average particle size is 100 μm.
m, the average particle size is preferably 100 μm or less from the viewpoint that the mechanical strength of the obtained product is lowered. Further, from the viewpoint that the balance between fluidity and mechanical strength is excellent, 0.5 It is particularly preferred that the thickness be 50 μm.

In the case of needles, the average fiber diameter is 10
It is preferably 0 μm or less and the aspect ratio is 100 or less, and from the viewpoint of the viscosity of the resin composition during molding, it is particularly preferable that the average fiber diameter is 30 μm or less and the aspect ratio is 80 or less. The average fiber diameter is usually 0.1 μm or more.

In the present invention, the compounding ratio of the powder of the silicate compound can be appropriately selected by those skilled in the art as long as a molded product can be obtained. From the point that sex is not impaired,
It is preferably 20 to 80 parts by volume with respect to the whole resin composition, and furthermore, it has a good balance of mechanical strength, crack resistance and moldability.
It is particularly preferred that the amount is from 70 to 70 parts by volume.

The epoxy resin composition for SF ₆ gas-insulated equipment of the present invention may contain an inorganic powder other than the silicate compound. In this case, there is an advantage of improving the mechanical strength and crack resistance of the obtained molded product.

As the inorganic substance other than the above silicate compound, any inorganic substance may be used as long as it is generally used as a filler for a resin composition. Examples thereof include fused silica, crystalline silica, alumina, hydrated alumina, and hollow glass beads. , Glass fiber, magnesium oxide, titanium oxide, calcium carbonate, magnesium carbonate, dolomite, talc, potassium titanate fiber, calcium hydroxide, magnesium hydroxide, antimony trioxide, anhydrous gypsum, barium sulfate,
Examples thereof include boron nitride, silicon carbide, aluminum fluoride, calcium fluoride, magnesium fluoride, and aluminum borate. These can be used alone or in any combination.

The shape of the inorganic powder other than the silicate compound, the average particle diameter in the case of fine particles, and the average fiber diameter and aspect ratio in the case of needles are as follows:
It may be the same as the silicate compound powder.

However, when blending an inorganic substance other than the above silicate compound, it should be noted that the blending is performed within a range that does not increase the induction ratio of a molded product obtained from the epoxy resin composition for SF ₆ gas insulating equipment of the present invention. Should. The specific mixing ratio of the powder other than the silicate compound is preferably from 3 to 90 parts by volume based on the whole inorganic filler containing the silicate compound, and furthermore, the mechanical strength, crack resistance and molding From the viewpoint of excellent balance of properties, it is particularly preferable that the amount is 5 to 70 parts by volume based on the whole inorganic filler containing the silicate compound.

Next, the epoxy resin composition for SF ₆ gas insulated equipment of the present invention contains a curing agent in order to chemically react with the epoxy resin to cure the epoxy resin. The curing agent is not particularly limited as long as it is generally used for a composition comprising an epoxy resin.
Phthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride,
Acid anhydrides such as methyltetrahydrophthalic anhydride, triethylenetetramine, bis (4-aminophenyl) methane, bis (3-aminophenyl) methane, bis (4-aminophenyl) sulfone, 1,4-phenylenediamine, Amines such as 2,4-naphthalenediamine, benzyldimethylamine, 1,5-naphthalenediamine, dicyandiamide, bisphenol A, bisphenol F, bisphenol S, phenol novolak resin, p
Polyhydric phenol compounds such as -hydroxystyrene resin, and imidazole-based compounds such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole. These may be used alone or in any combination. Can be.

Among these cured materials, phthalic anhydride, hexahydrophthalic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, trimellitic anhydride, It is preferable to use acid anhydrides such as pyromellitic acid, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

The mixing ratio of the curing agent may be within the same range as the amount used in the conventional epoxy resin composition. However, from the viewpoint of moldability, the curing agent is added in an amount of 40 to the stoichiometry of the epoxy resin. It is preferably from 140 to 140%, and particularly preferably from 60 to 120% with respect to the stoichiometric amount of the epoxy resin, since the obtained molded product has an excellent balance between heat resistance and mechanical strength. .

Further, the epoxy resin composition for SF ₆ gas insulated equipment of the present invention contains a curing accelerator for promoting a chemical reaction between the epoxy resin and the curing agent.

The curing accelerator is not particularly limited as long as it is a conventional one which serves as a catalyst for the reaction between the epoxy resin and the curing agent. Examples thereof include triphenylphosphine and triphenyl phosphite. Organic phosphorus compounds, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethylimidazole, 2-ethyl-4
Imidazoles such as -methylimidazole, 3- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, and 3 such as α-methylbenzylmethylamine.
Organic amines such as 1,8-diazabicyclo (5,4,0) undecene-7; and quaternary ammonium salts such as tetraethylammonium bromide, benzyltriethylammonium chloride and benzyltri-n-butylammonium bromide. And each can be used alone or in any combination.

The mixing ratio of the curing accelerator is as follows:
It is sufficient that the effect as an accelerator is exhibited and storage stability is not impaired. The amount is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the epoxy resin.

Further, the epoxy resin composition for SF ₆ gas-insulated equipment of the present invention has the following effects:
From the viewpoint of improving mechanical strength and crack resistance, the glass transition temperature is 140 ° C. or higher and the linear expansion coefficient at a temperature equal to or lower than the glass transition temperature is 40 ppm / ° C.
It may include organic powders or fibers that are: Such organic powders or fibers have been realized to reduce the coefficient of thermal expansion of organic components excluding inorganic fillers such as silicate compounds, improve heat resistance, and reduce the amount of fillers added. It plays a role in lowering the dielectric constant of the molded product.

Here, the glass transition temperature of the organic substance is 1
The requirement that the linear expansion coefficient at a temperature of 40 ° C. or more and the glass transition temperature or less be 40 ppm / ° C. or less is because the heat resistance of a molded article obtained at a glass transition temperature of less than 140 ° C. is reduced. This is because long-term reliability is lacking, and the coefficient of thermal expansion of the molded article whose linear expansion coefficient exceeds 40 ppm / ° C. becomes large, which causes cracks. The glass transition temperature and the coefficient of linear expansion are values specific to each organic substance, and those preferably used in the present invention as the organic substance satisfying the above requirements include, for example, polyimide, polyamide imide, polysulfone, polyphenyl ether, poly Benzimidazole, aramid, polyparaphenylenebenzobisoxazole and the like can be mentioned, and they can be used alone or in any combination.

Further, from the viewpoint of lowering the coefficient of expansion and increasing the heat resistance of the molded product, the linear expansion coefficient at a temperature of 200 ° C. or higher and lower than the glass transition temperature is 3 ° C.
The concentration is preferably 5 ppm / ° C. or less, and examples of those falling within this range include polyimide, polyamideimide, polybenzimidazole, aramid, and polyparaphenylenebenzobisoxazole.

When the organic substance is a powder, its shape may be in the form of particles, and the average particle size at that time is within a range where the mechanical strength and crack resistance are improved without impairing the moldability, for example, 0.1. It should just be 100 micrometers. In the case of a fiber, it is sufficient that the fiber does not increase the viscosity of the resin composition during molding, for example, the average fiber diameter is 100 μm or less.

The compounding ratio when the organic powder or fiber is blended may be within the range in which the molded product can be obtained, but the moldability is not impaired, and the mechanical strength and crack resistance of the obtained molded product are not impaired. In view of the improvement in the heat resistance, the content is preferably 1 to 90% by volume of the total amount of the organic powder or fiber and the inorganic filler, and the balance between the mechanical strength and the crack resistance of the molded product, which is considered to be moldability. In particular, the content is preferably 3 to 70% by volume of the total amount of the organic powder or fiber and the inorganic filler.

Further, the epoxy resin composition for SF ₆ gas insulating equipment of the present invention includes a coupling agent such as a silane-based, a titanium-based, and an aluminum-based, an acrylic rubber, a butadiene-based rubber, a nitrile-based rubber, and a styrene-based rubber. A compounding agent such as a flexibility-imparting agent, a modifying agent, a colorant, a pigment, a deterioration inhibitor, an internal mold release agent, and a surfactant may be added as long as the effects of the present invention are not impaired.

The mixing ratio when the coupling agent is compounded can be appropriately selected by those skilled in the art. However, from the viewpoint of improving the adhesiveness between the resin composition and the filler, 100% by weight of the filler is used. It is preferably 0.1 to 20 parts by weight based on parts.

The mixing ratio when the flexibilizing agent is compounded can be appropriately selected by those skilled in the art, but it is excellent in balance between moldability and crack resistance of the molded product. Therefore, the amount is preferably 1 to 40 parts by weight based on 100 parts by weight of the epoxy resin.

The epoxy resin composition for SF ₆ gas insulated equipment of the present invention can be produced by mixing the above-mentioned components in a conventional manner.

A molded article can be obtained by a conventional method, for example, a casting method, using the epoxy resin composition for SF ₆ gas-insulated equipment of the present invention. That is, the present invention also relates to the molded article.

The obtained molded product has a low dielectric constant,
Excellent in chemical substances and SiO in the composition _TwoContains ingredients
Despite SF₆Good gas properties
Fruit, SF₆Switchgear for gas insulated equipment, pipeline air transport
Support or electrical insulation of electrical equipment or other electrical equipment
Suitable for insulating members such as insulating spacers between members
I can do it.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0079]

EXAMPLES First, Table 1 shows components used in Examples 1 to 15.

[0080]

[Table 1]

Examples 1 to 11 First, according to the mixing ratio (% by volume) shown in Table 2, the components except for the powder of the silicate compound and the curing accelerator were mixed at room temperature and normal pressure for 10 minutes using a Raikai machine. . The powder of the silicate compound is added to the obtained mixture, mixed for 1 hour at room temperature and normal pressure, and then a curing accelerator is added and further mixed for 10 minutes under vacuum at room temperature to obtain the SF ₆ gas insulating device of the present invention. Epoxy resin compositions 1 to 11 were obtained.

The obtained resin compositions 1 to 11 were poured into a glass casting mold, heated and molded at 130 ° C. for 6 hours using a high-temperature bath, and further heated and molded at 150 ° C. for 6 hours. Molded products 1 to 11 (thickness: 3 mm) were obtained.

The obtained molded product was measured for SF ₆ gas resistance, dielectric constant, bending strength and crack resistance according to the following methods. Table 2 shows the results.

[Measurement Method] SF ₆ Gas Resistance After an electrode was attached to the obtained plate-like molded product, a mixed gas of SF ₆ gas and HF gas (SF ₆ gas: HF gas = 10)
0: 0.5 (volume ratio)).
A DC voltage of 500 V was applied, and after a lapse of one minute, the current value (A) was measured while the voltage was still applied. Surface resistance value is 1
The case of 0 ¹⁵ Ω or more was indicated by ○, the case of 10 ¹⁴ Ω or more and less than 10 ¹⁵ Ω was indicated by Δ, and the case of 10 ¹⁴ Ω or less was indicated by ×.

Dielectric constant After the electrodes were attached to the obtained plate-like molded product, it was connected to a dielectric constant measuring circuit, a DC voltage of 500 V was applied, and after a lapse of 1 minute, the dielectric constant (60 Hz) was kept applied. Was measured.

Bending strength The bending strength (kgf / mm ² ) of the obtained plate-like molded product was
It was measured by three-point bending according to IS-K6911.

Glass Transition Temperature The glass transition temperature Tg (° C.) of the obtained plate-like molded product was measured by thermomechanical analysis. From the coefficient of thermal expansion curve, Tg was determined from the intersection of the straight line portion of the glass region and the extension of the straight line portion of the rubber region of the molded product.

Crack Resistance Publication 455-2 (Pa
The crack resistance was examined according to the method described in rt2). However, an aluminum orifice washer was used as the orifice washer. FIG. 1 is a schematic explanatory diagram for explaining the method of the present test. FIGS. 1A and 1B are schematic explanatory views showing the shape of the orifice washer used in this test. FIG. 1C is a schematic explanatory view showing a test piece obtained by embedding an orifice washer in a resin composition.
As shown in FIG. 1C, a test piece embedded in a resin composition to be tested was used. In FIG. 1, 1 is an oliphant washer, and 2 is a resin composition. After curing, the test specimens were alternately exposed to high and low temperatures, starting with a gentle thermal shock, gradually increasing the temperature difference, and indicating the crack index at the time of cracking. The high temperature side uses an oven (30 minutes in the air), and the low temperature side uses a dry ice-alcohol solution (10 minutes in the liquid). Three or more test pieces were used, and the crack resistance was evaluated by arithmetically averaging the individual crack indices obtained according to Table 3.

[0089]

[Table 2]

From the results shown in Table 2, the dielectric constants of the resin molded products of Examples 1 to 11 are lower than those of the alumina filler of Comparative Example 1, and the dielectric constant of the resin molded product of the prior art with alumina is low. It was shown that the method was more effective for lowering the dielectric constant. In addition, the SF ₆ gas resistance of the resin molded products of Examples 1 to 11 was superior to that of the silica filler of Comparative Example 2.
Particularly, a resin molded product filled with a silicate powder that forms an olivine structure even with an independent silicate (Examples 1 to 5) or a resin molded product filled with a mixed filler thereof (Example 9,
Resistant SF ₆ gas of 10) shows the same characteristics as the alumina filler, it is revealed that the despite excellent characteristics containing the silicic acid component in the composition. But,
The SF ₆ gas resistance of Kali feldspar (Comparative Example 3) belonging to a three-dimensional network silicate having the same three-dimensional structure as silica was at the silica level. The crack resistance of the molded products of Examples 1 to 11 is higher than that of the alumina filler. In particular, zircon belonging to the independent silicate (Example 6) has a higher value than the others because of its low thermal expansion property. Was. The wollastonite belonging to the chain silicate (Example 8) exhibited high crack resistance despite the low filling amount in the resin composition.
Further, the bending strength and glass transition temperature (Tg) of the resin molded products of Examples 1 to 11 are equal to or higher than the alumina filler of Comparative Example 1, and are excellent in mechanical properties and heat resistance. It was shown that.

[0091]

[Table 3]

Examples 12 to 15 Epoxy resin for SF ₆ gas-insulated equipment according to the present invention in the same manner as in Example 1 except that forsterite having an average particle size shown in Table 4 was used as the silicate compound powder. Composition 12
To 15 and plate-like molded products 12 to 15, the same measurement as in Example 1 was performed. Table 4 shows the results.

Comparative Examples 1 to 3 Comparative resin compositions 1 to 3 and comparative molded products 1 to 3 were obtained in the same manner as in Example 1 except that the mixing ratios shown in Table 4 were changed. Was performed. The results are shown in Tables 2 and 4.

[0094]

[Table 4]

From the results shown in Table 4, Examples 1 and 12
The dielectric constants of the resin molded products of Comparative Examples 1 to 15 show lower values than those of the alumina-filled material of Comparative Example 1, and are effective in lowering the dielectric constant as compared with the resin molded product of the prior art which is filled with alumina. confirmed. The SF ₆ gas resistance of these examples was superior to that of the silica filler of Comparative Example 2. Further, the crack resistance and the glass transition temperature (Tg) of the resin molded products of Examples 1 and 12 to 15 were equal to or higher than the alumina filler of Comparative Example 1. Therefore, it was confirmed that the particle size of the filler had no effect on these properties.

Here, based on the results of Examples 1, 12 to 15 and Comparative Example 1, FIG. 2 shows the average particle size (μm) of the powder of the silicate compound (forsterite). The relationship with the bending strength (kgf / mm ² ) of a plate-like molded product is shown.

FIG. 2 shows that the bending strength of the molded product increases as the average particle size decreases. Also, it can be seen that when the average particle size approaches 100 μm, the bending strength becomes almost equal to the value of the conventional one using alumina of Comparative Example 1, and when it exceeds 100 μm, it is inferior to the conventional one. Thereby, the particle size of the silicate compound powder is 0.5 to 100 μm.
It can be said that m is preferable.

Experimental Examples 1 to 3 SF resistance in Examples 1 to 15 and Comparative Examples 1 to 3 described above.
_{6 In} the measurement of gas properties, after applying a DC voltage of 500 V, the time for exposing the plate-like molded product to a mixed gas of SF ₆ gas and HF gas was set to 0 minute, 10 minutes, 20 minutes, 30 minutes, Changes were made for 40, 60, 180 and 300 minutes. Then, the surface resistance value (Ω) of the plate-like molded product at each exposure time while the voltage was applied was determined according to JIS-K
It was measured according to 6911. The smaller the change in the surface resistance value, the better the SF ₆ gas resistance, which is preferable.

Experimental Example 1 corresponding to Examples 1 to 6 using independent silicates, Experimental Example 2 corresponding to Examples 7 to 8 using cyclic and chain silicates, and further using organic substances The results of Experimental Example 3 corresponding to Examples 9 to 11 are shown in FIGS.
It is shown in FIG. 3 to 5 show the relationship between the exposure time to a mixed gas of SF ₆ gas and HF gas and the surface resistance value.

FIG. 3 shows that the silica (SiO 2_Two)
The surface resistance value when filling is large immediately after gas injection.
Surface resistance is 10¹⁶From Ω to 10¹³Down to Ω
You can see that In contrast, the cans of Examples 1 to 5
When filled with independent silicates that form olivine structures
The shape decreases when gas is injected, but its value is 10 ^Fifteen
It is almost the same value as the conventional one using Ω and alumina.
Therefore, the rate of decrease is smaller than when silica is filled.
I understand that. Thus, the powder of independent silicate is filled.
The molding obtained is filled with SiO 2 in the composition._TwoContains
Despite the SF₆Shows excellent gas properties
Was done.

Also, from FIG. 4, the surface resistance of the molded article filled with the cyclic silicate powder (cordierite) of Example 7 starts to decrease immediately after gas injection, but the value is at a minimum point. Compared to 10 ¹⁴ Ω and silica filled,
Maintains high values. When the molded product filled with the chain silicate powder (wollastonite) is exposed to a mixed gas of SF ₆ / HF, the surface resistance slightly decreases.

Thus, the molded product filled with the powders of the independent silicate, the cyclic silicate and the chain silicate has a high S-resistance despite the fact that the composition contains SiO ₂ in the composition.
Excellent F ₆ gas properties were shown. In particular, a molded product filled with a silicate powder that forms a lanthanum structure even with an independent silicate exhibits SF ₆ gas resistance equivalent to that in the case of using alumina, and has excellent resistance to decomposition gas of SF ₆ gas. It was shown that.

Further, from FIG. 5, it was found that the SF ₆ gas resistance of the cured resin filled with the organic polymer powder was the same as that when alumina was used, and had no problem.

Table 5 shows the components used in Examples 16 to 36.

[0105]

[Table 5]

Examples 16 to 19 In accordance with the compounding ratios shown in Table 6, first, the components other than the silicate compound powder and the curing accelerator were mixed for 10 minutes at room temperature and normal pressure using a raikai machine. The powder of the silicate compound is added to the obtained mixture and mixed at normal temperature and normal pressure for 1 hour. Then, a hardening accelerator is added and the mixture is further vacuumed at normal temperature for 1 hour.
After mixing for 0 minutes, epoxy resin compositions 16 to 19 for SF ₆ gas insulated equipment of the present invention were obtained.

The obtained resin compositions 16 to 19 were poured into a glass casting mold, heated and molded at 130 ° C. for 6 hours using a high-temperature bath, and further heated and molded at 150 ° C. for 6 hours. Shaped products (thickness: 3 mm) 16 to 19 were obtained.

The obtained molded product was measured for SF ₆ gas resistance, dielectric constant, bending strength and crack resistance according to the following methods. Table 6 shows the results.

[0109]

[Table 6]

From the results shown in Table 6, the dielectric constants of the resin compositions of Examples 16 to 19 are all lower than that of the alumina filler of Comparative Example 4, and the resin molded products of the prior art which are filled with alumina It was shown that it is more effective in lowering the dielectric constant than that of. In addition, the resistance to S of the resin compositions of Examples 16 to 19 was
The F ₆ gas properties exhibited better properties than the silica-filled material of Comparative Example 5. In particular, the SF ₆ gas resistance of the resin molded products (Examples 16 and 19) filled with forsterite-based and montecelite-based powders shows the same properties as the alumina filler material, and the composition contains a silicic acid component. Despite the fact, it was found that they exhibited excellent properties. Example 16-
The crack resistance of the molded article No. 19 was higher than that of the alumina filler material, and the steatite type (Example 17) and the wollastonite type (Example 18) had a low filling amount in the resin composition. Regardless, it exhibited high crack resistance.
Further, the bending strength and the glass transition temperature (Tg) of the resin compositions of Examples 16 to 19 are equal to or higher than those of the alumina filler of Comparative Example 4, and are excellent in mechanical properties and heat resistance. It was shown that.

Examples 20 to 27 As silicate compound powders, forsterite-based fillers, steatite-based fillers, forsterite and magnesium oxide, forsterite and silica having the compositions shown in Table 7 were used. In the same manner as in Example 16, the S
The same measurement as in Example 16 was performed on the epoxy resin compositions 20 to 27 and the plate-like molded products 20 to 27 for F ₆ gas insulation equipment. Table 7 shows the results.

Comparative Examples 4 to 5 Comparative resin compositions 4 to 5 and comparative molded products 4 to 5 were obtained in the same manner as in Example 16 except that the mixing ratio was changed as shown in Table 7.
The same measurement as in Example 16 was performed. The results are shown in Table 7 and Table 7.

[0113]

[Table 7]

The results shown in Table 7 indicate that Examples 16 and 2
Resin molded product filled with 0-23 forsterite-based filler, resin composition filled with steatite-based filler of Examples 17 and 24-25, Forsterite and magnesium oxide of Example 26, and Example 27 The bending strength of the resin molded product filled with forsterite and silica was equal to or higher than that of the alumina filler of Comparative Example 4. Further, the crack resistance and the glass transition temperature (T of the resin molded products of Examples 16, 17 and 20 to 27)
g) showed a value equal to or more than that of the alumina filler of Comparative Example 4. Therefore, it was confirmed that these properties were not affected by the MgO content in the composition of the filler.

Based on the results of Examples 16, 17, 20 to 27 and Comparative Example 4, FIG.
Filler of silicate compound composed of iO ₂ (forsterite, steatite, magnesium oxide, silica)
The relationship between the content (% by weight) of the MgO composition therein and the dielectric constant of the obtained plate-like molded product is shown.

FIG. 6 shows that the higher the content (% by weight) of the MgO composition in the filler, the higher the dielectric constant of the molded product. The content of the MgO composition in the filler is 95% by weight.
Above, the dielectric constant becomes almost equal to the value of the conventional one using the alumina of Comparative Example 4, and it can be seen that the low dielectric constant effect is reduced. Thereby, it can be said that the content of the MgO composition in the filler is preferably less than 95% by weight.

Examples 28 to 36 The same procedures as in Example 16 were carried out except that forsterite-based fillers, wollastonite-based fillers and montecelite-based fillers having the compositions shown in Table 8 were used as the silicate compound powder. Similarly, the epoxy resin 28 for SF ₆ gas-insulated equipment of the present invention
To 36 and plate-like molded products 28 to 36, and the same measurement as in Example 16 was performed. Table 9 shows the results.

[0118]

[Table 8]

[0119]

[Table 9]

From the results shown in Table 9, Examples 18 and 2 were obtained.
Resin moldings filled with 8-31 wollastonite fillers, resin moldings filled with Montecelite-based fillers of Examples 19 and 32-35, and forsterite-based fillers and wollasts of Example 36 The bending strength of the resin molded product mixed with the knight filler was equal to or higher than that of the alumina filler of Comparative Example 4. Further, the crack resistance and the glass transition temperature (Tg) of the resin molded products of Examples 18, 19 and 28 to 36 were equal to or higher than the alumina filler of Comparative Example 4. Therefore, these properties are attributed to CaO or MgO in the filler composition.
It was confirmed that the content had no effect.

Here, based on the results of Examples 18, 28 to 31, and Comparative Example 4, FIG. 7 shows the CaO composition or the content (% by weight) of the CaO composition in the filler (wollastonite). The relationship between the obtained plate-like molded product and the dielectric constant is shown below.

FIG. 7 shows that the higher the content (% by weight) of the CaO composition in the wollastonite filler, the higher the dielectric constant of the molded product. When the content of the CaO composition in the wollastonite-based filler is 90% by weight or more, the dielectric constant becomes almost equal to the value of the conventional one using alumina of Comparative Example 4, and the low dielectric constant effect is reduced. . Thereby, CaO in the wollastonite-based filler is
It can be said that the content of the composition is preferably 90% by weight or less.

Further, based on the results of Examples 19, 32-36 and Comparative Example 4, FIG. 8 shows the total content of MgO and CaO in the filler (Montecellite and mixed filler) (FIG. 8). (% By weight) and the dielectric constant of the obtained plate-like molded product.

FIG. 8 shows that the dielectric constant of the molded product increases as the total content (% by weight) of the MgO and CaO compositions in the Montecelite-based filler and the mixed filler-based filler increases. When the total content of the MgO and CaO compositions in these fillers is 90% by weight or more, the dielectric constant becomes almost equal to that of the conventional one using the alumina of Comparative Example 4, and the low dielectric constant effect is reduced. . Thereby, it can be said that the total content of the MgO and CaO compositions in the filler is preferably 90% by weight or less.

Experimental Examples 4 to 8 S-resistance in Examples 16 to 36 and Comparative Examples 4 and 5 described above.
In the measurement of the F ₆ gas property, after applying an AC voltage of 500 V, the time for exposing the plate-like molded product to a mixed gas of SF ₆ gas and HF gas was set to 0 minute, 10 minutes, 20 minutes, 30 minutes.
Minutes, 40 minutes, 60 minutes, 180 minutes and 300 minutes. Then, the surface resistance value (Ω) of the plate-like molded product at each exposure time while applying the voltage was measured according to JIS-K
It was measured according to 6911. The smaller the change in the surface resistance value, the better the SF ₆ gas resistance, which is preferable.

Examples 16 to 19 using silicate compounds
Examples 16, 17, 21, and 23 in which the content of the MgO component of the silicate compound filler (forsterite and steatite) mainly composed of MgO and SiO ₂ was changed. Experimental Example 5 corresponding to Examples 24 and 25, Example 2 in which the content of MgO component in the filler was changed
Experimental Example 6 corresponding to Nos. 6 to 27, whose composition was mainly CaO and S
Examples 18 and 2 in which the CaO component content of the silicate compound filler (wollastonite) composed of iO ₂ was changed
Experimental Example 7 corresponding to Samples 8 and 31, the composition was mainly CaO and M
MgO and CaO in silicate compound fillers (montesenite and mixed fillers) consisting of gO and SiO ₂
Example 19, 32 to 36 in which the total content of components was changed
9 to 13 show the results of Experimental Example 8 corresponding to. Figure 9-13 shows a relationship between the exposure time and the surface resistance value of the mixed gas of SF ₆ gas and HF.

FIG. 9 shows that the silica (SiO ₂ ) of Comparative Example 5 was used.
It can be seen that the surface resistance value when the gas is filled greatly decreases immediately after gas injection, and the surface resistance value decreases from 10 ¹⁶ Ω to 10 ¹² Ω. On the other hand, the molded articles filled with the silicate compounds of Examples 16 to 19 (forsterite, steatite, wollastonite, montecelite) were compared with the molded articles filled with silica. It can be seen that the rate of decrease is small. Thus, it was shown that the molded product obtained by filling the powder of the silicate compound had excellent SF ₆ gas resistance despite the fact that the composition contained SiO ₂ .

Also, from FIG.
The composition of 1, 23, 24, 25 is mainly composed of MgO and SiO ₂
It can be seen that the decrease in the surface resistance value of the molded product filled with the silicate compound filler (forsterite type and steatite type) consisting of the above depends on the content of the MgO component in the filler. Molding when the MgO component is filled with silicate compound filler having a high content of 60 wt% or more, showed comparable anti-SF ₆ gas of the case using alumina, decomposition gas of SF ₆ gas It was shown to be excellent in resistance to The molded product when filled with a silicate compound filler having an MgO component content of 60% by weight or less starts to decrease immediately after gas injection, but the value is maintained higher than that when silica is filled. doing. However, MgO
It was shown that the molded product filled with the silicate compound filler having a component content of 15% by weight or less was reduced to the same level as the molded product filled with silica. Thus, it can be said that the content of the MgO composition in the filler is preferably 16% by weight or more from the viewpoint of SF ₆ gas resistance.

FIG. 11 shows the change in the surface resistance of the molded product obtained by combining the forsterite, magnesium oxide and silica in Examples 26 to 27 and changing the content of the MgO component in the filler. If high MgO content of the component in the filler (MgO ingredient content: 70 wt%) represents the equivalent resistance SF ₆ gas resistance in the case of using alumina, the better the resistance to decomposed gas of SF ₆ gas It has been shown. When the content of the MgO component in the filler is high (the content of the MgO component: 50% by weight), it can be seen that the rate of decrease is slower than that of the molded product filled with silica.

FIG. 12 shows that Examples 18, 28, 3
The rate of decrease in the surface resistance value of a molded product filled with a silicate compound filler (wollastonite type) mainly composed of CaO and SiO ₂ depends on the content of the CaO component in the filler I understand. Molded article when filled silicate compound filler having a high content of CaO component, showed comparable anti-SF ₆ gas resistance in the case of using alumina, the better the resistance to decomposed gas of SF ₆ gas It has been shown. The molded product filled with the silicate compound filler having a low CaO component content starts to decrease immediately after gas injection, but its value is maintained higher than that of the case filled with silica. However, it was shown that the molded product filled with the silicate compound filler having a CaO component content of 20% by weight was reduced to the same degree as the molded product filled with silica. Thereby, the content of the CaO composition in the filler is 20% by weight from the viewpoint of SF ₆ gas resistance.
The above is preferable.

Further, from FIG.
The ratio of the decrease in the surface resistance value of the molded product in which the composition of No. 36 was filled with a silicate compound filler (Monthesenite type and mixed filler type) mainly consisting of CaO, MgO and SiO ₂ was determined by the ratio of MgO and CaO It turns out that it depends on the total content of the components. The molded product when filled with a high silicate compound filler having a high total content of MgO and CaO components,
Shows SF ₆ gas resistance equivalent to the case of using alumina,
It was shown that SF ₆ gas had excellent resistance to decomposition gas. The molded product when filled with a silicate compound filler having a low total content of MgO and CaO components starts to decrease immediately after gas injection, but the value is maintained higher than that when silica is filled. doing. However, it was shown that the molded product when filled with a silicate compound filler having a total content of MgO and CaO components of 34% by weight was slightly higher than the molded product when filled with silica. Was done. Thus, from the viewpoint of SF ₆ gas resistance, it can be said that the total content of MgO and CaO components in the filler is preferably 20% by weight or more.

Thus, the molded product filled with the silicate compound (forsterite type, steatite type, wollastonite type, montecelite type), despite containing SiO ₂ in the composition, It was shown to be excellent in SF ₆ gas resistance. In particular, the molded product content of SiO ₂ component is filled with low silicate compound powder in the composition, showed comparable anti-SF ₆ gas of the case using alumina, resistance to decomposed gas of SF ₆ gas It was shown to be excellent.

[0133]

According to the first to fifth and twelfth aspects of the present invention, the durability, mechanical strength and crack resistance of SF ₆ gas against decomposition products (HF gas) are excellent in balance, and An epoxy resin composition capable of providing an insulating molded article having a low dielectric constant can be obtained.

According to the invention of claim 6 of the present invention, an epoxy resin composition having excellent SF ₆ gas resistance and excellent mechanical strength can be obtained.

According to the seventh aspect of the present invention, it is possible to obtain an epoxy resin composition excellent in low thermal expansion, high electrical insulation and arc resistance.

According to the invention of claim 8 of the present invention, an epoxy resin composition which is excellent in SF ₆ gas resistance and mechanical strength and does not contain toxic Be can be obtained.

According to the ninth aspect of the present invention, an epoxy resin composition having excellent SF ₆ gas resistance, mechanical strength, and crack resistance can be obtained.

According to the tenth aspect of the present invention, an epoxy resin composition having an excellent balance between fluidity and mechanical strength can be obtained.

According to the eleventh aspect of the present invention, an epoxy resin composition having excellent long-term reliability and a low coefficient of thermal expansion of a molded product can be obtained.

According to the thirteenth to nineteenth aspects of the present invention, it is possible to obtain an epoxy resin composition having excellent SF ₆ gas resistance, excellent mechanical strength, and a low dielectric constant.

According to the invention of the twentieth to twenty-first aspects of the present invention, the material has a low dielectric constant, is excellent in mechanical and thermal substances, and has a low S-resistance despite the fact that the composition contains a SiO ₂ component.
It has the effect of being excellent in F ₆ gas properties.

[Brief description of the drawings]

FIG. 1 is a view showing a shape of an aluminum orifice washer.

FIG. 2 is a graph showing the relationship between the average particle size of a silicate compound powder and the obtained bending strength of a molded product.

FIG. 3 is a view showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when an independent silicate is used as a silicate compound.

FIG. 4 is a graph showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when a cyclic silicate or a chain silicate is used as a silicate compound.

FIG. 5 is a diagram showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when an organic substance is used.

FIG. 6 is a diagram showing the relationship between the content of the MgO component in the silicate compound mainly composed of MgO and SiO ₂ and the dielectric constant of the obtained molded product.

FIG. 7 is a diagram showing the relationship between the content of a CaO component in a silicate compound mainly composed of CaO and SiO ₂ and the dielectric constant of a molded product.

FIG. 8 is mainly composed of CaO, MgO and SiO ₂
FIG. 4 is a graph showing the relationship between the content of MgO and CaO components in a silicate compound composed of and the dielectric constant of a molded product.

FIG. 9 shows a forsterite-based silicate compound,
FIG. 3 is a diagram showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when a steatite system, a wollastonite system, or a montecelite system is used.

FIG. 10 is a diagram showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when a silicate compound mainly composed of MgO and SiO ₂ is used.

FIG. 11: Forsterite and magnesium oxide (M
FIG. 6 is a diagram showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when gO) or a linker (SiO ₂ ) is used as a mixture.

FIG. 12 is a graph showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when a silicate compound mainly composed of CaO and SiO ₂ is used.

FIG. 13 is mainly composed of CaO, MgO and SiO
FIG. 3 is a diagram showing the relationship between the exposure time to a mixed gas and the surface resistance of a molded product when a silicate compound consisting of No. ₂ is used.

[Explanation of symbols]

 1 Resin composition, 2 Olyphant washers.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Kazuharu Kato 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsui Electric Co., Ltd. (72) Hirofumi Fujioka 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Inside Mitsubishi Electric Corporation (72) Inventor Yukio Ozaki 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation (72) Inventor Hiroyuki Huma 2-3-2 Marunouchi, Chiyoda-ku, Tokyo 3 Rishi Electric Co., Ltd.

Claims (21)

[Claims] 1. An epoxy resin composition for SF ₆ gas insulating equipment, comprising a silicate compound powder added to an epoxy resin. 2. An SF ₆ gas insulation apparatus comprising an epoxy resin and powder of two or more silicate compounds, or a powder of a silicate compound and an inorganic powder other than the silicate compound. Epoxy resin composition. 3. The epoxy resin composition for SF ₆ gas-insulated equipment according to claim 1, wherein the silicate compound is an independent silicate. 4. A silicate compound is a cyclic silicate claim 1 or 2 SF ₆ gas insulation apparatus epoxy resin composition described. 5. The epoxy resin composition for an SF ₆ gas-insulated device according to claim 1, wherein the silicate compound is a chain silicate. 6. The S according to claim 3, wherein the independent silicate is forsterite, fayalite, tephrite, knevelite or montecelite having an olivine structure.
Epoxy resin composition for F ₆ gas insulated equipment. 7. The method of claim 3, wherein the independent silicate is zircon.
The epoxy resin composition for an SF ₆ gas-insulated device as described above. 8. The method of claim 4 SF ₆ gas insulation apparatus epoxy resin composition described cyclic silicate is cordierite. 9. chain silicate is wollastonite belonging to the pyroxene group claim 5 SF ₆ gas insulation apparatus epoxy resin composition described. 10. The silicate compound powder having an average particle size of 1
The epoxy resin composition for SF ₆ gas-insulated equipment according to claim 1 or 2, comprising fine particles having a diameter of 00 µm or less or needles having an average fiber diameter of 100 µm or less. 11. A glass material having a glass transition temperature of 140 ° C. or higher and a linear expansion coefficient of 4 at a temperature lower than the glass transition temperature.
3. The epoxy resin composition for SF ₆ gas insulated equipment according to claim 1, further comprising an organic powder or fiber having a concentration of 0 ppm / ° C. or less. 12. An epoxy resin comprising an inorganic powder other than a silicate compound and an organic substance having a glass transition temperature of 140 ° C. or higher and a linear expansion coefficient of 40 ppm / ° C. or lower at a temperature lower than the glass transition temperature. An epoxy resin composition for SF ₆ gas insulation equipment, which is obtained by adding powder or fiber. 13. The composition of a silicate compound mainly composed of MgO
The epoxy resin composition for an SF ₆ gas-insulated device according to claim 1 or 2, which is a silicate compound composed of SiO ₂ and SiO ₂ . 14. An epoxy resin composition for SF ₆ gas insulated equipment, wherein the MgO component in the composition of the silicate compound according to claim 13 is 16 to 94% by weight based on all components. 15. The epoxy resin composition for an SF ₆ gas-insulated device according to claim 1, wherein the composition of the silicate compound is a silicate compound mainly composed of CaO and SiO ₂ . 16. An epoxy resin composition for SF ₆ gas insulated equipment, wherein the CaO component in the composition of the silicate compound according to claim 15 is 20 to 90% by weight based on all components. 17. The method of claim 1 or 2 SF ₆ gas insulation apparatus epoxy resin composition described composition the composition of the silicate compound is primarily silicate compound consisting of CaO and MgO and SiO _2. 18. The composition of the silicate compound according to claim 17, wherein the total of the MgO component and the CaO component is 20% in all components.
An epoxy resin composition for an SF ₆ gas insulation device, which is 90% by weight. 19. An S obtained by mixing one or more of the silicate compounds according to claim 13, 15 or 17
Epoxy resin composition for F ₆ gas insulated equipment. 20. SF _{6 according to} claim 1, 2 or 12
Molded article made of epoxy resin composition for gas insulation equipment. 21. An SF ₆ gas insulating device using the molded product according to claim 20.