JP3501905B2 - Molding resin composition, mold product for high-voltage equipment using the same, and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for molding, a molded product for high-voltage equipment using the same, and a method for producing the same. The present invention relates to, for example, a molded motor and a coil device formed by using the same.

[0002]

2. Description of the Related Art Conventionally, coil devices such as transformers and motors have been disclosed in, for example, Japanese Patent Application Laid-Open No. Hei 8-127441 and Japanese Patent Publication No. 56-2090, in which a wound coil portion is sealed with epoxy varnish. After dipping, the product has been commercialized by covering the outside with a steel plate or an aluminum die-cast frame. In this case, the number of manufacturing steps is large, workability and productivity efficiency are poor, and it is very difficult to make the product compact. On the other hand, by replacing the winding coil part, stator part outer periphery and die cast part with mold resin using epoxy resin composition, the product is more compact than before and the temperature rise of the coil part is suppressed. And the number of steps can be reduced.

[0003]

However, a more compact and higher performance molded coil has been proposed.
Since long-term reliability is required for molded motor products, there is no void in the mold resin that causes corona discharge, and high heat dissipation to suppress temperature rise inside the coil during motor operation, etc. Characteristics such as a long heat cycle and crack resistance against external stress are required.

[0004] The high heat dissipation of the mold resin can be achieved by injecting a resin having as high a thermal conductivity as possible without voids between the stator coils in the molded product. In addition, regarding the crack resistance of the mold resin, it is considered that cracks occur when the stress caused by the difference in the expansion coefficient from the insert embedded in the molded product exceeds the mechanical strength of the resin. The stress generated here is simply expressed by the following equation. σ = E × (α _R −α _I ) × (Tg−T ₀ ) σ: generated stress E: modulus of elasticity of mold resin α _R : coefficient of thermal expansion of mold resin α _I : coefficient of thermal expansion of insert Tg: mold Glass transition temperature T _{0 of} resin: lower limit temperature of heat cycle

From the above formula, since the mechanical strength of the conventional molding resin is not sufficient, the α _R is reduced by the addition of an inorganic filler such as silica, and the crack resistance is set by setting the Tg relatively low. It is possible to have.

[0006] In recent years, such molding devices have been made more compact and larger in capacity, and accordingly, there has been a demand for thinner molding resins and higher heat resistance levels. Improvements and improvements in thermal conductivity are issues.

[0007] The present invention has been made to solve the above problems, and a molding resin composition having high mechanical strength, high toughness, and improved heat resistance, and a molding resin having excellent thermal conductivity. An object of the present invention is to obtain a composition, a molded product for high-voltage equipment using the composition, and a method for producing the same.

[0008]

The first resin composition for molding according to the present invention has the general formula (I)

[0009]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
Represents an alkyl group of 4, X is an integer of 1 to 4, n is 0 to 2
Indicates 0. An epoxy resin (A1) having a molecular weight of 10,000 or less represented by the general formula (II):

[0011]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, and n represents 0 to 20. An epoxy resin (A2) having a molecular weight of 10,000 or less represented by the formula (III):

[0013]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, and n represents 0 to 20. An epoxy resin (A3) having a molecular weight of 10,000 or less represented by the formula (IV):

[0015]

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(Wherein R ₁ is a hydrogen atom or a group having 1 to 1 carbon atoms)
4 represents an alkyl group, and n represents 0 to 20. ), The epoxy resin (A4) containing at least one of the above (A1) to (A4), the acid anhydride (B), and the curing accelerator (C) ), A coupling agent (D), and a dispersed average particle diameter of 0.01 to 5 µm , and a molecular weight of 1,000 to 50,000.
Polyacrylate, polymethacrylate
Or its main copolymer or derivative thereof
Polymer particles of polyacrylic acid derivative (E3) such as salt and salt
An inorganic filler (F) containing at least one of a silica filler and an alumina filler, and a filament having an average length of 20 to 500 μm, and having a blending amount of 60 to 95% by weight based on the whole composition. And the filament is contained in an amount of 15% by weight or less based on the whole composition, and the mixing ratio of the silica filler and the alumina filler is alumina filler / (silica filler + alumina filler) × 100 ≧ 1.
0%.

The second molding resin composition according to the present invention comprises:
The epoxy resin (A) contains at least one of a bis-A epoxy resin and a bis-F epoxy resin in which a bromo group in the general formula (I) is substituted with a hydrogen group.

The third molding resin composition according to the present invention comprises:
The coupling agent (D) is at least one of an epoxysilane coupling agent, a phenylaminosilane coupling agent, a mercaptosilane coupling agent, and a titanate coupling agent, and is 0.05 to 0.05 parts by weight of the inorganic filler (F). It contained 5% by weight.

The first method for producing a molded product for a high-voltage device according to the present invention is characterized in that the curing resin composition is mixed with a curing accelerator (C) and a quantitative mixture comprising other components. This is a method in which a resin composition for molding is prepared, and the resin composition for molding is injected into a mold at a pressure of 5 to 100 kg / cm ² and molded.

The first molded product for a high-voltage device according to the present invention is obtained by the above-described manufacturing method.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The molding resin composition of the present invention comprises at least one epoxy resin selected from the epoxy resins (A1) to (A4) represented by the general formulas (I) to (IV). Resin (A), acid anhydride (B), curing accelerator (C), coupling agent (D), and fine polymer particles having an average particle diameter of 0.01 to 5 μm finely dispersed in the composition ( E) and an inorganic filler (F) containing filaments having an average length of 20 to 500 μm in an amount of 15% by weight or less based on the whole composition, and having a blending amount of 60 to 95% by weight based on the whole composition. It is blended.

The epoxy resins (A1) to (A4) relating to the molding resin composition of the present invention are bifunctional epoxy resins, and have a skeleton structure of a bis-brominated bis-A skeleton (A1) and a brominated bis-F skeleton (A1). ), A benzene ring monocyclic skeleton (A2),
Biphenyl skeleton (A3), arylated bis A skeleton (A
4), having a rigid skeleton such as an arylated bis F skeleton (A4), particularly having a high glass transition temperature, high mechanical strength,
It has excellent properties such as high toughness.

In the present invention, as the epoxy resin (A), at least one of a bis-A skeleton epoxy resin and a bis-F skeleton epoxy resin in which the bromo group is replaced by a hydrogen group in the above general formula (I) is mixed. The solid epoxy resin (A1 to A1)
4) can be reduced in viscosity.

If the epoxy equivalent of the epoxy resin (A) is too large, the viscosity of the molding resin composition obtained becomes high, and the glass transition temperature and mechanical strength of the cured product obtained from the molding resin composition. Is liable to be greatly reduced, and is preferably 10,000 or less, especially preferably 8,000 or less. The number (n) of the repeating units of the epoxy resin (A) is from 0 to 20, but it is preferable that the number is as low as possible in consideration of the tendency of lowering the glass transition temperature.

The acid anhydride (B) relating to the molding resin composition of the present invention reacts with the epoxy resin (A) to form a three-dimensional crosslinked network structure, and the cured product obtained from the molding resin composition is cured. It is intended to express excellent electrical and mechanical properties to a product. Representative examples of the acid anhydride (B) include, for example, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, hexahydroanhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, tetrabromo Including phthalic anhydrides such as phthalic anhydride and phthalic anhydride, methyl nadic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride,
Dodecenyl succinic anhydride and poly (ethyl octadecane diacid) anhydride, which can be used alone or as a mixture of two or more thereof. Among them, the viscosity is low at room temperature, and the resin composition for molding is used. From the viewpoint that the glass transition temperature of the cured product obtained from the product becomes relatively high, methyltetrahydrophthalic anhydride, methylnadic anhydride, and the like are preferable. The epoxy resin (A)
In consideration of lowering the viscosity of the mixture when mixed with the acid anhydride, the acid anhydride (B) is preferably a liquid at room temperature.

The compounding amount (parts by weight) of the acid anhydride (B) with respect to 100 parts by weight of the epoxy resin (A) is the compounding amount (parts by weight) of the following acid anhydride (B). = {Molecular weight of acid anhydride (B) / acid anhydride (b) number of acid anhydride groups in one molecule} × {number of acid anhydride groups of acid anhydride (B) / epoxy resin (A) Number of epoxy groups x 100
In the present invention, the ratio of the number of acid anhydride groups of the acid anhydride (B) to the number of epoxy groups of the epoxy resin (A) (acid If the value of (the number of anhydride groups / the number of epoxy groups) is too large or too small, the glass transition temperature is greatly reduced, and improvement in mechanical properties cannot be expected. As such, preferably 0.7
It adjusted so that it might be set to? 1.2.

The curing accelerator (C) relating to the molding resin composition of the present invention includes all kinds of imidazoles such as 2-ethyl-4-methylimidazole, 2-methylimidazole and 2-phenylimidazole and salts thereof. Phosphorus compounds represented by all kinds of organic phosphines such as triphenylphosphine, cyclic phosphine, tributylphosphine and tetraphenylphosphonium bromide, aliphatic amines, aliphatic polyamines, aromatic amines and tertiary amines Amines and salts thereof, dicyandiamide, all kinds of Lewis acid / base catalysts, Bronsted acid salts, organic metal salts such as zinc octylate and tin octylate, polymercaptans, microcapsule catalysts and 1,8-diaza Bicyclo (5,4 0) it is not well limited as long as undecene -7 (DBU) or a salt thereof curing accelerators which can be cured with conventional epoxy resins such as. These may be used alone or in combination of two or more. Among them, 2-ethyl-4-methylimidazole is preferred because it is easy to handle and has high reactivity.

If the compounding amount of the curing accelerator (C) is too large, heat generation becomes large, and furthermore, the curing reaction progresses rapidly and locally, and the reaction becomes non-uniform. Since the decrease in strength is large, the amount is adjusted so as to be about 10 parts by weight, preferably 6 parts by weight or less with respect to 100 parts by weight of the epoxy resin (A). Because it is too long, 0.0 parts with respect to 100 parts by weight of the epoxy resin (A)
It is adjusted so as to be at least 5 parts by weight, preferably at least 0.1 parts by weight.

The coupling agent (D) relating to the molding resin composition of the present invention has a high strength by chemically bonding and reinforcing the interface between the inorganic filler (F) and the organic component in the composition. For example, at least one selected from an epoxysilane-based coupling agent, a phenylaminosilane-based coupling agent, a mercaptosilane-based coupling agent, and a titanate-based coupling agent is used. Representative examples of epoxysilane-based coupling agents include, for example, γ-glycidoxypropyltrimethoxysilane, and phenylaminosilane-based coupling agents include, for example, N-phenyl-γ-aminopropyltrimethoxysilane. Examples of the mercaptosilane-based coupling agent include γ-mercaptopropyltrimethoxysilane, and examples of the titanate-based coupling agent include isopropyltriisostearoyl titanate and isopropyltri (dioctylphosphate) titanate. Within, without increasing the viscosity of the molding resin composition,
From the viewpoint that the mechanical strength of the obtained cured product can be improved, an epoxy silane coupling agent such as γ-glycidylpropyltrimethoxysilane or a titanate coupling agent is preferable.

The amount of the coupling agent (D) is determined based on the amount of the inorganic filler (F). When the amount of the coupling agent (D) is too large, Since the heat resistance of the cured product obtained from the resin composition is reduced, the content is adjusted to be 5 parts by weight or less, preferably 3 parts by weight or less based on 100 parts by weight of the inorganic filler (F). When the amount is small, the effect of improving the mechanical strength of the cured product is not sufficiently exhibited as compared with the case where the coupling agent is not used, so that the inorganic filler (F) 10
0.05 parts by weight or more, preferably 0.1 part by weight, per 0 parts by weight.
Adjust so that it is 1 part by weight or more.

The fine polymer particles (E) relating to the molding resin composition of the present invention have an average particle size of 0.01 to 5 μm,
It is not dissolved or melted in the composition, but is finely dispersed in the composition. With the above fine polymer particles, the molded coil product obtained by using the above epoxy resin composition for molding can further improve fracture toughness and reduce stress, so that crack resistance, productivity, moldability, etc. are significantly improved. Will be improved. When the average particle size is out of the above range, the effect of improving fracture toughness is reduced.

If the amount of the fine polymer particles (E) is too large, not only does the viscosity of the molding resin composition increase, but also the mechanical strength of the cured product obtained using the same decreases. Therefore, the amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on 100 parts by weight of all the organic components constituting the molding resin composition other than the inorganic filler (F). If the amount is small, the effect of blending the fine polymer particles (E) tends not to be sufficiently exerted. Therefore, the amount is preferably 3 parts by weight, especially 5 parts by weight or more based on 100 parts by weight of all the organic components.

The fine polymer particles (E) include at least one polyacrylic acid derivative (E) having a molecular weight of 1,000 to 500,000, such as a polymer having a skeleton of a polyacrylate or a polymethacrylate or a salt thereof.
3) is used. In order to further reinforce the interface by finely dispersing fine particles in an epoxy resin matrix and further improve crack resistance and moldability of a molded coil product obtained using the same, the above-mentioned polyacrylate or polymethacrylic acid is used. A functional group capable of reacting an ester group (—COOR portion) in the ester fine particles with an epoxy group of the epoxy resin (A) or an acid anhydride group of the acid anhydride (B);
For example, carboxyl group: —COOH amino group: —NH ₂ , —NRH, —NR _{2 ,} salt of carboxylic acid and amine: —COO ⁻ NR ₄ ⁺ , —COO ⁻
NR ₃ H ⁺ , —COO ⁻ NR ₂ H ₂ ⁺ , —COO ⁻ NRH ₃ ⁺

[0034]

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Hydroxyl group: having a molecular weight of 500 to 30 containing a functional group substituted by -R-OH or the like
More preferably, 000 polyacrylate particles are blended.

The functional groups of the fine polymer particles (E) react during the curing reaction of the obtained resin composition for molding, but the fine polymer particles (E) are prepared in advance by the epoxy resin (A) or the epoxy resin (A). It may be preliminarily reacted with the acid anhydride (B), and there is no particular limitation on the compounding time.

The inorganic filler (F) relating to the molding resin composition of the present invention contains 15% by weight or less of filaments having an average length of 20 to 500 μm. As the filaments, for example, inorganic filaments such as glass filaments and alumina filaments are used. But not limited thereto. The filament improves the fracture toughness and mechanical strength of the cured product, and further improves crack resistance and the like. When the average length of the filament is less than 20 μm, the improvement in fracture toughness and mechanical strength is small, and when it exceeds 500 μm, the viscosity rise is extremely inappropriate.

If the content of the filament is too small, the effect of blending the filament tends not to be sufficiently exerted. Therefore, the content is more than 0% by weight, preferably 1% by weight based on the molding resin composition. % Is preferable, and when it is too large, the viscosity of the resin composition for molding tends to be extremely high, so it is preferably 15% by weight or less, especially preferably 13% by weight or less.

The inorganic filler (F) according to the present invention comprises:
95% by weight or less 60% by weight in the molding resin composition of the present invention
The above is blended. The content of the inorganic filler (F) controls not only the elastic modulus and mechanical strength of the cured product obtained using the molding resin composition, but also the thermal conductivity.
That is, for example, from the viewpoint of suppressing a temperature rise during operation of a molded product for high voltage equipment such as a molded coil or a molded motor product, the thermal conductivity of a cured product obtained using the molding resin composition is 0.6 W / (M · K) or more. The thermal conductivity is greatly affected by the content of the inorganic filler (F). From this viewpoint, the blending ratio of the inorganic filler (F) is important. When the content exceeds 95% by weight, the viscosity of the molding resin composition becomes high, and the elasticity of the obtained cured product becomes high. When the content is less than 60% by weight, the elasticity of the obtained cured product becomes low and becomes soft. Since the mechanical strength is reduced and the effect of lowering the coefficient of thermal expansion is reduced, it becomes unsuitable as a molding material.

Inorganic filler (F) other than the above filaments
In terms of having an average particle size of 40 μm or less, broadening the particle size distribution and lowering the viscosity of the resin composition for molding, contains 5% by weight or more, preferably 10% by weight or more of particles having a particle size of 5 μm or less. It is preferable to adjust so that The average particle size is preferably 40 μm or less, more preferably 20 μm or less from the viewpoint of suppressing a decrease in mechanical strength of a cured product obtained from the molding resin composition, and the average particle size is If it is too small, the viscosity of the molding resin composition tends to be high, so it is preferably at least 0.05 μm, especially at least 0.1 μm. Further, in order to fill the molding resin composition over the details of a molded part such as an insert member, the maximum particle size is 200 μm or less, especially 1 μm.
It is preferably 50 μm or less.

As the inorganic filler (F) other than the filaments according to the present invention, for example, a silica filler and / or
Or an alumina filler is used. Silica filler is
Natural silica or synthetic silica may be used, such as crystalline silica and fused silica.
Crystalline alumina and the like can be mentioned. In addition, the shape of the silica filler and the alumina filler may be, for example, spherical or crushed. The mixing ratio of the silica filler and the alumina filler greatly affects the thermal conductivity of the molding resin composition of the present invention as described below.

The fact that the molding resin composition of the present invention obtains high heat radiation means that the thermal conductivity is practically 0.6 W / (m ·
K). 0.6W / (m ・
Below K), it is difficult to suppress the temperature rise during use. Various compositions having a thermal conductivity of 0.6 W / (m · K) or more can be considered. As a filler other than the filament of the inorganic filler (F), various amounts of the silica filler and the alumina filler were blended, and FIG. 1 shows (silica filler + alumina filler) in the molding resin composition. This is shown as a characteristic diagram showing the correlation between the content and the proportion of the alumina filler in the content. In the figure, the hatched portion has a thermal conductivity of 0.6 W / (m ·
K) indicates a composition region. That is, when the filling amount of the inorganic filler is near the lower limit of 60% by weight and the filament is approximately 0% by weight (silica filler + alumina filler = approximately 60% by weight), even if the alumina is approximately 0% by weight, the thermal conductivity = 0. .6W / (m
K) can be achieved, but the amount of the inorganic filler is the lower limit of 60% by weight and the maximum amount of the filament is 15%.
% By weight (silica filler + alumina filler = 45% by weight)
Requires 10% by weight or more of alumina. That is, the mixing ratio of the silica filler and the alumina filler is alumina filler / (silica filler + alumina filler) ×
If 100 ≧ 10%, the thermal conductivity of the molding resin composition is 0.6 W /
(M · K) or more.

Further, the molding resin composition of the present invention is usually blended to obtain a molded product or the like, for example, an antimony such as antimony trioxide, a flame retardant such as a phosphorus compound, an antioxidant, Desired additives such as a colorant such as carbon black may be appropriately blended.

In the method for producing a molded coil product using the epoxy resin composition for molding of the present invention, the curing resin (C) among the constituent components is mixed with a quantitative mixture comprising the other components to form a molding resin. Prepare the composition. In this case, the amount of the curing accelerator (C) is preferably 3 parts by weight or more based on 100 parts by weight of the epoxy resin (A) from the viewpoint that the curing time can be shortened. Next,
Before the resin composition for molding is cured, the resin composition for molding is injected into a mold having a desired shape at a predetermined pressure and molded, and then, after being appropriately trained, a desired mold coil or motor is obtained. Etc. can be obtained. If the pressure at the time of press-fitting the molding resin composition into the mold is too high, for example, when an insert member described later is provided in the mold, these may be deformed.
cm ² or less, preferably 80 kg / cm ² or less. If it is too low, the press-fitting time is too long or the molding resin composition does not enter the gaps between the insert members. cm ² or more, preferably 1
Adjust so as to be 0 kg / cm ² or more.

In order to accelerate the curing of the press-fitted molding resin composition, the mold may be heated. When heating the mold, the heating temperature is not particularly limited,
If the temperature is too high, the surface of the molded product tends to be discolored during molding. Therefore, the temperature is preferably about 200 ° C. or less, especially about 180 ° C. or less, and if it is too low, the curing time is shortened. However, improvement in workability cannot be expected, so that the temperature is about 80 ° C. or more, especially 10
The temperature is preferably about 0 ° C. or higher.

When the press-fitted molding resin composition is to be molded at a high speed, the curing accelerator (C) and another curing accelerator (C) are added to reduce the viscosity of the molding resin composition and to cure the molding resin composition at a higher speed. When mixing with the quantitative mixture consisting of components, these may be heated to about 40 to 80 ° C.
Further, the temperature and the time for culturing the forming pair after the completion of the forming are not particularly limited, and may be appropriately adjusted.

The cured product obtained from the epoxy resin composition for molding of the present invention thus obtained is, for example, 130
The glass transition temperature is as high as about 160 ° C., and especially, it has excellent mechanical properties such as high mechanical strength and high toughness and heat resistance. And a highly reliable molded coil product or the like can be manufactured.

[0048]

Next, the molding resin composition of the present invention, a molded product for high-voltage equipment using the same, and a method for producing the same will be described in detail.

Reference Examples 1 to 10. The components shown in Table 1 were mixed using a conventional mixing apparatus, and then vacuum defoamed to obtain a molding resin composition. In the table, (parts) is (parts by weight), and as the acid anhydride (B), methyltetrahydrophthalic anhydride (molecular weight 166) is used.
2-ethyl-4-methylimidazole is used as the curing accelerator (C), and γ-glycidoxypropyltrimethoxysilane (epoxysilane-based coupling agent) is used as the coupling agent (D). Product name: KBM403, Shin-Etsu Chemical Industrial Co., Ltd. was used.

[0050]

[Table 1]

The abbreviations other than the above components in Table 1 and Tables 3 and 5 below are as follows. A-1 used as epoxy resin (A):

[0052]

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An epoxy resin represented by the following formula (epoxy equivalent: 4
80, number average molecular weight 1320) A-2:

[0054]

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An epoxy resin represented by the following formula (epoxy equivalent: 4
10, number average molecular weight 1200) A-3:

[0056]

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An epoxy resin represented by the following formula (epoxy equivalent 2
80, number average molecular weight 580) A-4:

[0058]

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An epoxy resin represented by the following formula (epoxy equivalent: 5
00, number average molecular weight 1400) A-5:

[0060]

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An epoxy resin represented by the following formula (epoxy equivalent: 6)
E-807: bisphenol F type epoxy resin (epoxy equivalent: 170, number average molecular weight: 350) (trade name: Epicoat 807, manufactured by Yuka Shell Epoxy Co., Ltd.)

E-1 used as fine polymer particles (E): crosslinked rubber powder composed of acrylonitrile-butadiene copolymer (trade name: XER-91, manufactured by Nippon Synthetic Rubber Co., Ltd.)

RD-8 used as inorganic filler (F): silica filler (fused silica, average particle size 13 μm)
m, maximum particle size 130 μm, content of particles having a particle size of 5 μm or less 18% by weight) (trade name: RD-8, manufactured by Tatsumori) Crystallite 5X: silica filler (crystalline silica, average particle size) 1.5 μm, content of particles having a particle diameter of 5 μm or less 80
(% By weight or more) ｛Product name: Crystallite 5X, manufactured by Tatsumori Co., Ltd.｝ Filament: Glass filament (average length 300μ)
m)

Tables 3 and 5 following Table 1 also show the number of epoxy groups of the epoxy resin (A) and the number of acid anhydride groups of the acid anhydride (B). Reference Example 1
In the following Reference Examples 11 to 19, Example 1, and Comparative Examples 1 to 3, the ratio of the number of the acid anhydride groups of the acid anhydride (B) to the number of the epoxy groups of the epoxy resin (A) was determined. The values were all adjusted to be 0.9.

The resin composition for molding of each of the above compositions was applied to a thickness of 5 m.
A glass resin spacer having a thickness of 3 mm or 6 mm is sandwiched between two glass plates having a thickness of 3 m, and the molding resin composition is poured into the formed space.
Cured at 20 ° C. for 4 hours and 160 ° C. for 12 hours,
Test pieces (thickness 3 mm or 6 mm) were prepared. As physical properties of the obtained test piece, a bending elastic modulus, a bending strength, a glass transition temperature, a thermal expansion coefficient, a fracture toughness value, and a thermal conductivity were measured according to the following methods. Table 2 shows the results.

[0066]

[Table 2]

The methods for measuring the properties shown in Table 2 and Tables 4 and 6 below are shown below. (B) Flexural modulus and bending strength According to the method described in JIS K6911, the thickness is 3 mm.
The flexural modulus (kg / mm ² ) and the flexural strength (kg / mm ² ) were measured using the test pieces of Example 1. (B) Glass transition temperature Thermomechanical analysis was performed using the thermal expansion method, and the glass transition temperature (T
g) (° C) was measured. (C) Thermal expansion coefficient The thermal expansion coefficient is obtained from the slope of the linear part of the glass region (40 to 90 ° C.) of the thermal expansion curve obtained when performing the thermomechanical analysis by the thermal expansion method in the measurement of the glass transition temperature (b). (℃
^-1 ) was measured. (D) Fracture toughness FIG. 2 is a plan view of a test piece for measuring general fracture toughness. That is, the test piece obtained as described above was used as a test piece 13 having a thickness of 6 mm, a length of 12 mm, and a width of 80 mm, and a notch 14 having a width of 0.5 mm and a length of 4.5 mm was inserted in the center thereof. A fracture toughness test piece having a preliminary crack 15 having a width of 0.1 mm and a length of 1.5 mm was prepared. The test piece was supported by a fulcrum 16 at two points 15 mm from the end of the test piece 13. A load was applied in the direction of A, and the fracture toughness value (K1C) (N / mm ^3/2 ) was determined based on the load when the crack 17 was formed. (E) Thermal conductivity The thermal conductivity (W / (m · K)) was measured using a test piece having a thickness of about 1 mm in accordance with the method described in JIS C2141.

(F) Crack Characteristics FIG. 3 is a block diagram of a general hardening accelerator separation type molding apparatus (hereinafter also referred to as molding apparatus). In the figure, 1 is a curing accelerator separation type molding apparatus, 2 and 3 are input ports, 4 is a mixer,
Reference numeral 5 denotes a mold, and reference numeral 6 denotes an injection port for the molding resin composition. First, a curing accelerator (C) is introduced from the inlet 2 of the molding apparatus 1 and a quantitative mixture comprising components other than the curing accelerator (C) is introduced from the inlet 3 and mixed in the mixer 4 to form a molding resin. After the composition was adjusted, the molding resin composition was injected into a mold (having a shape adapted to the stator portion of the mold motor) 5 heated to 150 ° C. through the injection port 6 at 30 kg / c.
injection at a pressure of m ² , molding while maintaining the pressure for 10 minutes,
After culturing at 170 ° C. for 5 hours, a molded motor having the shape shown in FIG. 4 was obtained. FIG. 4 is a partially cutaway explanatory view of a general molded motor. In this figure, reference numeral 21 denotes a stator portion formed from a molding resin composition, 22 denotes a stator core portion, and 23 denotes a coil portion. When manufacturing such a molded motor, the stator core portion 22 is formed by combining 100 iron steel plates (thickness: 0.5 mm), and the coil portion 23 is formed of a polyurethane-coated conductive wire (having a diameter of 0.1 mm).
5 mm). The obtained molded motor was subjected to a heat cycle test in which 200 cycles of 4 hours at −50 ° C. and 4 hours at 130 ° C. were performed.
The presence or absence of cracks was evaluated (in the table, ば indicates that no cracks occurred, Δ indicates that slight cracks occurred, and x indicates significant cracks, and so forth). However, in the molding resin composition used for the mold motor prepared in the above (f) crack property test, the curing accelerator (C)
Is 5 parts per 100 parts by weight of the epoxy resin (A).
Parts by weight were used.

Comparative Examples 1 to 3. The composition was as shown in Table 3, and a molding resin composition was obtained in the same manner as in Reference Examples 1 to 10. The properties were measured, and the results are shown in Table 4.

[0070]

[Table 3]

[0071]

[Table 4]

Reference Examples 11 to 19, Embodiment 1. Referential Examples 1 to 10 except that the composition was changed as shown in Table 5.
In the same manner as in the above, a molding resin composition was obtained.

[0073]

[Table 5]

Using the obtained resin composition for molding, physical properties were examined in the same manner as in Reference Examples 1 to 10. Table 6 shows the results.
Shown in

[0075]

[Table 6]

The abbreviations in Table 5 are as follows. E-3 used as fine polymer particles (E):

[0077]

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Fine particles of polybutyl methacrylate having a repeating unit represented by the following formula (number-average molecular weight: 37000,
Average particle diameter 0.8 μm)

G-1: Butadiene-acrylonitrile copolymer elastomer containing a carboxyl group at both ends (molecular weight: 3)
500, acrylonitrile amount 17% ｛Product name: CTBN
1300 × 8, manufactured by Ube Industries, Ltd.

J-1 used as polydimethylsiloxane rubber powder: Fine powder of crosslinked rubber-like silicone polymer having a siloxane skeleton obtained by using 83% by weight of dimethylsiloxane, 17% by weight of methylvinylsiloxane and dichlorobenzoyl peroxide (Average particle size 1.5
μm)

K-1 used as dimethylsiloxane polymer (K):

[0082]

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A dimethylsiloxane polymer having a repeating unit represented by the following formula (number average molecular weight 7560, hydroxyl equivalent 2
100)

AS-20 used as inorganic filler (F): Alumina filler (average particle diameter: 20 μm, maximum particle diameter: 150 μm, content of particles having a particle diameter of 5 μm or less: 15% by weight) {trade name: AS— 20, manufactured by Showa Denko KK

From the results shown in Tables 2, 4 and 6, the cured product obtained from the molding epoxy resin composition obtained in Example 1 has a high glass transition temperature, a high flexural modulus, The strength and the coefficient of thermal expansion are small, compared to the cured product obtained from the molding resin composition obtained in Comparative Examples 1 to 3,
It can be seen that the material has a high fracture toughness, a high bending strength, excellent mechanical properties, and a high thermal conductivity, and thus has excellent heat dissipation.

Further, the mold motor manufactured using the molding resin composition of Example 1 is different from those of Comparative Examples 1 to 3, in which the occurrence of cracks after the heat cycle test is observed. It can be seen that the steel had excellent crack resistance.

Embodiment 2 In FIG. 3, the curing accelerator (C) is supplied from the inlet 2 of the curing accelerator separate mold device 1 (hereinafter, also referred to as molding device 1).
, A quantitative mixture of components other than the curing accelerator (C) is charged through the charging port 3, and the mixture is, for example, from room temperature to 8 in the mixer 4.
After adjusting the resin composition for molding by heating and mixing at about 0 ° C., press-fitting the resin composition for molding into a mold 5 provided with an insert member at a pressure of 5 to 100 kg / cm ² to mold. As a result, a desired molded product was obtained at a high speed. In addition, the molding resin composition mixed in the mixer 4 can be pressed and molded under predetermined conditions, for example, by a resin transfer molding method or an injection molding method, and a desired molded product can be obtained at a high speed. There is no particular limitation on the apparatus used for the method of manufacturing the molded coil and the motor product, and
In order to shorten the curing time, the molding resin composition of the present invention is heated at about 80 to 200 ° C. for about 30 seconds to 20 hours. Further, the material of the insert member is not particularly limited, but may be, for example, iron, copper, aluminum, or the like that is commonly used for motors and coil products.

According to the production method of the present invention, as described above, the epoxy resin composition for molding, which has a high glass transition temperature of the cured product, exhibits excellent mechanical properties and heat resistance, and exhibits a higher thermal conductivity than the conventional one. Is used, the mechanical properties at high temperatures are improved, and the mechanical use limit temperature is increased, and it becomes possible to manufacture more reliable molded products for high-voltage equipment such as molded motors and molded coils. This enables miniaturization and mass production of molded products.

In the above embodiments and examples, a molded motor or a molded coil product is shown as a molded product for high-voltage equipment using the molding resin composition of the present invention. However, the present invention is not limited to these. Not something.

[0090]

According to the first molding resin composition of the present invention, an epoxy resin containing at least one of the epoxy resins (A1) to (A4) represented by the general formulas (I) to (IV) (A), acid anhydride (B), and curing accelerator (C)
, A coupling agent (D) and a dispersed average particle size of 0.0
Polya having a molecular weight of 1,000 to 500,000 at 1 to 5 μm
Acrylates, polymethacrylates or polymethacrylates
Polymers mainly composed of these or their derivatives and salts
It contains fine polymer particles of a acrylic acid derivative (E3), at least one of a silica filler and an alumina filler, and a filament having an average length of 20 to 500 μm ,
An inorganic filler (F) having a blending amount of 60 to 95% by weight based on the whole composition is blended, the filament is contained in an amount of 15% by weight or less based on the whole composition, and the silica filler and the alumina filling are contained. Since the compounding ratio of the agent is alumina filler / (silica filler + alumina filler) × 100 ≧ 10%, the thermal conductivity is 0.6 W (m · K) or more, and high mechanical strength is achieved. The effect of improving toughness and heat resistance is obtained.

According to the second molding resin composition of the present invention, the epoxy resin (A) is a bis-A epoxy resin and a bis-F epoxy resin in which the bromo group in the general formula (I) is replaced by a hydrogen group. By containing at least one kind of resin, an effect that the viscosity can be reduced can be obtained.

According to the third molding resin composition of the present invention, the coupling agent (D) is an epoxysilane coupling agent, a phenylaminosilane coupling agent, a mercaptosilane coupling agent and a titanate coupling agent. At least one of the above, the amount is 0.05 to 5% by weight based on the inorganic filler (F),
The effect that high strength can be obtained is obtained.

According to the first method for producing a molded product for a high-voltage device of the present invention, the molding resin composition
A curing resin (C) and a quantitative mixture comprising other components are mixed to prepare a molding resin composition, and the molding resin composition is injected into a mold at a pressure of 5 to 100 kg / cm ^2. By performing the molding, it is possible to produce a product having excellent productivity, moldability, particularly excellent crack resistance, and having reliability, and further has an effect that compactness and mass production can be achieved.

The first molded product for a high-voltage device of the present invention is obtained by the above-described manufacturing method, and has an effect of being particularly excellent in crack resistance and having high reliability.

[Brief description of the drawings]

FIG. 1 is a characteristic diagram showing the correlation between the (silica filler + alumina filler) content and the proportion of the alumina filler in the resin composition for molding.

FIG. 2 is a plan view of a test piece for measuring general fracture toughness.

FIG. 3 is a configuration diagram of a general curing accelerator separation type molding apparatus.

FIG. 4 is an explanatory diagram showing a part of a general molded motor cut away.

[Explanation of symbols]

1 Molding device with separate curing accelerator, 2, 3 inlet, 4
Mixer, 5 mold, 6 molding resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 33/06 C08L 33/06 63/00 63/00 Z H01F 27/32 H01F 27/32 A (72) Inventor Yuzo Kanegae Tokyo 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation (72) Inventor Chosei Yatsushiro 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation (72) Inventor Yoichi Ikeda Marunouchi, Chiyoda-ku, Tokyo 2-3-2, Mitsubishi Electric Corporation (72) Inventor, Mutsuji Suzuki 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation (72) Inventor, Ichiro Takahashi 2-6-1, Miwa, Mita City, Hyogo Prefecture No. 1 Ryoden Kasei Co., Ltd. (56) References JP-A-7-242732 (JP, A) JP-A-1-271455 (JP, A) JP-A-2-138361 (JP, A) JP-A -97976 (JP, A) JP flat 8-12741 (JP, A) Tokuoyake Akira 56-2090 (JP, B2) (58 ) investigated the field (Int.Cl. ^7, DB name) C08G 59/42 C08L 63/00-63/10 C08L 33/02 C08L 33/06-33/12 C08K 3/22 C08K 3/36 C08K 7/02 H01F 27/32

Claims (5)

(57) [Claims] 1. A compound of the general formula (I) (In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X represents an integer of 1 to 4, and n represents 0 to 20.)
An epoxy resin having a molecular weight of 10,000 or less (A
1), general formula (II) (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0 to 20).
0000 or less epoxy resin (A2), general formula (III) (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0 to 20).
0000 or less epoxy resin (A3), and general formula (IV) (Wherein, R ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n represents 0 to 20).
0000 or less epoxy resin (A4), epoxy resin (A) containing at least one of the above (A1) to (A4), acid anhydride (B), curing accelerator (C), and coupling agent (D), a polyacrylate ester having a dispersed average particle size of 0.01 to 5 μm and a molecular weight of 1,000 to 500,000.
, Polymethacrylic acid esters or those mainly
Induction of polyacrylic acid such as copolymer or its derivative or salt
Fine polymer particles of the conductor (E3) and at least one of a silica filler and an alumina filler;
And an inorganic filler (F) containing a filament having an average length of 20 to 500 μm and having a blending amount of 60 to 95% by weight based on the whole composition. % Or less, and the mixing ratio of the silica filler and the alumina filler is alumina filler / (silica filler + alumina filler) ×
A molding resin composition wherein 100 ≧ 10%. 2. The epoxy resin (A) contains at least one of a bis A epoxy resin and a bis F epoxy resin in which a bromo group in the general formula (I) is substituted with a hydrogen group. The resin composition for molding according to the above. 3. The coupling agent (D) is at least one of an epoxy silane coupling agent, a phenylamino silane coupling agent, a mercapto silane coupling agent and a titanate coupling agent, and the blending amount is an inorganic filler (F). The molding resin composition according to claim 1, wherein the amount is 0.05 to 5% by weight based on the weight of the resin composition. 4. A molding resin composition according to any one of claims 1 to 3, a curing accelerator (C), the mixture to molding resin composition and a quantitative mixture consisting other components The molding resin composition was adjusted to 5 to 100 kg /
A method for producing a molded product for a high-voltage device, which is injected into a mold at a pressure of ² cm ² and molded. 5. A molded product for high-voltage equipment obtained by the production method according to claim 4 .