JP6563823B2 - Mold resin material for high voltage equipment and method of manufacturing high voltage equipment - Google Patents

Description

  The present invention relates to a molding resin material for a high voltage device and a method for manufacturing the high voltage device.

  In power devices such as stationary machines, circuit breakers, and rotating machines, miniaturization and weight reduction are in progress. Along with this, the wiring density of devices and the density of parts and the thinning of insulating layers are progressing. For this reason, the mold resin is required to have a low viscosity in order to easily fill the narrow space with the insulating material. Further, a cured product of a mold resin that covers a metal or ceramic part is required to have high toughness and low thermal expansion in order to suppress cracks. Furthermore, the mold resin is also required to have excellent storage stability for the purpose of cost reduction. A cured product of an epoxy resin is excellent in heat resistance, adhesiveness, chemical resistance, mechanical strength, and the like, and is preferably used as a mold resin for electric power equipment such as a stationary device, a breaker, and a rotating machine. However, the epoxy resin itself has a relatively high viscosity, and its cured product is hard and brittle. In order to improve this, mold resin which mix | blended various additives with the epoxy resin has been developed.

  Patent Document 1 discloses a mold resin in which a low molecular weight radical polymerizable monomer such as a styrene compound, a maleimide compound and a divinylbenzyl polyoxyalkylene oxide compound is blended with a diamine curable epoxy resin. By adding a specific radical polymerizable monomer to the epoxy resin, the cured product exhibits high toughness. Further, since the radical polymerizable monomer is a low molecular weight substance, it can be expected that the viscosity of the mold resin is lowered.

  Patent Document 2 discloses an epoxy resin, a radical polymerizable monomer such as styrene having a viscosity of 100 cps or less at 25 ° C., a curing accelerator for epoxy resin, and an organic solvent having a decomposition temperature of 60 ° C. or more with a half-life of 10 hours. A liquid epoxy resin composition comprising a first liquid composed of a mixture of oxides and a second liquid composed of a carboxylic acid anhydride in which a maleimide compound such as bismaleimide is dissolved is disclosed. According to the invention according to Patent Document 2, each liquid is very excellent in storage stability, and the viscosity of the mixture of the first liquid and the second liquid is very low and the workability is excellent. It is said to have advantages.

  In addition, a technique for improving crack resistance by a technique of dispersing an inorganic filler such as glass fiber in an epoxy resin has been disclosed. Patent Document 3 contains (a) an epoxy resin, (b) a curing agent, and (c) an inorganic filler containing glass fiber, fused silica and crystalline silica, and the glass fiber has an average diameter of 3 to 20 μm. An epoxy resin composition is disclosed wherein the average length is 10 to 300 μm, the average particle size of the fused silica is 2 to 10 μm, and the average particle size of the crystalline silica is 2 μm or less. According to the invention according to Patent Document 3, an epoxy resin that has excellent fluidity and has a low coefficient of thermal expansion after curing, and can form a high-strength resin layer by preventing cracks regardless of the material of the insert. It is said that a composition can be provided.

  Patent Document 4 discloses an insulating casting resin for electrical equipment used in electrical equipment, which is at least of fine elastomer particles having polarity in a state dispersed in an epoxy resin and liquid elastomer having molecules having polarity. Disclosed is an insulating casting resin for electrical equipment, characterized by containing a filler formed on at least one of an inorganic compound and an inorganic compound whose surface is modified with an organic molecule. Yes. According to the invention according to Patent Document 4, it is possible to maintain the strength of the high-voltage electrical device even with a smaller amount of use, which can contribute to the reduction in size, weight, and life of the high-voltage electrical device. It is said that it can be improved.

JP 2007-106787 A JP 06-107770 A JP-A-10-316839 JP 2011-1424 A

  Since the mold resin described in Patent Document 1 is a one-component resin, a curing reaction proceeds during storage, leading to thickening and gelation of the mold resin. In Patent Document 1, in order to avoid this problem, a process of casting and curing immediately after manufacturing a mold resin is disclosed in an example. However, in this method, the production process of the mold resin and the molded product becomes complicated and is not suitable for mass production.

  In Patent Document 2, it is considered that the storage stability of the mold resin is improved as compared with Patent Document 1 by separating the epoxy resin and the carboxylic acid anhydride which is a curing agent of the epoxy resin. However, both the first liquid and the second liquid contain a radical polymerizable monomer and a maleimide compound, and the radical polymerizable monomer containing the maleimide compound is prone to spontaneous polymerization, compared to epoxy resins and carboxylic acid anhydrides. Inferior storage stability. Although this problem can be avoided by refrigerated storage of the mold resin, there arises a problem that it is necessary to newly install a refrigeration storage facility and a preheating facility for the mold resin.

  In Patent Document 3 and Patent Document 4, a method of adding an elastomer, an inorganic filler, or the like is employed in order to improve crack resistance. Addition of this elastomer, inorganic filler, etc. improves the cracking property of the cured product, while increasing the viscosity of the epoxy resin, it causes a major problem in the manufacturing process, such as a decrease in castability and defoaming property. Yes. Further, when the viscosity of the epoxy resin is lowered, the filler is settled and a configuration for redispersion is required, but this increases the manufacturing cost.

In view of the above circumstances, an object of the present invention is to provide a mold resin material for a high voltage device and a method for manufacturing the high voltage device that improve the storage stability of the mold resin material, and suppress the filler sedimentation and improve the casting property. It is to provide.

In order to solve the above-mentioned problems, it contains a main agent containing an epoxy resin and a radical polymerization initiator which are liquid at room temperature and have an epoxy equivalent of 200 g / eq or less, and an acid anhydride and an epoxy resin curing catalyst which are liquid at room temperature A curing agent that is liquid at room temperature, a radically polymerizable monomer that is liquid at room temperature, and a reactive diluent containing maleic anhydride or phenylmaleimide as a copolymerization agent . Each of them contains 73 to 89% by mass of organic / inorganic filler, and the organic / inorganic filler contains 33 to 97% by mass of crushed crystalline silica having an average particle size of 5 to 25 μm and 0 to 5% of fused silica having an average particle size of 5 to 25 μm. 65% by weight and a core-shell rubber particles having an average particle diameter of 0.1~1μm comprises 1-3 wt%, divided the main agent, curing agent and the reactive diluent each Providing a molding resin material for high voltage equipment, characterized in that stored. In order to solve the above problems, a main agent containing an epoxy resin and a radical polymerization initiator that are liquid at room temperature and have an epoxy equivalent of 200 g / eq or less, an acid anhydride that is liquid at room temperature, and an epoxy resin curing catalyst And a reactive diluent containing maleic anhydride or phenylmaleimide as a copolymerization agent, and a liquid polymerizable monomer at room temperature and a radical polymerizable monomer liquid at room temperature. The molding resin material for high-voltage equipment is cast on a member constituting the high-voltage equipment and cured, and the main agent and the curing agent each contain 73 to 89% by mass of an organic-inorganic filler, The organic-inorganic filler comprises 33 to 97% by mass of crushed crystalline silica having an average particle size of 5 to 25 μm, and 0 to 65% of fused silica having an average particle size of 5 to 25 μm. Provided is a method for producing a high-voltage device comprising 1 to 3% by mass of core-shell rubber particles having a mass% and an average particle size of 0.1 to 1 μm.

  According to the present invention, it is possible to provide a molding resin material for a high voltage device and a method for manufacturing the high voltage device that improve the storage stability of the molding resin material and suppress the filler sedimentation and improve the casting property. .

  Problems, configurations, and effects other than those described above will become apparent from the following description of embodiments.

It is a cross-sectional schematic diagram which shows an example of the vacuum circuit breaker produced using the manufacturing method of the high voltage apparatus which concerns on this invention.

[Mold resin material for high voltage equipment]
As described above, the mold resin material for high-voltage equipment according to the present invention is a liquid containing liquid at room temperature and an epoxy resin having an epoxy equivalent of 200 g / eq or less and a main agent containing a radical polymerization initiator (hereinafter referred to as “main agent A”). Or a curing agent containing an acid anhydride that is liquid at room temperature and an epoxy resin curing catalyst (hereinafter also referred to as “curing agent B” or simply “B”), and room temperature. A reactive diluent containing a liquid acid anhydride, a radically polymerizable monomer and a copolymer (hereinafter also referred to as “reactive diluent C” or simply “C”), It is characterized by being stored separately.

  In the present invention, the “mold resin material for high-voltage equipment” (hereinafter, also simply referred to as “mold resin material”) is a resin material for molding a constituent member of a high-voltage equipment. ~ C) means the material set before mixing. Further, “room temperature” is synonymous with “room temperature” and is 20 to 30 ° C. (20 ° C. or more and 30 ° C. or less).

  The mold resin material according to the present invention is characterized in that A to C are divided. In the invention described in the above-mentioned patent documents, one or both of the components corresponding to A or B according to the present invention contain the component corresponding to C according to the present invention. C which is a radical polymerizable monomer is a highly reactive component. When A or B contains C, A or B may be deteriorated by polymerization of C during transportation or storage (preservation). Since C is separated from A and B in the present invention, the storage stability of A and B is improved, and self-polymerization occurs only in C containing a radically polymerizable monomer, minimizing the loss of mold resin material. Can be suppressed.

  In addition, the mold resin material according to the present invention has a composition in which the viscosity is not excessively lowered (greater than 20 mPa · s) when A, B, and C are mixed. If the viscosity is too low, casting becomes easy, but the additive (filler) contained in the resin will settle. Dispersing the settled filler again is not preferable because it requires a dispersing device, which increases the manufacturing cost. However, if the viscosity becomes too high, casting becomes difficult. The present invention balances storage stability and viscosity by storing A and B and C separately.

  Furthermore, the mold resin material according to the present invention reacts with the radical polymerizable monomer and the copolymerizing agent during the curing reaction to produce a copolymer, thereby producing a phase separation structure in the cured epoxy resin. This phase separation structure suppresses the progress of cracks in the cured epoxy resin and contributes to the improvement of crack resistance. In addition, since the radical polymerizable monomer is a copolymer, the heat resistant temperature is higher than when the radical polymerizable monomer is polymerized alone, and the heat resistance of the cured epoxy resin is not impaired.

  Hereinafter, the composition of the mold resin material according to the present invention will be described in detail.

(1) Epoxy resin As an epoxy resin used by this invention, the epoxy resin which is liquid at normal temperature and whose epoxy equivalent is 200 g / eq or less is preferable. From the viewpoint of reducing the resin viscosity, those having an epoxy equivalent of 200 g / eq or less are used. Bisphenol A type or bisphenol F type epoxy resin is preferred.

  Specifically, EPICLON 840 (epoxy equivalent 180 to 190 g / eq, viscosity 9000 to 11000 mPa · s / 25 ° C) manufactured by DIC Corporation, EPICLON 850 (epoxy equivalent 183 to 193 g / eq, viscosity 11000 to 15000 mPa · s / 25 ° C) ), EPICLON 830 (epoxy equivalent 165 to 177 g / eq, viscosity 3000 to 4000 mPa · s / 25 ° C.) jER manufactured by Mitsubishi Chemical Corporation (“jER” is a registered trademark of Mitsubishi Chemical Corporation) 827 (epoxy equivalent 180 to 190 g) / Eq, viscosity 9000 to 11000 mPa · s / 25 ° C), jER828 (epoxy equivalent 184 to 194 g / eq, viscosity 12000 to 15000 mPa · s / 25 ° C), jER806 (epoxy equivalent 160 to 170 g / eq, viscosity 1500 to 2500 mPa ·). / 25 ℃), jER807 (epoxy equivalent 160~175g / eq, include viscosity 3000~4500mPa · s / 25 ℃) or the like. From the viewpoint of heat resistance, it is preferable to use a bisphenol A type epoxy resin, and from the viewpoint of reducing the viscosity, it is preferable to use a bisphenol F type epoxy resin. Moreover, in order to balance both characteristics, these epoxy resins can also be mixed and used.

(2) Acid anhydride The acid anhydride is preferably an acid anhydride that is liquid at room temperature. Examples thereof include Hitachi Chemical Co., Ltd. HN-2000 (anhydride equivalent 166 g / eq, viscosity 30-50 mPa · s / 25 ° C.), HN-5500 (acid anhydride equivalent 168 g / eq, viscosity 50- 80 mPa · s / 25 ° C.), MHAC-P (acid anhydride equivalent 178 g / eq, viscosity 150 to 300 mPa · s / 25 ° C.), DIC Corporation EPICLON B-570H (acid anhydride equivalent 166 g / eq, viscosity 40 mPa · s / 25 ° C.).

(3) Radical polymerizable monomer The radical polymerizable monomer is preferably liquid at room temperature in order to lower the viscosity of the mold resin, and examples thereof include styrene, methyl methacrylate, acrylonitrile and acrylate.

(4) Copolymerizing agent The copolymerizing agent is one that is copolymerized with a radically polymerizable monomer, and the copolymerizing agent is preferably maleic anhydride, phenylmaleimide, or the like that increases the glass transition temperature of the cured product from the viewpoint of heat resistance. .

(4) Epoxy resin curing catalyst Examples of the epoxy resin curing catalyst that accelerates the curing reaction between the epoxy resin of the present invention and an acid anhydride include tertiary amines such as trimethylamine, triethylamine, tetramethylbutanediamine, and triethylenediamine. Amines such as dimethylaminoethanol, dimethylaminopentanol, tris (dimethylaminomethyl) phenol, N-methylmorpholine, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium iodide, dodecyltrimethylammonium bromide, Dodecyltrimethylammonium chloride, dodecyltrimethylammonium iodide, benzyldimethyltetradecylammonium chloride, benzyldimethyl Quaternary ammonium salts such as rutetradecylammonium bromide, allyldodecyltrimethylammonium bromide, benzyldimethylstearylammonium bromide, stearyltrimethylammonium chloride, benzyldimethyltetradecylammonium acetylate, 2-methylimidazole, 2-ethylimidazole, 2- Undecylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-azine-2-methylimidazole Imidazoles such as 1-azine-2-undecyl, metal salts of amines with zinc octoate, cobalt, etc., 1,8-diaza-bicyclo (5,4,0) -undecene-7, N-methyl-piperazine, Amine tetraphenylborate such as tetramethylbutylguanidine, triethylammonium tetraphenylborate, 2-ethyl-4-methyltetraphenylborate, 1,8-diaza-bicyclo (5,4,0) -undecene-7-tetraphenylborate , Triphenylphosphine, triphenylphosphonium tetraphenylborate, aluminum trialkylacetoacetate, aluminum trisacetylacetoacetate, aluminum alcoholate, aluminum acylate and sodium alcoholate.

  The addition amount of the epoxy resin curing catalyst is preferably in the range of 0.2 to 2.0 parts by mass or less with respect to 100 parts by mass of the epoxy resin, thereby enabling high-speed curing.

(5) Radical polymerization initiator Examples of the radical polymerization initiator (catalyst) include benzoin compounds such as benzoin and benzoinmethyl, acetophenone, acetophenone compounds such as 2,2-dimethoxy-2-phenylacetophenone, and thioxanthone. Thioxanthone compounds such as 2,4-diethylthioxanthone, 4,4′-diazidochalcone, 2,6-bis (4′-azidobenzal) cyclohexanone, bisazide compounds such as 4,4′-diazidobenzophenone, Azo compounds such as azobisisobutyronitrile, 2,2-azobispropane, m, m'-azoxystyrene, hydrazone, 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne 3, dicumyl peroxide, t-butylperoxymaleic acid, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Organic peroxides such as hexyne and dicumyl peroxyside. Among these, from the viewpoint of storage stability, a radical polymerization initiator having a 10-hour half-life temperature of 100 ° C. or higher can be preferably used.

  The addition amount of the radical polymerization initiator is such that the total amount of the radical polymerizable monomer and the copolymer is 100 parts by mass, and is in the range of 0.3 part by mass to 1.0 part by mass. It is preferable from the viewpoint of adjustment.

  The mold resin material according to the present invention includes the components (1) to (5). The compounding ratio of main agent A, curing agent B and reactive diluent C is such that the equivalent number of acid anhydride is in the range of 0.95 to 1 when the equivalent number of epoxy resin in main agent A is 1. A to C are weighed and blended. If it is less than 0.95, the curing agent is insufficient, and if it exceeds 1, the curing agent is excessive, and the curing reaction between the epoxy resin and the curing agent is insufficient. By setting the amount within the above range, it is possible to prevent shortage of the curing reaction between the epoxy resin and the acid anhydride.

  Moreover, the compounding quantity of the reactive diluent C is the range of 20-35 mass% with respect to the total amount of the epoxy resin which the main ingredient A contains, the acid anhydride which the hardening | curing agent B contains, and the reactive diluent C. It is preferable from the viewpoint of increasing toughness.

  Furthermore, the mold resin material according to the present invention includes an organic inorganic filler, a silane coupling agent, and a dispersing agent in addition to A to C constituted by the above (1) to (5). May be. The organic inorganic filler includes silica (crushed crystalline silica and fused silica) and core-shell rubber particles. Below, each component is explained in full detail.

(6) Silica Crushed crystalline silica and fused silica are preferable from the viewpoint of improving crack resistance, high thermal conductivity, and low thermal expansion of the cured resin. The crushed crystalline silica is preferably added as composite fine particles because it has low thermal expansion and high thermal conductivity and is inexpensive. The preferable average particle diameter is 5 μm to 25 μm. Examples of such silica include SQ-H22 and SQ-H18 manufactured by Hayashi Kasei Co., Ltd. and CRYSTALITE manufactured by Tatsumori Co., Ltd. (“CRYSTALITE” is a registered trademark of Tatsumori Co., Ltd.).

  Fused silica has lower thermal conductivity, lower thermal expansion coefficient, and less thickening effect on the mold resin than crushed crystalline silica. Therefore, it is preferable to use in combination with crushed crystalline silica in consideration of the characteristics required for the mold resin. The preferable average particle diameter of the fused silica is 5 μm to 25 μm. Examples of such silica include FD-5D, FB-12D, and FB-20D manufactured by Denki Kagaku Kogyo Co., Ltd.

(7) Core-shell rubber particles The core-shell rubber particles are excellent in dispersibility with respect to the epoxy resin and suppress the development of cracks to a minimum. Examples of the core-shell rubber particles include: Rohm & Haas, trade name: Paraloid ("Paraloid" is a registered trademark of Rohm & Haas) EXL2655 (average particle diameter 200 nm), Gantz Kasei Co., Ltd., trade name: Staphyloid AC3355 (Average Particle size 0.1-0.5 μm) and Zefiac F351 (average particle size 0.3 μm). Thus, the average particle diameter of the core-shell rubber particles is preferably 0.1 μm to 1 μm.

  The blending amount of the organic inorganic filler composed of the above-mentioned crushed crystalline silica, fused silica and core-shell rubber particles is preferably in the range of 73 to 89% by mass with respect to the main agent A and the curing agent B, respectively. If it is less than 73 mass%, the improvement of characteristics, such as thermal conductivity, toughness, thermal shock resistance, low thermal expansion, and heat resistance, which are the effects of the organic / inorganic filler, is not sufficient. On the other hand, when the blending amount exceeds 89% by mass, the resin viscosity is remarkably increased. More specifically, the crushed crystalline silica is preferably 33 to 97 mass%, the fused silica is 0 to 65 mass%, and the core-shell rubber particles are preferably 1 to 3 mass%. The composition range of these fillers is preferably adjusted according to the target physical properties.

(8) Coupling agent As the coupling agent, various silane-based and titanate-based coupling agents can be used. Preferred examples of the silane coupling agent include epoxy silanes and vinyl silanes such as KBM-402, KBM-403, KBM-502 and KBM-504 manufactured by Shin-Etsu Chemical Co., Ltd. Examples of titanate coupling agents include S-151, S-152 and S-181 manufactured by Nippon Soda Co., Ltd.

(9) Dispersant As the dispersant, various nonionic surfactants are preferable. Examples thereof include BYK-W903, BYK-W980, BYK-W996, and BYK-W9010 manufactured by BYK Chemie Japan. I can do it.

  The coupling agent and dispersant described above contribute to the reduction of the resin viscosity by chemically bonding or adsorbing to the surface of the organic / inorganic filler to modify the surface. Therefore, even if added excessively, it cannot be chemically bonded or adsorbed on the surface of the organic / inorganic filler, and a further low viscosity effect cannot be expected. Excessive blending is not preferable because it lowers the glass transition temperature and thermal decomposition start temperature of the cured resin. From the above, the blending amount of the coupling agent and the dispersant is in the range of 0.2 to 0.9 parts by mass and 0.5 to 0.8 parts by mass, respectively, with respect to 100 parts by mass of the total amount of the organic / inorganic filler. It is preferable to use it.

[Manufacturing method of high voltage equipment]
The manufacturing method of the high voltage apparatus which concerns on this invention has the process of casting and molding the mold resin material for high voltage apparatuses which concerns on this invention mentioned above to the member which comprises a high voltage apparatus, It is characterized by the above-mentioned. The mold resin material for high-voltage equipment according to the present invention is excellent in storage stability, suppresses filler sedimentation, and is excellent in castability, thereby realizing improvement in manufacturability and reduction in production cost of high-voltage equipment. be able to. In addition, there is no limitation in particular in the manufacturing method and casting method of AC, The conventional technique can be used.

  According to the method of manufacturing a high voltage device according to the present invention, various power devices (such as a vacuum circuit breaker and a transformer) can be manufactured. FIG. 1 is a schematic cross-sectional view showing an example of a vacuum circuit breaker manufactured using the method for manufacturing a high-voltage device according to the present invention. As shown in FIG. 1, the vacuum circuit breaker 10 includes an insulating resin layer 1, a fixed electrode 2, a movable electrode 3, a fixed side end plate 4, a movable side end plate 5, a vacuum insulating container (alumina) 6, a bellows 7, and the like. Composed. The vacuum circuit breaker 10 uses the above-described mold resin material for high voltage equipment according to the present invention for forming the insulating resin layer 1. Since others are well-known structures, detailed description is abbreviate | omitted.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

(I) Test sample jER828: bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 190 g / eq
EP-4901: ADEKA bisphenol F type epoxy resin, epoxy equivalent of about 170 g / eq
HN-5500: Hitachi Chemical Co., Ltd. 3- or 4-methyl-hexahydrophthalic anhydride, acid anhydride equivalent 168 g / eq, acid anhydride having no unsaturated double bond in the structure 2E4MZ-CN: Shikoku Chemical Industries ( Co., Ltd. 1-cyanoethyl-2-ethyl-4-methylimidazole, epoxy resin curing catalyst Perhexin 25B: NOF Corporation 1,2,5-dimethyl-2,5-di (t-butylperoxy) hexyne , Radical polymerization initiator, 10 hour half-life temperature 128.4 ° C
XJ-7: Crystalline crushed silica manufactured by Tatsumori Co., Ltd., particle size of about 6.3 μm, crushed crystalline silica FB-20D: fused silica manufactured by Denki Kagaku Kogyo Co., Ltd., particle size of about 22 μm, fused silica KBM -503: Shin-Etsu Chemical Co., Ltd. 3-methacryloxypropyltrimethoxysilane, silane coupling agent KBM-403: Shin-Etsu Chemical Co., Ltd. 3-glycidoxypropyltrimethoxysilane, silane coupling agent Core-shell rubber particles: Staphyroid AC3355 manufactured by Ganz Kasei Co., Ltd., average particle size 0.1 to 0.5 μm
Dispersant: BYK-W9010 manufactured by Big Chemie Japan
M3130: Trimethylol-propane EO modified triacrylate manufactured by Toyo Chemicals Co., Ltd. Styrene: Tokyo Chemical Industry Co., Ltd. styrene, containing 30 ppm 4-tert-butylcatechol as a radical polymerization inhibitor Maleic anhydride: Wako Pure Chemical Industries, Ltd. N -Phenylmaleimide: N-phenylmaleimide manufactured by Tokyo Chemical Industry Co., Ltd. Mold resin materials of Comparative Examples 1 to 4 and Examples 1 to 4 were produced in the following manner using the above test materials.

(Ii) Preparation of resin The above specimens were blended at a predetermined blending ratio, and stirred for 3 minutes with an AR-100 type rotation / revolution mixer manufactured by Sinky Co., Ltd. Comparative Examples 1 to 4 and Examples 1 to 4 A resin composition (mixture before curing) was prepared. The composition of the mold resin material of Comparative Examples 1 to 4 is shown in Table 1 described later, and the composition of the mold resin material of Examples 1 to 4 is shown in Table 2. The material composition in Table 1 is a mass ratio.

(Iii) Measurement of resin viscosity The viscosity of the resin composition was measured at 40 ° C using an E-type viscometer. Table 1 to be described later shows the viscosities of the molding resin materials of Comparative Examples 1 to 4, and Table 2 shows the viscosities of the molding resin materials of Examples 1 to 4.

(Iv) Presence or absence of sedimentation of filler The presence or absence of sedimentation in A to C was confirmed visually. Table 1 described below shows the presence or absence of sedimentation of the fillers of Comparative Examples 1 to 4, and Table 2 shows the presence or absence of sedimentation of the fillers of Examples 1 to 4.

[Comparative Example 1]
M3130 as a radical polymerizable monomer and maleic anhydride as a copolymerizer are contained in the curing agent B, and because of the two-component configuration (configuration in which A to C are not separated), the viscosity of the curing agent B is 30 mPa · Lower than s, filler sedimentation occurred in curing agent B after storage at 40 ° C. for 168 hours.

[Comparative Example 2]
M3130 as a radical polymerizable monomer and N-phenylmaleimide as a copolymerizer are contained in the curing agent B. The viscosity of the curing agent B is lower than 30 mPa · s due to the two-component structure, and is cured after storage at 40 ° C. for 168 hours. In the agent B, sedimentation of the filler occurred.

[Comparative Example 3]
Styrene as a radically polymerizable monomer and maleic anhydride as a copolymerizer are contained in the curing agent B. Due to the two-component structure, the viscosity of the curing agent B is lower than 30 mPa · s, and the curing agent after storage at 40 ° C. for 168 hours. In B, sedimentation of the filler occurred.

[Comparative Example 4]
Styrene as a radical polymerizable monomer and N-phenylmaleimide as a copolymerizing agent are contained in the curing agent B. Due to the two-component structure, the viscosity of the curing agent B is lower than 30 mPa · s and is cured after storage at 40 ° C. for 168 hours. In the agent B, sedimentation of the filler occurred.

  The mold resin material of Example 1 is an epoxy resin (jER260, E-4901) in which the equivalent of an epoxy resin that is liquid at room temperature is 200 g / eq or less, and a main agent A containing a radical polymerization initiator (perhexine 25B), Curing agent B containing acid anhydride (HN-5500) and epoxy resin curing catalyst (2E4MZ-CN) which are liquid at normal temperature, acid anhydride (HN-5500) and radical polymerizable monomer (M3130) which are liquid at normal temperature And a reactive diluent C agent containing a copolymer (maleic anhydride). Further, the main agent A and the curing agent B contain silica, an organic inorganic filler, a dispersant, and a silane coupling agent within the scope of the present invention. As a result, the viscosities of the main agent A and the curing agent B were greater than 20 mPa · s, and no sedimentation of fillers occurred in A and B even after storage for 168 hours at 40 ° C.

  The mold resin material of Example 2 is composed of a main agent A containing an epoxy resin (jER260, E-4901) radical polymerization initiator (Perhexine 25B) having an equivalent amount of an epoxy resin that is liquid at room temperature of 200 g / eq or less at room temperature. A curing agent B containing a liquid acid anhydride (HN-5500) and an epoxy resin curing catalyst (2E4MZ-CN), a liquid acid anhydride (HN-5500) and a radical polymerizable monomer (M3130) at room temperature It consists of 3 liquids of the reactive diluent C agent containing a polymerization agent (N-phenylmaleimide). Furthermore, silica, an organic inorganic filler, a dispersant, and a silane coupling agent are contained within the scope of the present invention. As a result, the viscosities of the main agent A and the curing agent B were larger than 20 mPa · s, and even after storage at 40 ° C. for 168 hours, there was no sedimentation of filler as shown in Table 2 in A and B.

  The mold resin material of Example 3 is composed of a main agent A containing an epoxy resin (jER260, E-4901) in which the equivalent of an epoxy resin that is liquid at room temperature is 200 g / eq or less and a radical polymerization initiator (Perhexine 25B), and room temperature. And a curing agent B containing an acid anhydride (HN-5500) and an epoxy resin curing catalyst (2E4MZ-CN), an acid anhydride (HN-5500) and a radical polymerizable monomer (styrene) at room temperature It is composed of three liquids of a reactive diluent C containing a copolymer (maleic anhydride). Furthermore, silica, an organic inorganic filler, a dispersant, and a silane coupling agent are contained within the scope of the present invention. As a result, the viscosities of the main agent A and the curing agent B were larger than 20 mPa · s, and even after storage at 40 ° C. for 168 hours, there was no sedimentation of filler as shown in Table 2 in A and B.

  The mold resin material of Example 4 is composed of a main agent A containing an epoxy resin (jER260, E-4901) in which the equivalent of an epoxy resin that is liquid at room temperature is 200 g / eq or less and a radical polymerization initiator (Perhexine 25B), and room temperature. A liquid acid anhydride (HN-5500), an epoxy resin curing catalyst (curing agent B containing 2E4MZ-CN, a liquid acid anhydride (HN-5500) and a radical polymerizable monomer (styrene) at room temperature. Consists of three liquids of a reactive diluent C containing a polymerization agent (N-phenylmaleimide) and further contains silica, an organic inorganic filler, a dispersant and a silane coupling agent within the scope of the present invention. As a result, the viscosities of the main agent A and the curing agent B are larger than 20 mPa · s, and even when stored at 40 ° C. for 168 hours, the viscosity is shown in Table 2 as A and B. Sedimentation of the filler in Suyo did not.

  The viscosities of the mixtures A to C of Examples 1 to 4 are all 28 mPa · s or less at 40 ° C., and have sufficient castability.

  25 kg of the liquid resin compositions of Examples 1 to 4 were prepared. The liquid resin composition was heated to 80 ° C. and degassed at 1 torr for about 10 minutes. The resin viscosity at 80 ° C. was 3.0 Pa · s. The mold of the model vacuum circuit breaker was heated to 80 ° C., 25 kg of the degassed liquid resin composition was poured, and vacuum degassed again at 1 torr for 20 minutes. Then, it hardened | cured on condition of 100 degreeC / 5 hours and 170 degreeC / 7 hours in air | atmosphere. Subsequently, it cooled to 50 degreeC over 8 hours, the type | mold was removed, and the model vacuum circuit breaker shown in FIG. 1 was produced.

  As a result of observation of the appearance and cross section of the vacuum circuit breaker, no cracks or voids were observed inside the cured epoxy resin, and a vacuum circuit breaker capable of realizing high heat resistance, crack resistance and insulation reliability could be obtained.

  As described above, according to the present invention, it is possible to provide a molding resin material for high-voltage equipment and a method for manufacturing a high-voltage equipment that improve the storage stability of the molding resin material and suppress the filler sedimentation and improve the casting property. It was demonstrated that The mold resin of the present invention is suitable as an insulating material and a structural material for electric power equipment because it has excellent storage stability and is well balanced in reducing viscosity and improving crack resistance.

  Note that the above-described embodiments have been specifically described in order to help understanding of the present invention, and the present invention is not limited to having all the configurations described. For example, a part of the configuration of one embodiment can be replaced with the configuration of another embodiment, and the configuration of another embodiment can be added to the configuration of one embodiment. Further, a part of the configuration of each embodiment can be deleted, replaced with another configuration, or added with another configuration.

  DESCRIPTION OF SYMBOLS 1 ... Insulating resin layer, 2 ... Fixed electrode, 3 ... Movable electrode, 4 ... Fixed side end plate, 5 ... Movable side end plate, 6 ... Vacuum insulation container (alumina), 7 ... Bellows.

Claims (8)

A main agent containing an epoxy resin that is liquid at room temperature and has an epoxy equivalent of 200 g / eq or less and a radical polymerization initiator;
A curing agent containing a liquid acid anhydride and an epoxy resin curing catalyst at room temperature;
An acid anhydride that is liquid at normal temperature, a radically polymerizable monomer that is liquid at normal temperature, and a reactive diluent containing maleic anhydride or phenylmaleimide as a copolymer,
The main agent and the curing agent each contain 73 to 89% by mass of an organic inorganic filler, and the organic and inorganic filler contains 33 to 97% by mass of crushed crystalline silica having an average particle size of 5 to 25 μm and an average particle size of 5 0 to 65% by weight of fused silica of -25 μm and 1 to 3% by weight of core-shell rubber particles having an average particle size of 0.1 to 1 μm,
The main resin, the curing agent, and the reactive diluent are stored separately, and a mold resin material for a high voltage device.   The mold resin material for high-voltage devices according to claim 1, wherein the main agent and the curing agent have a viscosity at 40 ° C of greater than 20 mPa · s. The main agent and the curing agent each include a coupling agent and a dispersing agent,
The content of the coupling agent is 0.2 to 0.9 parts by mass with respect to 100 parts by mass of the organic / inorganic filler, and the content of the dispersant is 0.5% with respect to 100 parts by mass of the organic / inorganic filler. molding resin material for high voltage equipment according to claim 1, wherein it is 0.8 parts by weight. A main agent containing an epoxy resin that is liquid at room temperature and has an epoxy equivalent of 200 g / eq or less and a radical polymerization initiator;
A curing agent containing a liquid acid anhydride and an epoxy resin curing catalyst at room temperature;
Mold resin for high-voltage equipment in which acid anhydrides that are liquid at normal temperature, radical polymerizable monomers that are liquid at normal temperature, and reactive diluents containing maleic anhydride or phenylmaleimide as a copolymerization agent are separately stored the material was cast into a member constituting the high-voltage equipment, have a step of curing,
The main agent and the curing agent each contain 73 to 89% by mass of an organic inorganic filler, and the organic and inorganic filler contains 33 to 97% by mass of crushed crystalline silica having an average particle size of 5 to 25 μm and an average particle size of 5 A method for producing a high-voltage device, comprising 0 to 65% by mass of fused silica of -25 μm and 1 to 3% by mass of core-shell rubber particles having an average particle size of 0.1 to 1 μm . The method for producing a high-voltage device according to claim 4, wherein the viscosity of the main agent and the curing agent at 40 ° C is greater than 20 mPa · s. The main agent and the curing agent each include a coupling agent and a dispersing agent,
The content of the coupling agent is 0.2 to 0.9 parts by mass with respect to 100 parts by mass of the organic / inorganic filler, and the content of the dispersant is 0.5% with respect to 100 parts by mass of the organic / inorganic filler. The method for producing a high-voltage device according to claim 4 , wherein the amount is ˜0.8 parts by mass. 5. The method of manufacturing a high voltage device according to claim 4, wherein the high voltage device is a power device. 8. The method of manufacturing a high voltage device according to claim 7, wherein the power device is a vacuum circuit breaker.

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