JP2015002095A - Resin composition for electric insulation and manufacturing method of insulated electric appliance using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for electric insulation affording a favorable work environment and a favorable heat releasability and especially useful as an impregnation varnish for electric appliances.SOLUTION: The provided resin composition for electric insulation includes, as indispensable materials, (A) an unsaturated polyester using, as indispensable components, an α,β-unsaturated dibasic acid and an alcohol having at least one hydroxyl group, (B) a reactive diluent having an unsaturated group exhibiting, at 20°C, a vapor pressure of 0.1 mmHg or less, (C) an alkylbenzene-formaldehyde resin, (D) a monofunctional (meth)acrylate possessing an aliphatic principal chain and/or a compound including one intramolecular hydroxyl group, possessing an aliphatic principal chain, and including an allyl group at the molecule terminal thereof, (E) a silane coupling agent including 2 or 3 methyloxy groups, and (F) an inorganic filler.

Description

The present invention relates to a resin composition for electrical insulation and a method for producing an electrical equipment insulator.
Furthermore, in detail, it has a flexible cured film without reducing the impregnation of coils for electrical equipment such as generators, motors such as induction coils, transformers, armatures (rotors), stators (stator), Resin composition for electrical insulation that can be cured in a short time, has high adhesiveness, has heat dissipation, has low odor during work, and has a favorable work environment, and method for producing electrical equipment insulation using the same About.

  Conventionally, coil impregnated varnishes have been used in devices such as rotating machines and transformers for the purposes of fixation, insulation reinforcement, vibration isolation, rust prevention, and the like. The coil-impregnated varnish is roughly classified into two types, a solvent-type varnish and a solvent-free varnish, and is appropriately selected depending on the type of equipment, processing method, and the like.

  The solvent-type varnish is obtained by dissolving an alkyd resin with naphtha or the like. Therefore, there is a problem that a large amount of solvent is naturally scattered during the heat curing treatment. In addition, the solventless varnish is generally obtained by dissolving a resin having an unsaturated group in a reactive monomer such as styrene, and the solvent is not scattered as in the solvent varnish during the heat curing process. Due to the stimulating properties of styrene, the effect on the handling operator is great despite the small amount of scattering, and there is a problem that the working environment deteriorates. As described above, no problems have been solved in any varnish with respect to workers and work environment problems.

  And recently, from the reasons of high workability (short processing time), resource saving, rust prevention performance, etc., examination from a solvent type to a solventless type has been advanced. One example of the solventless varnish is an unsaturated polyester varnish. Unsaturated polyester varnish consists of unsaturated polyester and crosslinkable monomer, and is harmonized in terms of mechanical, electrical and thermal properties, workability, economy, etc., so FRP laminates, linings, etc. It is used for many purposes including building equipment.

  The requirements for this solventless impregnated varnish include low temperature, short time curing, reduction of solvent volatilization from the varnish (no solvent) and imparting high adhesion.

  As a method corresponding to this requirement, a method of reducing the styrene content or a method of reducing a styrene volatilization amount by blending an additive is adopted. However, these methods are basically resins that contain styrene, and are still insufficient as countermeasures against odor. Many methods using other polymerizable unsaturated monomers in place of styrene have been reported. For example, a monomer containing an oligoethylene glycol alkyl ether methacrylate such as diethylene glycol monomethyl ether methacrylate as an essential component as a polymerizable unsaturated monomer, or an oligo ether monoalkyl ether methacrylate such as dipropylene glycol monoethyl ether methacrylate as an essential component Resin composition using the contained monomer, resin composition using oligoethylene glycol di (meth) acrylate and / or oligopropylene glycol di (meth) acrylate as an essential component as a polymerizable unsaturated monomer, There is a resin composition containing alkyl cyclohexyl (meth) acrylate as an essential component as a saturated monomer.

  In addition, for example, a resin composition containing a macromonomer having a polymerizable unsaturated bond group and an oligoether monoalkyl ether (meth) acrylate of a diol having 2 to 4 carbon atoms as a polymerizable unsaturated monomer, or a molecular terminal A resin composition containing a resin having at least two (meth) acryloyl groups, a monomer having a (meth) acrylate group and an acetyllactone compound, a dicyclopentadiene-modified unsaturated polyester oligomer, a cyclohexene ring, and Various reports have been made on ester compounds having an allyl ether group and unsaturated polyester resin compositions containing hydroxyalkyl methacrylate as essential components.

  Further, for high adhesion, an epoxy resin is an epoxy resin containing a epoxidized product of a condensate of phenols dimethylol and naphthols and a bisphenol F type epoxy resin in a ratio of 50 to 95:50 to 5 (weight ratio). A resin mixture, an epoxy resin composition containing the epoxy resin mixture, a curing agent and a curing accelerator, and a method using the cured product, an epoxy resin, a mixture of nitrile rubber, a curing agent, an imidazole compound, borofluoride, and octylic acid A method using a thermosetting fixing agent composed of one or more curing accelerators selected from salts, an epoxy resin, an acid anhydride, and an epoxy resin composition containing an ammonium salt Various methods have been reported.

  Furthermore, recent electrical equipment has become smaller, lighter, higher in output, and more efficient, resulting in higher heat storage temperatures, especially transformers and reactors used in electrical equipment such as microwave ovens and inverter air conditioners. Coils tend to accumulate heat without being dissipated due to excessive load during operation, and the temperature of electrical equipment tends to rise, so each material used must have higher heat resistance and heat dissipation. Has come to be. Among these, as for the method of imparting heat dissipation to the treatment varnish, application of various fillers including metal, which has a different thermal conductivity from the resin composition, has become common. However, these fillers have problems of dispersibility, stability, and permeability to electrical equipment to be processed, and are not generally used.

Japanese Patent Laid-Open No. 7-2106040 JP-A-9-151225 Japanese Patent Laid-Open No. 10-87770 Japanese Patent Laid-Open No. 2002-114829 Japanese Patent Laid-Open No. 10-36461 JP 2003-268054 A JP 2003-89709 A Japanese Patent Laid-Open No. 5-140261 Japanese Patent Laid-Open No. 11-131042 JP 2005-139289 A JP-A-6-032875 JP 2010-105104 A JP 2001-002740 A JP 2002-184238 A

  In view of such problems, the present invention is an electrically insulating resin composition particularly useful as an impregnating varnish for an electrical device having a good working environment and good heat dissipation, which can soften the varnish film and is a conventional liquid. The present invention provides a resin composition capable of exhibiting a cured product characteristic such as good adhesion and electrical insulation equivalent to or better than that of a resin composition of a type, and good stability. The present invention provides a method for producing an electrical device using the insulating resin composition.

The present invention relates to the following.
1. An unsaturated polyester (A) using an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components, and a reaction having an unsaturated group with a vapor pressure at 20 ° C. of 0.1 mmHg or less Diluent (B), alkylbenzene / formaldehyde resin (C), aliphatic monofunctional (meth) acrylate having a main chain and / or an aliphatic main chain having one hydroxyl group in the molecule and an allyl group at the end of the molecule A resin composition for electrical insulation comprising, as essential materials, a compound (D) having a silane coupling agent (E) containing 2 or 3 methyloxy groups and an inorganic filler (F).
2. Item 2. The resin composition for electrical insulation according to Item 1, wherein the unsaturated polyester (A) has a number average molecular weight in the range of 1,000 to 10,000.
3. Item 2. The reactive diluent (B) having an unsaturated group with a vapor pressure at 20 ° C. of 0.1 mmHg or less is contained in an amount of 50 to 400 parts by weight with respect to 100 parts by weight of the unsaturated polyester (A). The resin composition for electrical insulation according to any one of the above.
4). Alkylbenzene-formaldehyde resin (C) is 0 with respect to 100 parts by weight of the total amount of the reactive polyester having the unsaturated polyester (A) and the unsaturated group having an unsaturated group whose vapor pressure at 20 ° C. is 1 mmHg or less. Item 4. The resin composition for electrical insulation according to Item 3, which contains 1 to 20 parts by weight.
5. The main chain is an aliphatic monofunctional (A) component with respect to 100 parts by weight of the total amount of the reactive polyester having unsaturated polyester as the component (A) and the unsaturated group having a vapor pressure at 20 ° C. of the component (B) of 1 mmHg or less. Item 3 or 4 comprising 1 to 100 parts by weight of (meth) acrylate and / or a compound (D) in which the main chain having one hydroxyl group in the molecule is aliphatic and has an allyl group at the molecular end. The resin composition for electrical insulation as described.
6). 2 or 3 methyloxy groups are added to 100 parts by weight of the total amount of the reactive polyester having unsaturated polyesters of component (A) and unsaturated groups having a vapor pressure at 20 ° C. of 1 mmHg or less of component (B). The silane coupling agent to contain (E) The resin composition for electrical insulation in any one of claim | item 3-5 formed by containing 0.01-20 weight part.
7). As inorganic filler (F), silicon dioxide having an average particle size of 0.5 to 5 μm is reacted with unsaturated polyester (A) and unsaturated group (B) having an unsaturated group whose vapor pressure at 20 ° C. is 1 mmHg or less. Item 7. The resin composition for electrical insulation according to any one of Items 3 to 6, comprising 20 to 200 parts by weight with respect to 100 parts by weight of the total amount of the functional diluent.
8). An electrical apparatus is coated with an electrical insulating resin composition obtained by further containing a polymerization initiator in the electrical insulating resin composition according to any one of Items 1 to 7, and is cured. Manufacturing method of equipment insulation.

  Since the resin composition for electrical insulation according to the present invention is excellent in flexibility of a varnish cured product, it is possible to provide a film in which cracks and the like are unlikely to occur even when stress is applied. Moreover, since the viscosity and surface drying property of the resin composition are the same as those of conventional products, the resin composition can be widely applied to the impregnation method. Furthermore, it is highly reliable because it has a cured product characteristic such as electrical insulation and adhesion that is equal to or better than conventional liquid type resin compositions, low dielectric constant and high thermal conductivity, and exhibits good stability. Electrical equipment can be provided.

  The unsaturated polyester (A) using an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components in the present invention is an acid component and an alcohol component having an unsaturated dibasic acid as essential components, Further, it can be obtained by reacting a modifying component as necessary.

  As the unsaturated dibasic acid, maleic anhydride, maleic acid, fumaric acid and the like are used, and these may be used alone or in combination.

  As the acid component, in addition to the α, β-unsaturated dibasic acid described above, a saturated acid and an ester of a lower alkyl of this saturated acid (which does not have a reactive unsaturated bond) can be used in combination. Saturated acids include aromatic, alicyclic, such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, adipic acid, and sebacic acid Or an aliphatic saturated dibasic acid etc. are mentioned. Examples of the ester of a saturated acid lower alkyl include monoesters such as monomethyl terephthalate and diesters such as dimethyl terephthalate. These may be used alone or in combination.

  Furthermore, edible oil fatty acids such as soybean oil fatty acid, linseed oil fatty acid and tall oil fatty acid can be used in combination.

  The amount of unsaturated acid (having a reactive unsaturated bond) is preferably selected in the range of 50 to 90 equivalent% in the total acid component.

  As the alcohol component, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol and the like are used, and these may be used alone or in combination. May be.

  Examples of the modified component used as needed in the synthesis of the unsaturated polyester (A) include linseed oil, soybean oil, tall oil, dehydrated castor oil, coconut oil, dicyclopentadiene, cyclopentadiene, and the like. It is done.

  The number average molecular weight of the unsaturated polyester (A) of the present invention (measured by gel permeation chromatography and converted using a standard polystyrene calibration curve, the same applies hereinafter) is set to 1000 to 10,000. Preferably, it is 1500-5000. If the number average molecular weight is too small, the curability and resin cured product properties of the resin composition tend to be extremely poor, and if the number average molecular weight is too large, the viscosity is too high and impregnation workability tends to deteriorate.

  As a manufacturing method of unsaturated polyester (A) used for this invention, it can be based on a conventionally well-known method. For example, only α, β? Unsaturated dibasic acid, which is an essential component, and an alcohol having one or more hydroxyl groups, or a polybasic acid component and a polyhydric alcohol component are used in combination to cause a condensation reaction, and both components react. The process is carried out while removing the condensed water sometimes generated from the system. The total alcohol component is preferably used in the range of 1 to 2 equivalents relative to 1 equivalent of the total acid component.

  Removal of the condensed water to the outside of the system is preferably carried out by natural distillation or vacuum distillation by passing an inert gas. In order to promote the distillation of the condensed water, a solvent such as toluene or xylene can be added to the system as an azeotropic component. The progress of the reaction can be generally known by measuring the amount of distillate produced by the reaction, quantifying the functional group at the end, and measuring the viscosity of the reaction system.

  The reaction temperature during the synthesis of the unsaturated polyester (A) is preferably 150 to 250 ° C. For this reason, a glass, stainless steel or the like is selected as the reaction apparatus, and a stirring apparatus, a fractionation apparatus for preventing distillation of alcohol components due to azeotropy of water and alcohol components, and raising the temperature of the reaction system. It is preferable to use a reactor equipped with a heating device, a temperature control device for the heating device, and the like. The pressure in the reactor adjusted to carry out the polycondensation reaction in the synthesis can proceed without any problem even at normal pressure, but the reaction can be promoted by increasing the boiling point of the polyhydric alcohol by pressurization. it can. In this case, it is preferable to carry out in the range of normal pressure to 0.1 MPa.

  The reactive diluent (B) having an unsaturated group having a vapor pressure at 20 ° C. of 0.1 mmHg or less used in the present invention is used for the purpose of obtaining a low-odor resin composition, and is an unsaturated polyester. Resin (A), alkylbenzene / formaldehyde resin (C), monofunctional (meth) acrylate whose main chain is aliphatic and / or main chain having one hydroxyl group in the molecule is aliphatic and has an allyl group at the molecular end Those that dissolve the compound (D) are selected. Specific examples of polymerizable monofunctional (meth) acrylates that satisfy this requirement include dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate, and phenol ethylene oxide. Examples thereof include modified acrylates and phenol ethylene oxide modified methacrylates. In addition, (meth) acrylate having a hydroxyl group such as (poly) caprolactone monoethoxy (meth) acrylate such as 2-hydroxyethyl methacrylate, Plaxel FA1, FA2D, FM1D, FM2D, FM3 (all are Daicel brand names) Can be used. It is also possible to use an unsaturated monobasic acid which is a reaction product of a monofunctional (meth) acrylate having one hydroxyl group in the molecule and a saturated dibasic acid. These can be used alone or in combination of two or more.

  In addition, in this specification, (meth) acrylate means an acrylic ester compound or a methacrylic ester compound.

  The amount of the unsaturated polyester (A) and the reactive diluent (B) having an unsaturated group is such that the vapor pressure at 20 ° C. is 0.1 mmHg or less with respect to 100 parts by weight of the unsaturated polyester (A). The reactive diluent (B) having an unsaturated group is preferably in the range of 50 to 400 parts by weight. If there is too little reactive diluent (B) having an unsaturated group, the viscosity of the resulting resin composition will be too high, and not only will it adhere to the transformer surface thickly, but the internal permeability will tend to be poor, On the other hand, if the amount is too large, the appearance of the resin composition becomes turbid and the varnish viscosity is too low, which may cause a problem that the resin deposit that has penetrated inside flows out during heat curing.

  The (C) component alkylbenzene / formaldehyde resin used in the present invention is a resol type obtained by reacting alkylbenzene such as toluene / xylene and formaldehyde in the presence of an alkali catalyst such as sodium hydroxide, ammonia, trieramine and the like. Resin. Examples of commercially available xylene / formaldehyde resins include Nicanol L, Nikanol LL, and Nikanol LLL (all of which are trade names of Fudo Co., Ltd.).

  The amount of the alkylbenzene / formaldehyde resin used as the component (C) used in the present invention is such that the unsaturated polyester as the component (A) and the reactive group having an unsaturated group whose vapor pressure at 20 ° C. of the component (B) is 1 mmHg or less. The alkylbenzene / formaldehyde resin (C) is preferably 0.1 to 50 parts by weight, more preferably 1 to 15 parts by weight, and further preferably 5 to 10 parts by weight with respect to 100 parts by weight of the total diluent. Part. If the amount of alkylbenzene / formaldehyde resin is too much, the surface drying time and the curing time of the resin composition will be prolonged, making it difficult to cure. Conversely, if the amount is too little, the cured film of the resin composition will not be flexible. there's a possibility that.

  The component (D) used in the present invention may have one hydroxyl group in the molecule, is a monofunctional (meth) acrylate having an aliphatic main chain, and is 1,4-butane Diol monomethacrylate, 1,6-hexanediol monomethacrylate, 1,9-nonanediol monomethacrylate, octyl acrylate, octyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isodecyl acrylate, isodecyl methacrylate, Examples include lauryl acrylate, lauryl methacrylate, tridecyl acrylate, tridecyl methacrylate, stearyl acrylate, stearyl methacrylate, and the like. In addition, a mixture of (meth) acrylates having a long-chain alkyl group having 12 to 15 carbon atoms (for example, Kyoeisha's light ester L-7, light ester L-8, Nippon Oil & Fats' Blemmer SLMA, Blemmer CMA, etc.) Can be used. Among these, it is preferable to select and use in consideration of the odor of the monomer. Particularly preferably, monomethacrylate compounds of long-chain alkyl alcohols such as lauryl methacrylate and a mixture of methacrylates having a long-chain alkyl group having 12 to 15 carbon atoms can be used, and these are used alone or in combination of two or more. You can also

  Examples of the compound having one hydroxyl group and allyl group in the molecule include 1,5-pentanediol monoallyl ether, 1,6-hexanediol monoallyl ether, trimethylolpropane diallyl ether, glyceryl diallyl ether, Examples include allyl ether compounds of polyhydric alcohols such as pentaerythritol triallyl ether, polyethylene glycol monoallyl ether, and polypropylene glycol monoallyl ether. These may be used alone or in combination of two or more.

  The amount of the compound (D) in which the main chain is an aliphatic monofunctional (meth) acrylate and / or the main chain having one hydroxyl group in the molecule and the main chain having an aliphatic group and an allyl group at the molecular end is ( The amount of the unsaturated polyester as the component A) and the reactive diluent having an unsaturated group having a vapor pressure at 20 ° C. of 1 mmHg or less as the component (B) should be in the range of 1 to 100 parts by weight. The range is preferably 1 to 50 parts by weight. If the amount of the component (D) is too small, the resulting resin composition will have too high a viscosity, resulting in a cloudy appearance of the resulting resin composition, and not only thick adhesion to the surface of the impregnated electrical equipment, but also poor internal permeability. On the other hand, if the amount is too large, the appearance of the resin composition becomes turbid, and the viscosity of the varnish is too low, so that there is a possibility that a resin deposit that has penetrated inside flows out during heat curing.

又は一般式（２）

で表される化合物がある。ただし、一般式（１）または（２）において、Ｒは、ビニル基、スチリル基、アクリル基、メタクリル基、アクリロイル基、メタクリロイル基、オキシラン基、アミノ基、メルカプト基等の官能基を含む有機基（脂肪族基、脂環式基または芳香族基）であり、Ｘは、メトキシ基である）で示されるシランカップリング剤が挙げられる。 The silane coupling agent containing 2 or 3 methyloxy groups as component (E) used in the present invention is not particularly limited as long as it is a silane coupling agent having a methyloxy group as a functional group. General formula (1)

Or general formula (2)

There is a compound represented by: However, in the general formula (1) or (2), R represents an organic group containing a functional group such as a vinyl group, a styryl group, an acrylic group, a methacryl group, an acryloyl group, a methacryloyl group, an oxirane group, an amino group, or a mercapto group. (An aliphatic group, an alicyclic group, or an aromatic group), and X is a methoxy group).

  Specific examples of the component (E) include vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, and 3-methacrylic acid. Roxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like. Moreover, these can also be used individually or in combination of 2 or more types.

  The amount of the silane coupling agent containing 2 or 3 methyloxy groups as the component (E) used in the present invention is such that the unsaturated polyester as the component (A) and the vapor pressure at 20 ° C. as the component (B) The amount of the silane coupling agent (E) containing 2 or 3 methyloxy groups is 0.01 to 20 parts by weight with respect to 100 parts by weight of the total amount of the reactive diluent having unsaturated groups of 1 mmHg or less. The amount is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

  Even if the silane coupling agent containing 2 or 3 methyloxy groups is added in excess of 20 parts by weight, the volatilization amount is reduced, but the sticking property is reduced, and the surface drying time and the resin are reduced. The curing time of the composition is extended and it is difficult to cure. On the other hand, when the blending amount is less than 0.1 parts by weight, there arises a problem that the fixing strength of the obtained resin composition is lowered.

  If it is silicon dioxide with the average particle diameter of 0.5-5 micrometers of (F) component used for this invention, it will not specifically limit. This average particle size is preferably 0.7 to 3 μm, and more preferably 1 to 2 μm. If this average particle size is too large, the viscosity will be low and the permeability will be improved, but the settling of the filler will be severe and the stability will tend to be poor. On the other hand, if the average particle size is too small, the viscosity increases and a problem of poor permeability occurs. The amount of silicon dioxide used having an average particle size of 0.5 to 5 μm is that of the reactive diluent having an unsaturated group having an unsaturated polyester as the component (A) and a vapor pressure at 20 ° C. of the component (B) of 1 mmHg or less. It is preferable to set it as 20-200 weight part with respect to 100 weight part in total. If the amount of the component (F) is too small, it is difficult to obtain heat-radiating curing. If the amount is too large, the viscosity of the resin composition for insulating electrical equipment will increase too much, and the permeability to the actual machine to be processed will deteriorate, resulting in poor insulation. May be uniform.

  In order to obtain a higher thermal conductivity, it is desirable to mix an inorganic filler such as aluminum hydroxide and calcium silicate in addition to the inorganic filler (F) in the resin composition for insulating electrical equipment of the present invention. . An inorganic filler may be used independently or may be used in mixture of 2 or more types.

  In order to cure the electrically insulating resin composition according to the present invention, a curing agent is further added, but the timing may be just before use or before that. At the same time, it is preferable to add a stabilizer.

  Curing agents used for curing the resin composition for electrical insulation according to the present invention include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, and dialkyl peroxides. Examples include peroxides such as oxides, peroxyesters, and alkylperesters. The amount of the curing agent is determined in accordance with the curing conditions and the appearance, characteristics, etc. of the cured resin product. From the viewpoint of storage stability of the material and molding cycle, the total amount of the reactive diluent having an unsaturated group (A) and an unsaturated group having a vapor pressure at 20 ° C. of component (B) of 1 mmHg or less is 100 parts by weight. 0.5 to 10% by weight is preferable, and 1 to 5% by weight is more preferable.

  Stabilizers used as necessary in the present invention include p-benzoquinone, hydroquinone, naphthoquinone, p-toluquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p-benzoquinone, p-tert-butyl. Catechol, 2,5-di-tert-butylhydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol and the like can be mentioned. The blending amount is conveniently determined by the storage stability of the resin composition, the curing temperature and the curing time during actual machine processing, and the blending amount is usually the unsaturated polyester (A) and the component (B). Is preferably 0.5 parts by weight or less, more preferably 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the total amount of the reactive diluent having unsaturated groups whose vapor pressure at 20 ° C. is 1 mmHg or less. is there.

  Moreover, it is preferable to add various well-known commercially available additives etc. which have the air blocking effect of the hardened | cured material surface as needed to the resin composition for electrical insulation of this invention. By blending these additives, the surface curing (surface drying) time can be shortened. As an example of an additive for shortening the surface curability, low volatility such as paraffin waxes of various melting points, BYK-S740, BYK-S750 (all of which are commercially available from Big Chemie Japan). Agents and the like. The blending amount of the waxes is 100 parts by weight of the total amount of the reactive diluent having an unsaturated polyester having an unsaturated polyester (A) and a vapor pressure of 20 ° C. of the component (B) of 1 mmHg or less. 0.05 to 1 part by weight, preferably 0.1 to 0.5 part by weight.

  Insulation treatment using the resin composition for electrical insulation according to the present invention is performed by a known method, but after the electrical device is immersed in the resin composition for electrical insulation according to the present invention for 2 to 20 minutes, it is pulled up. It is desirable to carry out by a method of curing the resin composition by heating at 100 to 160 ° C. for 1 to 5 hours.

  The resin composition for electrical insulation according to the present invention has less odor and not only good workability, but also heat dissipation, and the resulting varnish film has flexibility, such as transformers and motors. It is suitable for a typical electric equipment impregnation treatment. In particular, since it is used at a high voltage, it is optimal for insulation treatment of electrical equipment such as high-frequency transformers and switching transformers using non-metallic materials such as ferrite that are likely to become high temperature.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the examples, “parts” means “parts by weight” unless otherwise specified.

  In a 3 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirrer, 1474 parts (11 moles) of dipropylene glycol, 498 parts (3 moles) of isophthalic acid, 392 parts (4 moles) of maleic anhydride ), Tetrahydrophthalic anhydride (456 parts, 3 moles) and hydroquinone (0.22 parts) were added and heat condensed at 210 ° C. for 10 hours to synthesize an unsaturated polyester (A-1) having an acid value of 21.5.

  100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (C), ( D) 60 parts of methacrylate n-lauryl (Kyoeisha Chemical Co., Ltd. light ester L) as component (E) 3-methacryloxypropyltrimethoxysilane (KBE-503, Shin-Etsu Chemical Co., Ltd.) 5 parts and 120 parts of silicon dioxide having an average particle diameter of 2 μm as component (F) and 4.5 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) The unsaturated polyester composition a-1 was obtained by blending.

  100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts trimethylolpropane diallyl ether (Daiso Co., Ltd., trade name Neoallyl T-20) as component, 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) as component (E) 3. 1.5 parts and 120 parts of silicon dioxide having an average particle size of 2 μm as component (F) and 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) 5 parts was blended to obtain an unsaturated polyester composition a-2.

  100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd. light ester L) as component, 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) 1.5 as component (E) As a component and (F) component, 300 parts of silicon dioxide having an average particle diameter of 2 μm and 4.5 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) Unsaturated polyester composition a-3 was obtained.

Comparative Example 1
100 parts of unsaturated polyester (A-1), 40 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (C), (D ) 60 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd. light ester L) as component, 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) 1.5 as component (E) And 120 parts of silicon dioxide having an average particle diameter of 2 μm and 3.3 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) Unsaturated polyester composition a-4 was obtained.

Comparative Example 2
100 parts of unsaturated polyester (A-1), 450 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd., trade name Nikanol LL) as component (D), (D ) As a component, 60 parts of n-lauryl methacrylate (Light Ester L, manufactured by Kyoeisha Chemical Co., Ltd.), and 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) as a component (E) 5 parts and (F) component are 9.5 parts of silicon dioxide having an average particle diameter of 2 μm and 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.). An unsaturated polyester composition a-5 was obtained.

Comparative Example 3
100 parts of unsaturated polyester (A-1), 450 parts of 2-hydroxyethyl methacrylate as component (B), 60 parts of n-lauryl methacrylate (light ester L manufactured by Kyoeisha Chemical Co., Ltd.) as component (D), As component (E), 1.5 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and as component (F) 120 parts of silicon dioxide having an average particle diameter of 2 μm and 1,1-di 4.2 parts of (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) was blended to obtain unsaturated polyester composition a-6.

Comparative Example 4
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (C), (E ) 1.5 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) as component and 80 parts of silicon dioxide having an average particle size of 2 μm as component (F) and 1,1-di (tarsha) 3.6 parts of (Libutyl Peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) was blended to obtain an unsaturated polyester composition a-7.

Comparative Example 5
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) As a component, 120 parts of n-lauryl methacrylate (light ester L manufactured by Kyoeisha Chemical Co., Ltd.), and 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 1.5 as component (E) 1.5 120 parts of silicon dioxide having an average particle diameter of 2 μm and 5.4 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) Unsaturated polyester composition a-8 was obtained.

Comparative Example 6
100 parts of unsaturated polyester (A-1), 120 parts of styrene monomer instead of 2-hydroxyethyl methacrylate as component (B), xylene / formaldehyde resin as component (C) (trade name Nikanol LL, Fudou Co., Ltd.) 20 parts, (D) component n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd. light ester L) 120 parts, (E) component as 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. KBM- 503) 1.5 parts and 120 parts of silicon dioxide having an average particle diameter of 2 μm as component (F) and 1,1-di (tertiarybutylperoxy) cyclohexane (product name: Trigonox 22E-70, manufactured by Kayaku Akzo) .5 parts was blended to obtain unsaturated polyester composition a-9.

Comparative Example 7
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd. light ester L) as component, 120 parts of silicon dioxide having an average particle size of 2 μm as component (F), and 1,1-di (tertiary butyl peroxy) cyclohexane (Chemicals Akzo Co., Ltd. product name Trigonox 22-70E) was blended in an amount of 4.5 parts to obtain an unsaturated polyester composition a-10.

Comparative Example 8
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of trimethylolpropane diallyl ether (trade name Neoallyl T-20, manufactured by Daiso Co., Ltd.) as component, and 120 parts of silicon dioxide having an average particle diameter of 2 μm as component (F) and 1,1-di (tertiary butyl par) 4.5 parts of oxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) was blended to obtain unsaturated polyester composition a-11.

Comparative Example 9
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of n-lauryl methacrylate (light ester L manufactured by Kyoeisha Chemical Co., Ltd.) as component, and 65 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) as component (E) In addition, 120 parts of silicon dioxide having an average particle diameter of 2 μm and 5.5 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) are blended as component (F). Unsaturated polyester composition a-12 was obtained.

Comparative Example 10
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) Component as trimethylolpropane diallyl ether (Daiso Co., Ltd., trade name Neoallyl T-20), component (E) as 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) 65 parts In addition, 120 parts of silicon dioxide having an average particle diameter of 2 μm and 5.5 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) are blended as component (F). Unsaturated polyester composition a-13 was obtained.

Comparative Example 11
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of n-lauryl methacrylate (Light Ester L manufactured by Kyoeisha Chemical Co., Ltd.) as the component and 90 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) as the component and 5.9 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) was blended to obtain an unsaturated polyester composition a-14.

Comparative Example 12
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd. light ester L) as component, 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) 1.5 as component (E) Part and (F) component are 30 parts of silicon dioxide having an average particle size of 2 μm and 4.5 parts of 1,1-di (tertiarybutylperoxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) The unsaturated polyester composition a-15 was obtained by blending.

Comparative Example 13
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), 20 parts of xylene / formaldehyde resin (Fudo Co., Ltd. trade name Nikanol LL) as component (D), (D ) 60 parts of n-lauryl methacrylate (Kyoeisha Chemical Co., Ltd. light ester L) as component, 3-methacryloxypropyltrimethoxysilane (KBM-503, Shin-Etsu Chemical Co., Ltd.) 1.5 as component (E) As a component and (F) component, 350 parts of silicon dioxide having an average particle diameter of 2 μm and 4.5 parts of 1,1-di (tertiary butyl peroxy) cyclohexane (product name: Trigonox 22-70E, Kayaku Akzo Co., Ltd.) Then, an unsaturated polyester composition a-16 was obtained.

Test Example For the resin compositions of Examples and Comparative Examples, viscosity measurement, gelation time measurement, odor test, volatilization measurement, surface drying property, hardness of cured product, and adhesion strength test were performed as follows. The test results are shown in Table 2 and Table 3 together with the formulation.

  Viscosity measurement: Measured by Brookfield viscometer method according to JIS C 2105.

  Gelation time measurement: Gelation time was measured by a test tube method in accordance with JIS C 2105.

  Odor test: 100 g each of the resin compositions of Examples and Comparative Examples were placed in a plastic beaker having a diameter of 70 mm and a height of 140 mm, capped, and the odor after being left for 1 hour in a thermostatic bath at 25 ° C. was evaluated by a sensory test. did. The sensory test for odor was performed in a four-step evaluation using the evaluation criteria shown in Table 1.

  Measurement of volatilization amount: Each 10 g of the resin compositions of Examples and Comparative Examples were placed in a metal petri dish of φ = 60 mm, and left in a constant temperature bath at 120 ° C. for 2 hours, and the volatilization amount was measured by weight change.

Surface drying property: In accordance with JIS C 2105, it was applied to a 50 mm × 180 mm tin plate, and left in a constant temperature bath at 120 ° C. to measure the time when there was no stickiness on the surface.
Hardness of cured product: 20 g of the resin composition is placed in a metal petri dish having a diameter of 60 mm and heated at 130 ° C. for 1.5 hours to prepare a cured product. This cured product was kept at 23 ° C. and measured using a Shore D hardness meter.

Adhesive strength: In accordance with JIS C 2105, a PEW wire with a diameter of 2 mm made by Hitachi Magnet Wire was used to prepare a tester test piece. This was impregnated with a resin composition and cured at 130 ° C. for 1.5 hours to prepare a test piece. Using this test piece, the distance between fulcrums was 80 mm, and a load was applied to the center of the test piece at a speed of 5 mm / min using an autograph made by Shimadzu Corporation. The load at which the test piece breaks was defined as the fixing force.

  Thermal conductivity: A resin composition for electrical insulation is poured into a disk-shaped mold having a diameter of 50 mm and a depth of 10 mm, and cured at a temperature of 130 ° C. for 1.5 hours to prepare a test piece, and the thermal conductivity is measured. It measured using the apparatus (The Dynatec Co., Ltd. make, Cimatec (brand name)).

Claims (8)

  An unsaturated polyester (A) using an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components, and a reaction having an unsaturated group with a vapor pressure at 20 ° C. of 0.1 mmHg or less Diluent (B), alkylbenzene-formaldehyde resin (C), monofunctional (meth) acrylate whose main chain is aliphatic and / or an aliphatic main chain having one hydroxyl group in the molecule and allyl at the end of the molecule A resin composition for electrical insulation comprising a compound (D) having a group, a silane coupling agent (E) containing 2 or 3 methyloxy groups, and an inorganic filler (F) as essential materials.   The resin composition for electrical insulation according to claim 1, wherein the unsaturated polyester (A) has a number average molecular weight in the range of 1,000 to 10,000.   The reactive diluent (B) having an unsaturated group whose vapor pressure at 20 ° C is 0.1 mmHg or less is contained in an amount of 50 to 400 parts by weight with respect to 100 parts by weight of the unsaturated polyester (A). The resin composition for electrical insulation according to any one of the above.   Alkylbenzene-formaldehyde resin (C) is 0 with respect to 100 parts by weight of the total amount of the reactive polyester having the unsaturated polyester (A) and the unsaturated group having an unsaturated group whose vapor pressure at 20 ° C. is 1 mmHg or less. The resin composition for electrical insulation according to claim 3, containing 1 to 20 parts by weight.   The main chain is an aliphatic monofunctional (A) component with respect to 100 parts by weight of the total amount of the reactive polyester having unsaturated polyester as the component (A) and the unsaturated group having a vapor pressure at 20 ° C. of the component (B) of 1 mmHg or less. The meta-acrylate and / or the main chain having one hydroxyl group in the molecule is aliphatic and contains 1 to 100 parts by weight of the compound (D) having an allyl group at the molecular end. The resin composition for electrical insulation according to any one of the above.   2 or 3 methyloxy groups are added to 100 parts by weight of the total amount of the reactive polyester having unsaturated polyesters of component (A) and unsaturated groups having a vapor pressure at 20 ° C. of 1 mmHg or less of component (B). The resin composition for electrical insulation in any one of Claims 3-5 formed by containing 0.01-20 weight part of silane coupling agents (E) to contain.   As inorganic filler (F), silicon dioxide having an average particle size of 0.5 to 5 μm is reacted with unsaturated polyester (A) and unsaturated group (B) having an unsaturated group whose vapor pressure at 20 ° C. is 1 mmHg or less. The resin composition for electrical insulation according to any one of claims 3 to 6, comprising 20 to 100 parts by weight with respect to 100 parts by weight of the total amount of the functional diluent.   An electrical apparatus is covered with the resin composition for electrical insulation obtained by further containing a polymerization initiator in the resin composition for electrical insulation according to any one of claims 1 to 7, and is cured. Manufacturing method of electrical equipment insulation.