JP2009295379A - Method of manufacturing resin composition for electric insulation and electric equipment insulator using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for electric insulation in which working environment is superior, softening of a varnish film can be made, and superior electric insulation characteristics, curing characteristics, and stability which are equal to or more than those of a liquid type resin composition in the prior art, and to provide a method of manufacturing electric equipment. <P>SOLUTION: The resin composition for electric insulation is provided which is composed of indispensable materials such as unsaturated polyester resin using alcohol having α, β-unsaturated dibasic acid and one or more of hydroxy groups as indispensable component (A), a reactive diluent having unsaturated group of a vapor pressure of ≤0.1 mmHg at 20°C (B), an alkylbenzene-formaldehyde resin (C), and a compound in which a main chain having one hydroxy group in the molecule and is aliphatic monofunctional (meth)acrylate and/or in which the main chain having one hydroxy group in the molecule and is aliphatic and having one allyl group at the molecule end (D). The method of manufacturing an electric equipment insulated material is provided in which the electric equipment is covered with the resin composition for electric insulation and curing is made. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a resin composition for electrical insulation and a method for producing an electrical equipment insulator using the same, and more specifically, electric such as a motor, a transformer, an armature (rotor), and a stator (stator). Resin composition for electrical equipment insulation treatment, which has a flexible cured film without lowering the impregnation property of equipment coils, can be cured in a short time, has less odor during work, and has a good work environment. The present invention relates to a method of manufacturing an electrical equipment insulator using a ceramic.

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 solventless varnish, and is appropriately selected depending on the type of equipment, the 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 does not scatter as in the solvent-type varnish during the heat curing treatment. Due to the stimulation characteristics, the influence on the handling operator is great despite the small amount of scattering, and there is a problem that the working environment deteriorates. Thus, regarding the worker and the work environment problem, any varnish has not been solved at all. 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 of the solventless varnishes 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 and reduction of solvent volatilization from the varnish (solvent free).
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, as an essential component, an oligoethylene glycol alkyl ether methacrylate such as diethylene glycol monomethyl ether methacrylate as a polymerizable unsaturated monomer as described in Japanese Patent Application Laid-Open Nos. 07-2116040 and 09-151225 And a resin composition using a monomer containing an oligoether monoalkyl ether methacrylate such as dipropylene glycol monoethyl ether methacrylate as an essential component, polymerizable unsaturated as described in JP-A-10-87770 Resin composition using oligoethylene glycol di (meth) acrylate and / or oligopropylene glycol di (meth) acrylate as an essential component as a monomer, As described in 2-114829, JP-alkyl cyclohexyl (meth) acrylate is a resin composition containing as essential components a polymerizable unsaturated monomer.
Also, for example, as described in JP-A-10-36461, a macromonomer having a polymerizable unsaturated bond group and an oligoether monoalkyl ether (meth) of a diol having 2 to 4 carbon atoms as the polymerizable unsaturated monomer A resin composition containing an acrylate, a resin having at least two (meth) acryloyl groups at a molecular end, a monomer having a (meth) acrylate group, and acetyl as described in JP-A-2003-268054 A resin composition containing a lactone compound, a dicyclopentadiene-modified unsaturated polyester oligomer as disclosed in JP-A-2003-89709, an ester compound having a cyclohexene ring and an allyl ether group, and a hydroxyalkyl methacrylate are essential components. Unsaturated polyester resin composition, etc. People have been reported.

JP 07-2104040 A JP 09-151225 A 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

  In view of such problems, the present invention can provide a resin composition for electrical insulation and a method for producing an electrical device using the same for the purpose of providing an impregnated varnish for an electrical device having a favorable working environment. The present invention also provides a resin composition for electrical insulation that can exhibit cured product characteristics such as good electrical insulation and good stability equivalent to or better than those of conventional liquid type resin compositions. The present invention provides a method for producing an electrical device using the resin composition for electrical insulation.

The present invention relates to [1] an unsaturated polyester (A) using an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components, a vapor pressure at 20 ° C. of 0.1 mmHg. A reactive diluent (B) having an unsaturated group, an alkylbenzene / formaldehyde resin (C), an aliphatic monofunctional (meth) acrylate having one hydroxyl group in the molecule, and / or The present invention relates to a resin tree composition for electrical insulation comprising a compound (D) having an aliphatic main chain having one hydroxyl group in the molecule and an allyl group at the molecular end as an essential material.
Moreover, this invention relates to the resin tree composition for electrical insulation as described in said [1] whose number average molecular weights of [2] unsaturated polyester (A) are the range of 1000-10000.
The present invention also provides [3] a reactive diluent (B) having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less, based on 100 parts by weight of the unsaturated polyester (A), 50 to 400. It is related with the resin composition for electrical insulation as described in said [1] or said [2] containing a weight part.
The present invention also provides [4] any one of [1] to [3] above, wherein 0.1 to 20 parts by weight of alkylbenzene / formaldehyde resin (C) is contained per 100 parts by weight of the resin composition for electrical insulation. It relates to the resin composition for electrical insulation described in 1.
The present invention also relates to [5] 100 parts by weight of an electrically insulating resin composition, wherein the main chain having one hydroxyl group in the molecule is an aliphatic monofunctional (meth) acrylate and / or in the molecule. The electrical insulation according to any one of [1] to [4] above, wherein the main chain having one hydroxyl group is aliphatic and contains 1 to 100 parts by weight of the compound (D) having an allyl group at the molecular end. The present invention relates to a resin composition.
The present invention also relates to [6] an electrically insulating resin composition comprising the resin composition according to any one of [1] to [5] above and further containing a polymerization initiator and a stabilizer.
Furthermore, the present invention provides [7] electrical equipment insulation, wherein the electrical equipment is coated with the resin composition for electrical insulation according to any one of [1] to [6] and cured. Regarding the method.

  The resin composition for electrical insulation of the present invention can provide an impregnated varnish for electrical equipment with a good working environment, and has excellent flexibility of the varnish cured product. Can be provided. 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) which uses an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components used in the present invention requires an α, β-unsaturated dibasic acid. It can be obtained by reacting an acid component as a component, an alcohol component having one or more hydroxyl groups, and, if necessary, a modifying component.
As the α, β-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 a diester of this saturated acid lower alkyl can be used in combination.
For example, terephthalic acid diesters such as monomethyl terephthalate and lower alkyl diesters of terephthalic acid such as dimethyl terephthalate are used. Further, isophthalic acid, adipic acid, phthalic acid, sebacic acid and the like can also be used.
Saturated acids include saturated dibasic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, tetrahydrophthalic acid, hexahydrophthalic anhydride, hexahydrophthalic acid, adipic acid, and sebacic acid. Can be mentioned.
As a diester of a saturated acid lower alkyl, for example, dimethyl terephthalate is used. 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 the unsaturated acid is preferably selected in the range of 50 to 90 equivalent% in the total acid component.

  As the alcohol component having one or more hydroxyl groups, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol and the like are used. It may be used alone or in combination. Examples of the modifying component used as necessary include linseed oil, soybean oil, tall oil, dehydrated castor oil, coconut oil, dicyclopentadiene, and cyclopentadiene.

  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 preferably 1000 to 10,000. More preferably, it is 1500-5000. If it is less than 1000, the curability and resin cured product properties of the resin composition are extremely inferior, and if it exceeds 10,000, the viscosity is too high and impregnation workability deteriorates.

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 the 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 proceeds while removing the condensed water generated during the process. 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 out of the system is preferably carried out by natural distillation or reduced pressure distillation through 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 for carrying out the synthesis reaction 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 inside the reactor adjusted to carry out the polycondensation reaction in the synthesis can proceed without any problem even at normal pressure, but the reaction is accelerated by increasing the boiling point of the polyhydric alcohol by pressurization. be able to. In this case, it is preferable to carry out in the range of normal pressure to 0.1 MPa.

  As the reactive diluent (B) having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less used in the present invention, the vapor pressure is 0.1 mmHg for the purpose of obtaining a low-odor resin composition. (20 ° C.) or lower, and further unsaturated polyester resin (A), alkylbenzene / formaldehyde resin (C), and monofunctional (meth) acrylate having a main chain having one hydroxyl group in the molecule and an aliphatic group And / or a compound in which the main chain having one hydroxyl group in the molecule is aliphatic and the compound (D) having an allyl group at the molecular end is dissolved. Examples of the reactive diluent (B) that satisfies this requirement include polymerizable monofunctional (meth) acrylates. Specific examples thereof include dicyclopentenyloxyethyl (meth) acrylate and dicyclopentanyl (meta). ) Acrylate, phenol ethylene oxide modified (meth) acrylate, and the like. Moreover, it has a hydroxyl group such as (poly) caprolactone monoethoxy (meth) acrylate such as 2-hydroxyethyl methacrylate, Plaxel FA1, FA2D, FA3, FM1D, FM2D, FM3 (trade name, manufactured by Daicel Chemical Industries, Ltd.) ) Acrylate 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.

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 a saturated group is preferably in the range of 50 to 400 parts by weight. When the amount is less than 50 parts by weight, the viscosity of the resulting resin composition is too high and not only thickly adheres to the transformer surface, but also the internal permeability deteriorates.
Moreover, if a reactive diluent having an unsaturated group with a vapor pressure at 20 ° C. of 0.1 mmHg or less is added in an amount of 400 parts by weight or more, the appearance of the resin composition becomes cloudy and the varnish viscosity is too low, This causes a problem that the resin adhering material that has permeated the resin flows out during heat curing.

The component (C) 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 Generalite 30, Generalite 50, and Generalite 100 manufactured by General Petrochemical Co., Ltd., Nikanol L, Nikanol LL, and Nikanol LLL manufactured by Mitsubishi Gas Chemical Co., Ltd.
The amount of the alkylbenzene / formaldehyde resin used as the component (C) used in the present invention is the reactivity of the 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. With respect to 100 parts by weight of the diluent, the component (C), the component (D), the polymerization initiator, and the total amount of the stabilizer (resin composition for electrical insulation), 0.1 to 20 parts by weight of the alkylbenzene / formaldehyde resin (C) It is preferably 1 to 15 parts by weight, more preferably 5 to 10 parts by weight. If the alkylbenzene / formaldehyde resin (C) is added in an amount exceeding 20 parts by weight, the surface drying time and the curing time of the resin composition are extended, and it becomes difficult to cure. On the other hand, when the blending amount is less than 0.1 parts by weight, a problem that the cured film of the resin composition does not become flexible occurs.

  The main chain having one hydroxyl group in the molecule of component (D) used in the present invention is an aliphatic monofunctional (meth) acrylate, such as 1,4-butanediol monomethacrylate, 1,6-hexanediol. Monomethacrylate, 1,9-nonanediol monomethacrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, ( Examples include stearyl methacrylate. Also, a mixture of (meth) acrylate monomers having a long-chain alkyl group having 12 to 15 carbon atoms (for example, Kyoeisha Chemical Co., Ltd. Light Ester L-7, Light Ester L-8, Nippon Oil & Fats Co., Ltd. Bremer SLMA , Bremer CMA, etc.) can also be used. It is preferable to select and use the odor of the monomer among these. Preferably, long-chain alkyl alcohol monomethacrylates such as lauryl (meth) acrylate and a mixture of (meth) acrylate monomers having a long-chain alkyl group having 12 to 15 carbon atoms can be used, and these can be used alone or Two or more kinds can be used in combination.

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

The main chain having one hydroxyl group in the molecule is aliphatic monofunctional (meth) acrylate and / or the main chain having one hydroxyl group in the molecule is aliphatic and has an allyl group at the molecular end. The amount of the compound (D) used is a reactive diluent having an unsaturated group having an unsaturated polyester (A) component and a vapor pressure of 20 ° C. of the component (B) of 1 mmHg or less, an alkylbenzene-formaldehyde resin (C ) And (D) components, a polymerization initiator, and a total amount of the stabilizer (resin composition for electrical insulation) are preferably in the range of 1 to 100 parts by weight. If the amount is less than 1 part by weight, the viscosity of the resulting resin composition is too high, the resulting resin composition becomes cloudy and not only thickly adheres to the surface of the electrical equipment to be impregnated, but also the internal permeability deteriorates.
Moreover, when it exceeds 100 weight part, while the external appearance of a resin composition will become muddy, the varnish viscosity is too low and the malfunction which the resin deposit | penetration which penetrate | infiltrated the inside will flow out at the time of heat-curing will generate | occur | produce.

The resin composition for electrical insulation of the present invention preferably further contains a polymerization initiator and a stabilizer.
Examples of the polymerization initiator used in the present invention include ketone peroxides, peroxydicarbonates, hydroperoxides, diacyl peroxides, peroxyketals, dialkyl peroxides, peroxyesters, alkylperesters. And the like. The amount of the polymerization initiator is determined according to each of the curing conditions and the aspects such as the appearance and characteristics of the cured resin product. From the viewpoint of storage stability of the material and molding cycle, the content is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, based on the total amount of the unsaturated polyester resin (A) and (D) component.
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 depending on the storage stability of the resin composition, the curing temperature and the curing time during actual machine processing, and the blending amount is usually 0.00 with respect to 100 parts by weight of the total amount of the resin composition. The amount is preferably 5 parts by weight or less, more preferably 0.01 to 0.1 part by weight.

  In the present invention, a polymerization inhibitor can be used as necessary. As polymerization inhibitors, p-benzoquinone, hydroquinone, naphthoquinone, p-toluquinone, 2,5-diphenyl-p-benzoquinone, 2,5diacetoxy-p-benzoquinone, p-tert-butylcatechol, 2,5-di- Examples include tert-butyl hydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol. The blending amount is conveniently determined by the curability of the resulting resin composition, but the blending amount is preferably 0.01 to 5.0 parts by weight, more preferably 0 to 100 parts by weight of the resin composition. 0.5 to 3 parts by weight.

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 of this invention. By blending these additives, the surface curing (surface drying) time can be shortened. Examples of additives for shortening the surface curability include paraffin waxes having various melting points, and low volatility agents such as BYK-S740 and BYK-S750 (trade name, manufactured by BYK Chemie).
The blending amount of the wax is 0.05 to 1 part by weight, preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of the resin composition.

The insulation treatment of the electrical equipment using the resin composition of the present invention is performed by a known method, but after the electrical equipment is immersed in the resin composition of the present invention for 2 to 20 minutes, it is pulled up and 100 to 160 ° C. It is desirable to be carried out by a method of curing the resin composition by heating for 1 to 5 hours.
The resin composition of the present invention is suitable not only for low odor and good workability, but also for the impregnation treatment of electrical equipment represented by transformers and motors because the varnish film obtained has flexibility. It is. In particular, it is most suitable for the insulation treatment of electrical equipment such as high-frequency transformers and switching transformers using ferrite used at high voltages.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited to these. In the examples, “parts” means “parts by weight” unless otherwise specified.
(1) Synthesis of unsaturated polyester (A-1) In a 3 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirring device, 1474 parts (11 mol) of dipropylene glycol and 498 parts of isophthalic acid (3 moles), 392 parts (4 moles) of maleic anhydride, 456 parts (3 moles) of tetrahydrophthalic anhydride and 0.22 parts of hydroquinone, heat-condensed at 210 ° C. for 10 hours, and an acid value of 21.5 mgKOH / g The unsaturated polyester (A-1) was synthesized. The number average molecular weight of the obtained unsaturated polyester (A-1) was 2500.

(Example 1)
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), and xylene-formaldehyde resin (trade name Nicanol LL manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C) ) 20 parts, (D) component, lauryl (meth) acrylate (Kyoeisha Chemical Co., Ltd. light ester L) 60 parts and 1,1-di (tert-butyl peroxy) cyclohexane (Kayaku Akzo Corporation) Product, product name Trigonox 22E-70) was blended in an amount of 4.5 parts to obtain a resin tree composition a-1 for electrical insulation. In addition, the vapor pressure at 20 degrees C of 2-hydroxyethyl methacrylate of (B) component is 0.08 mmHg.

(Example 2)
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), and xylene-formaldehyde resin (trade name Nicanol LL manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C) ) 20 parts, as component (D), 60 parts of trimethylolpropane diallyl ether (manufactured by Daiso Corporation, trade name Neoallyl T-20) and 1,1-di (tert-butylperoxy) cyclohexane ( 4.5 parts of a product name Trigonox 22E-70) manufactured by Kayaku Akzo Corporation was blended to obtain a resin tree composition a-2 for electrical insulation.

(Comparative Example 1)
100 parts of unsaturated polyester (A-1), 40 parts of 2-hydroxyethyl methacrylate as component (B), and xylene-formaldehyde resin (trade name: Nicarol LL, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C) ) 20 parts, (D) component, lauryl (meth) acrylate (Kyoeisha Chemical Co., Ltd. light ester L) 60 parts and 1,1-di (tert-butyl peroxy) cyclohexane (Kayaku Akzo Corporation) Product, product name Trigonox 22E-70) was mixed with 3.3 parts to obtain a resin tree composition a-3 for electrical insulation.

(Comparative Example 2)
100 parts of unsaturated polyester (A-1), 450 parts of 2-hydroxyethyl methacrylate as component (B), and xylene / formaldehyde resin (trade name Nicanol LL manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C) ) 20 parts, (D) component, lauryl (meth) acrylate (Kyoeisha Chemical Co., Ltd. light ester L) 60 parts and 1,1-di (tert-butyl peroxy) cyclohexane (Kayaku Akzo Corporation) 9.5 parts of manufactured product Trigonox 22E-70) was blended to obtain resin tree composition a-4 for electrical insulation.

(Comparative Example 3)
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), and 60 parts of lauryl (meth) acrylate (light ester L manufactured by Kyoeisha Chemical Co., Ltd.) as component (D) And 4.2 parts of 1,1-di (tert-butyl peroxy) cyclohexane (product name: Trigonox 22E-70, manufactured by Kayaku Akzo Co., Ltd.), and resin tree composition for electrical insulation a-5 Obtained.

(Comparative Example 4)
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), and xylene-formaldehyde resin (trade name Nicanol LL manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C) ) 20 parts and 3.6 parts of 1,1-di (tert-butyl peroxy) cyclohexane (product name: Trigonox 22E-70, manufactured by Kayaku Akzo Co., Ltd.), and resin tree composition for electrical insulation a -6 was obtained.

(Comparative Example 5)
100 parts of unsaturated polyester (A-1), 120 parts of 2-hydroxyethyl methacrylate as component (B), and xylene-formaldehyde resin (trade name Nicanol LL manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C) ) 20 parts, as component (D), lauryl (meth) acrylate (Light Ester L, manufactured by Kyoeisha Chemical Co., Ltd.) 200 parts and 1,1-di (tert-butylperoxy) cyclohexane (Kayaku Akzo Corporation) 6.6 parts of product name product Trigonox 22E-70) was blended to obtain resin tree composition a-7 for electrical insulation.

(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 (product manufactured by Mitsubishi Gas Chemical Co., Ltd., product) as component (C) (Nicanol LL) 20 parts, (D) component, lauryl (meth) acrylate (Kyoeisha Chemical Co., Ltd. light ester L) 60 parts and 1,1-di (tert-butyl peroxy) cyclohexane ( 4.5 parts of product name Trigonox 22E-70) manufactured by Kayaku Akzo Corporation was blended to obtain a resin tree composition a-8 for electrical insulation.

About the resin composition for electrical insulation of an Example and a comparative example, the viscosity, varnish specific gravity, gelation time, odor, volatilization amount, surface drying property, and hardness of hardened | cured material were measured and tested as follows.
[1] Viscosity measurement: Measured by the Brookfield viscometer method according to JIS C 2105.
[2] Varnish specific gravity measurement: Measured by a buoyancy method according to JIS C 2105.
[3] Gelation time: Gelation time was measured by a test tube method in accordance with JIS C 2105.
[4] Odor test: 100 g of each of the resin compositions of Examples and Comparative Examples was placed in a polyvinyl beaker having a diameter of 70 mm and a height of 140 mm, covered, and the odor after being left in a thermostatic bath at 25 ° C. for 1 hour. The sensory test evaluated. The sensory test of odor was performed in a four-step evaluation using the evaluation criteria shown in Table 1.

[5] Measurement of volatilization amount: 10 g each of the resin compositions of Examples and Comparative Examples were placed in a metal petri dish with a diameter of 60 mm, and left in a constant temperature bath at 120 ° C. for 2 hours, and the volatilization amount was measured by weight change. .
[6] Surface drying property: Based on 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.
[7] Hardness of cured product: 20 g of the resin composition was 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. The cured product was kept at 23 ° C., and the hardness was measured using a Shore D hardness meter.
The obtained results are summarized and shown in Table 2 together with the composition ratio of the composition.

In Comparative Example 6, a styrene monomer is blended, but the odor is strong, the working environment is deteriorated, and the cured product is hardened. In contrast, by using 2-hydroxyethyl methacrylate having a vapor pressure at 20 ° C. of 0.1 mmHg or less as the component (B) as in Examples 1 and 2, the odor is greatly improved and the flexibility is improved. Excellent. In Comparative Example 1 in which the amount of the component (B) is relatively small, the varnish is turbid, the viscosity is high, and the impregnation property is poor. Conversely, Comparative Example 2 in which the amount of component (B) is too large is good with little odor, but the gelation time is long, the volatilization amount is large, and the surface drying time is long. In Comparative Example 3 not using the component (C), the varnish becomes turbid and the cured product becomes hard. Moreover, in the comparative example 4 which does not use the (D) component, the varnish is turbid, the viscosity is high, and in the comparative example 5 in which the (D) component is excessive, the surface drying time becomes long.
Since the resin composition for electrical insulation of the present invention is excellent in the flexibility of the varnish cured product, it can 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.

Claims (7)

an unsaturated polyester (A) using an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components, and an unsaturated group having a vapor pressure at 20 ° C. of 0.1 mmHg or less. Reactive diluent (B) having alkylbenzene / formaldehyde resin (C), monofunctional (meth) acrylate having a main chain having one hydroxyl group in the molecule and / or one hydroxyl group in the molecule A resin tree composition for electrical insulation comprising, as an essential material, a compound (D) having an aliphatic main chain and an allyl group at the molecular end. The resin tree composition for electrical insulation according to claim 1, wherein the unsaturated polyester (A) has a number average molecular weight in the range of 1000 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). Item 3. The resin composition for electrical insulation according to Item 2. The resin composition for electrical insulation according to any one of claims 1 to 3, comprising 0.1 to 20 parts by weight of an alkylbenzene / formaldehyde resin (C) with respect to 100 parts by weight of the resin composition for electrical insulation. For 100 parts by weight of the resin composition for electrical insulation, the main chain having one hydroxyl group in the molecule is an aliphatic monofunctional (meth) acrylate and / or the main chain having one hydroxyl group in the molecule. The resin composition for electrical insulation according to any one of claims 1 to 4, comprising 1 to 100 parts by weight of an aliphatic compound (D) having an allyl group at a molecular end. A resin composition for electrical insulation comprising the resin composition according to any one of claims 1 to 5 and further containing a polymerization initiator and a stabilizer. A method for producing an electrical equipment insulator, wherein the electrical equipment is coated with the resin composition for electrical insulation according to any one of claims 1 to 6 and cured.