JP2016017082A - Unsaturated polyester resin composition, resin composition for electrical insulation using the same, and method for manufacturing electrical equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which provides a good work environment and in which a volatilization quantity is reduced, for a purpose of providing an impregnation varnish for electrical equipment with good work environment, and further to provide the unsaturated polyester resin composition with reduced odor.SOLUTION: The unsaturated polyester resin composition contains, as essential materials, an unsaturated polyester (A), a reactive diluent (B), a non-silicon surface control agent (C), and an organic peroxide (D) which initiates a curing reaction at less than 80°C. The reactive diluent (B) is preferably a reactive diluent having a vapor pressure of 0.1 mmHg or less at 20°C and having an unsaturated group.SELECTED DRAWING: None

Description

  The present invention relates to an unsaturated polyester resin composition, a resin composition for electrical insulation using the same, and a method for producing an electrical device.

  More specifically, in the molding of generators, induction coils and other motors, transformers, armatures (rotors), coils for electrical equipment such as stators (stators), and insulation treatments such as casting. The present invention relates to an unsaturated polyester resin composition that improves the working environment while improving the fixing force and improves the working environment, an electrical insulating resin composition using the same, and a method for manufacturing an electrical device.

  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. For example, because of its irritation characteristics such as styrene, it has a large effect on the handling operator despite a small amount of scattering, and has a problem that the working environment is deteriorated. 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 varnish include a reduction in the amount of solvent volatilization from the varnish (no solvent) and an improvement in adhesion.

  As a method corresponding to such a demand, a method of reducing the content of styrene which is a reactive diluent or a method of reducing a styrene volatilization amount by adding an additive is adopted. 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. However, these methods narrow the choice of reactive diluents that can be used, and the degree of improvement is limited.

  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. However, these methods also narrow the choice of materials that can be used, and the degree of improvement is limited.

  In addition, for high sticking property, epoxy resin is epoxidized as a condensate of phenols dimethylol and naphthols and bisphenol F type epoxy resin is 50 to 95:50 to 5 (weight ratio). ), An epoxy resin mixture containing the epoxy resin mixture, a curing agent and a curing accelerator, and a method of using the cured product, an epoxy resin, a mixture of nitrile rubber, a curing agent, an imidazole compound, A method using a thermosetting fixing agent comprising one or more curing accelerators selected from borofluoride and octylate, an epoxy resin, an acid anhydride, and an ammonium salt containing an ammonium salt Various methods such as a method using a resin composition and a method using a silicon-based surface conditioner containing siloxane have been reported. Among these, in the method using a silicon-based surface conditioner containing siloxane, there is a problem that the life of the drying equipment is shortened due to the silica component generated during curing.

  In recent years, electrical equipment has become smaller, lighter, higher in output, and more efficient, so the heat storage temperature has become higher. In particular, transformers and reactor coils used in electrical equipment such as microwave ovens and inverter air conditioners Because the heat generated by an excessive load during operation tends to be stored without being dissipated and the temperature of the electrical equipment rises, each material used is required to have higher heat resistance and adhesion. It has become.

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 firstly provides an unsaturated polyester resin composition with a small amount of volatilization, and secondly provides an unsaturated polyester resin composition with reduced odor. Thirdly, the present invention provides an unsaturated polyester resin composition having improved adhesion and the like, and further, a resin composition for electrical insulation and electrical equipment insulation using such an unsaturated polyester resin composition. The manufacturing method of a thing is provided.

The present invention relates to the following.
1. An unsaturated polyester (A), a reactive diluent (B), a non-silicone surface conditioner (C), and an organic peroxide (D) that initiates a curing reaction at less than 80 ° C. as essential materials. Saturated polyester resin composition.
2. The unsaturated polyester resin composition according to Item 1, wherein the acid value of the unsaturated polyester (A) is 15 or less.
3. Item 3. The unsaturated polyester resin according to Item 1 or 2, wherein the reactive diluent (B) is a reactive diluent having an unsaturated group and a vapor pressure at 20 ° C of 0.1 mmHg or less. Composition.
4). Item 4. The unsaturated polyester resin composition according to any one of Items 1 to 3, comprising 25 to 400 parts by weight of the reactive diluent (B) with respect to 100 parts by weight of the unsaturated polyester (A).
5). Item 5. The unsaturated polyester resin composition according to any one of Items 1 to 4, wherein the non-silicone surface conditioner (C) is a vinyl surface conditioner or an acrylic surface conditioner.
6). Item 1 in which the non-silicon-based surface conditioner (C) contains 0.001 to 10.0 parts by weight with respect to 100 parts by weight of the total amount of the unsaturated polyester (A) and the reactive diluent (B). The unsaturated polyester resin composition according to any one of 5.
7). 0.1 to 5 parts by weight of organic peroxide (D) that initiates the curing reaction at less than 80 ° C. with respect to 100 parts by weight of the total amount of unsaturated polyester (A) and reactive diluent (B). The unsaturated polyester resin composition in any one of claim | item 1 -6.
8). Item 8. A resin composition for electrical insulation comprising the unsaturated polyester resin composition according to any one of Items 1 to 7.
9. A method for producing an electrical equipment insulator, which is coated with the resin composition for electrical insulation according to Item 8 and cured.

  The unsaturated polyester resin composition according to the present invention is a solventless resin composition having a reduced volatilization amount. This effect can not only reduce the odor by the amount of volatilization, but also better reduce the odor by selecting the reactive diluent to be used. In particular, by using a reactive diluent having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less as the reactive diluent (B), it is effective in reducing the volatile amount and odor. Furthermore, since the effect is large and the odor is small, a better working environment can be provided.

In addition, the use of non-silicon-based surface conditioner (C) can improve the adhesive strength, and multiple varnish treatments are used to maintain the adhesive strength with large-diameter wires that were previously used in large equipment. Can be processed at a time, and the varnish treatment time is shortened, which reduces the amount of volatilization and reduces odor. In addition, the effect is large and the odor is low, providing a better working environment. it can.

  In addition, the use of organic peroxides (D) improves curability, especially because it can be cured even at relatively low temperatures, so it can be applied to the work of large equipment where drying equipment cannot be used. Based on the properties, it contributes to the reduction of volatilization amount, and hence the odor.

  In addition, the unsaturated polyester resin composition according to the present invention can have a relatively low viscosity by appropriately selecting a reactive diluent, and thus can be widely applied to impregnation and casting work methods.

  Since it is as described above, the resin composition for electrical insulation according to the present invention also has the same effect, the method for manufacturing an electrical equipment insulator according to the present invention has good workability and can improve the fixing force, Furthermore, the problem of volatilization amount and odor can be solved.

Front view (A) and side view (B) of test piece used for measurement of shear adhesive force

  The unsaturated polyester (A) can be obtained by reacting an acid component having an α, β-unsaturated dibasic acid as an essential 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 α, β-unsaturated dibasic 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.

  Examples of the cycloaliphatic unsaturated polybasic acid and derivatives thereof include tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and the like. These may be used alone or in combination of two or more. good.

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

  The acid value of the unsaturated polyester (A) of the present invention is preferably 15 or less from the viewpoint of compatibility with the reactive diluent (B) having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less. 10 or less is more preferable. When the acid value of the unsaturated polyester (A) of the present invention exceeds 15, when mixed with the reactive diluent (B), a problem that the appearance of the solution becomes turbid with time tends to occur.

  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 that is an essential component and an alcohol having one or more hydroxyl groups, or other components that can be used as necessary are subjected to a condensation reaction, and condensation occurs during the reaction. The reaction proceeds while removing water out of the system. The total alcohol component is preferably used in the range of 1 to 2 equivalents, more preferably in the range of 1.05 to 1.7 equivalents with respect 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. The internal pressure of the reactor is preferably in the range of normal pressure to 0.1 MPa.

  As the reactive diluent (B) in the present invention, those known as reactive diluents for unsaturated polyester resins can be generally used, and in particular, unsaturated groups having a vapor pressure at 20 ° C. of 0.1 mmHg or less. The reactive diluent having the above is preferable for the purpose of obtaining a resin composition having low odor. As the reactive diluent having an unsaturated group having a vapor pressure at 20 ° C. of 0.1 mmHg or less, those capable of dissolving the unsaturated polyester (A) are preferably used.

  As the reactive diluent (B) having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less, a monofunctional (meth) acrylate compound whose main chain is a polymerizable aliphatic [monofunctional acrylate A compound or a monofunctional methacrylate compound is meant. And / or a compound having an aliphatic main chain having one hydroxyl group in the molecule and an allyl group at the molecular end.

As the monofunctional (meth) acrylate compound, 1,4-butanediol monomethacrylate, 1,6-hexanediol monomethacrylate, 1,9-nonanediol monomethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl Examples include methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, and 2-hydroxybutyl methacrylate. In addition, (meth) acrylate monomers having a long-chain alkyl group having 12 to 15 carbon atoms (for example, Kyoeisha's light ester L-7 (long-chain alkyl methacrylate), Nippon Oil &Fats' Bremer SLMA (C _12-13 methacrylate) , Bremer CMA (cetyl methacrylate) and the like can also be used. Among these, it is preferable to select and use in consideration of the odor of the monomer. 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. It can also be used in combination with more than one species.
Moreover, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenol ethylene oxide modified (meth) acrylate, etc. can be used as the monofunctional (meth) acrylate having an aliphatic main chain. In addition, (meth) acrylate having a hydroxyl group such as (poly) caprolactone monoethoxy (meth) acrylate such as Plaxel FA1, FA2D, FA3, FM1D, FM2D, FM3 (Daicel Chemical Industries) [caprolactone adduct of HEMA] is used. be able to. 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.

  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 may be used alone or in combination of two or more.

  It is preferable that the usage-amount of unsaturated polyester (A) and a reactive diluent (B) is 25-400 weight part with respect to 100 weight part of unsaturated polyester (A). When the amount is less than 30 parts by weight, the viscosity of the resulting resin composition tends to be too high, and the workability tends to decrease. When the amount exceeds 400 parts by weight, the varnish viscosity becomes too low, and the workability tends to decrease. is there. For example, if the varnish viscosity becomes too low, the resin deposits that have penetrated into the inside flow out during heat curing, and the characteristics may not be sufficiently exhibited.

  As a method for improving the fixing strength of the unsaturated polyester resin composition according to the present invention, a non-silicon-based surface conditioner (C) is blended.

  The non-silicon-based surface conditioner (C) can be selected from vinyl-based surface conditioners, acrylic-based surface conditioners, and fluorine-based surface conditioners. Moreover, this surface conditioner can be used individually or in combination of 2 or more types. For example, such commercially available surface conditioners include BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, BYK-382, BYK-392. , BYK-394, BYK-399, BYK-3440, BYK-UV3535 (above, manufactured by BIC Chemie Japan, trade name), OX-880EF, OX-881, OX-883, OX-70, OX-77EF, OX-710, 1970, P-410EF, 1970, 230, LF-1980, LF-1982, LF-1983, LF-1984, LF-1985, LHP-90, LHP-96 (manufactured by Enomoto Kasei Co., Ltd., Product name) Polyflow No. 3, Polyflow No. 7, Polyflow No. 50E, Polyflow No. 50EHF, Polyflow No. 54N, Polyflow No. 55, Polyflow No. 64, polyflow no. 75, Polyflow No. 77, Polyflow No. 85, Polyflow No. 85HF, Polyflow No. S, Polyflow No. 90, polyflow no. 90D-50, Polyflow No. 95, Polyflow No. 300, Polyflow No. 460, polyflow WS, polyflow WS-30, polyflow WS-314 (trade name, manufactured by Kyoeisha Chemical Co., Ltd.) and the like. These may be used alone or in combination of two or more.

  The amount of the non-silicon-based surface conditioning agent (C) used is preferably 0.001 to 10.0 parts by weight with respect to 100 parts by weight of the total amount of the unsaturated polyester (A) and the reactive diluent (B). It is more preferable to set it as 01-5.0 weight part, and it is further more preferable to set it as 0.05-3.0 weight part. If it is less than 0.001 part by weight, there is a problem that the obtained fixing force is lowered. Moreover, even if it adds exceeding 10 weight part, the malfunction that the adhering force does not improve and the adhering force with the hardened | cured material obtained on the contrary will generate | occur | produce.

  As a curing method for curing the unsaturated polyester resin composition according to the present invention, an organic peroxide (D) that starts a curing reaction at less than 80 ° C. is blended.

  Examples of the organic peroxide (D) that initiates the curing reaction at less than 80 ° C. include bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-methoxyethylperoxydicarbonate, di-3-methoxybutylperoxydi. Percarbonates such as carbonate, di-2-methylhexylperoxydicarbonate, di-isopropylperoxydicarbonate; 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumeneperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxydi-2-ethylhexa Noate, t-hexyl peroxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxysobutyrate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, t -Alkyl peroxides such as amylperoxy 2-ethylhexanoate; organic peroxides such as diacyl peroxides such as isobutyroyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide . These organic peroxides may be used alone or in combination of two or more.

  The amount of the organic peroxide (D) that starts the curing reaction at less than 80 ° C. is 0.1 to 5 parts by weight relative to 100 parts by weight of the total amount of the unsaturated polyester (A) and the reactive diluent (B). Is preferably 0.2 to 3 parts by weight, and more preferably 0.5 to 2 parts by weight. If it is less than 0.1 part by weight, curing is slow and curability is impaired. Moreover, even if it adds exceeding 5 weight part, sclerosis | hardenability will not accelerate | stimulate and the malfunction that the adhering force with the hardened | cured part obtained will generate | occur | produce.

  You may mix | blend the stabilizer used as needed with the unsaturated polyester resin composition which concerns on this invention. Stabilizers include p-benzoquinone, hydroquinone, naphthoquinone, p-toluquinone, 2,5-diphenyl-p-benzoquinone, 2,5-diacetoxy-p-benzoquinone, p-tert-butylcatechol, 2,5-di-tert. -Butylhydroquinone, di-tert-butyl-p-cresol, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol and the like. When the stabilizer is blended, the blending amount is conveniently determined by the storage stability of the unsaturated polyester resin composition, the curing temperature and the curing time during the actual machine treatment, and the reactive polyester and reactive dilution. 0.5 parts by weight or less is preferable with respect to 100 parts by weight of the total amount of the agent (B), more preferably 0.01 to 0.1 parts by weight.

  The unsaturated polyester resin composition according to the present invention is useful as a resin composition for electrical insulation, but has low odor and good workability as well as good curability and improved adhesion. Therefore, it is particularly suitable as an electrical insulating material for impregnation treatment of electrical equipment represented by a transformer, a motor and the like.

  The unsaturated polyester resin composition according to the present invention is also suitable for casting.

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

(1) Synthesis of unsaturated polyester (A) 1107 parts of isophthalic acid and 760 parts of propylene glycol were charged into a 3 liter flask equipped with a thermometer, a nitrogen blowing tube, a rectifying column and a stirrer. In the air stream, it heated with the mantle heater, and heated up to 230 degreeC over 8 hours. Thereafter, the mixture was kept warm, cooled when the acid value reached 2.4, 19600 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 6 hours. When the acid value reached 12.9 mgKOH / g, the reaction was terminated by cooling. The number average molecular weight at this time was 2780.

(2) Preparation of unsaturated polyester resin composition (a-1) After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) and thoroughly mixing and confirming the appearance. Then, 0.5 parts of Polyflow WS (manufactured by Kyoeisha Chemical Co., Ltd.) is used as the component (C), 1 part of t-butylperoxybenzoate is used as the component (D), and 0.05 part of hydroquinone is used as the other material. Mixing was performed to obtain an unsaturated polyester resin composition a-1.

(Preparation of unsaturated polyester resin composition (a-2))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1, and thoroughly mixing and confirming the appearance, BYK- 350 (by Big Chemie Japan Co., Ltd.) 0.5 part (D) component, 1 part t-butylperoxybenzoate, and 0.05 parts hydroquinone as other materials, mixed well, unsaturated polyester resin composition a-2 was obtained.

(Preparation of unsaturated polyester resin composition (a-3))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) (Kyoeisha Chemical Co., Ltd.) 5 parts (D) As a component, 1 part of t-butyl peroxybenzoate, and 0.05 parts of hydroquinone as other materials are mixed and mixed well, and unsaturated polyester resin composition a-3 is obtained. Obtained.

(Preparation of unsaturated polyester resin composition (a-4))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) (Manufactured by Kyoeisha Chemical Co., Ltd.) 10 parts (D) As a component, 1 part of t-butyl peroxybenzoate, and 0.05 parts of hydroquinone as other materials are blended and mixed well, and unsaturated polyester resin composition a-4 is obtained. Obtained.

(Preparation of unsaturated polyester resin composition (a-5))
After adding 20 parts of 2-hydroxyethyl methacrylate as the component (B) to 80 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as the component (C) (Kyoeisha Chemical Co., Ltd.) 0.5 part (D) As component (1 part) t-butyl peroxybenzoate, as other materials, 0.05 part hydroquinone is blended and mixed well, unsaturated polyester resin composition a- 5 was obtained.

(Preparation of unsaturated polyester resin composition (a-6))
After adding 80 parts of 2-hydroxyethyl methacrylate as a component (B) to 20 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) (Kyoeisha Chemical Co., Ltd.) 0.5 part (D) As component (1 part) t-butyl peroxybenzoate, as other materials, 0.05 part hydroquinone is blended and mixed well, unsaturated polyester resin composition a- 6 was obtained.

(Preparation of unsaturated polyester resin composition (a-7))
After adding 80 parts of 2-hydroxyethyl methacrylate as a component (B) to 20 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) (Made by Kyoeisha Chemical Co., Ltd.) 0.5 part (D) As a component, 5 parts of t-butyl peroxybenzoate and 0.05 parts of hydroquinone as other materials are blended and mixed well, and the unsaturated polyester resin composition a- 7 was obtained.

(Preparation of unsaturated polyester resin composition (a-8))
After adding 50 parts of styrene as the component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1 and thoroughly mixing and confirming the appearance, Polyflow WS (Kyoeisha Chemical Co., Ltd.) is used as the component (C). 0.5 part (D) component, 1 part t-butyl peroxybenzoate as component, and 0.05 parts hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-8. .

(Preparation of unsaturated polyester resin composition (a-9))
After adding 15 parts of 2-hydroxyethyl methacrylate as the component (B) to 85 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as the component (C) (Kyoeisha Chemical Co., Ltd.) 0.5 part (D) As component (1 part) t-butyl peroxybenzoate, as other materials, 0.05 part hydroquinone is blended and mixed well, unsaturated polyester resin composition a- 9 was obtained.

(Preparation of unsaturated polyester resin composition (a-10))
After adding 85 parts of 2-hydroxyethyl methacrylate as the component (B) to 15 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as the component (C) (Kyoeisha Chemical Co., Ltd.) 0.5 part (D) As component (1 part) t-butyl peroxybenzoate, as other materials, 0.05 part hydroquinone is blended and mixed well, unsaturated polyester resin composition a- 10 was obtained.

[Comparative Example 1]
(Preparation of unsaturated polyester resin composition (a-11))
After adding 85 parts of 2-hydroxyethyl methacrylate as a component (B) to 15 parts of the unsaturated polyester (A) obtained in Example 1, and thoroughly mixing and confirming the appearance, t- 1 part of butyl peroxybenzoate and 0.05 part of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-11.

(Preparation of unsaturated polyester resin composition (a-12))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) (Manufactured by Kyoeisha Chemical Co., Ltd.) 15 parts as component (D), 1 part of t-butyl peroxybenzoate, and 0.05 parts of hydroquinone as other materials are mixed and mixed well to obtain unsaturated polyester resin composition a-12. Obtained.

[Comparative Example 2]
(Preparation of unsaturated polyester resin composition (a-13))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) 0.5 parts (manufactured by Kyoeisha Chemical Co., Ltd.) and 0.05 parts of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-13.

(Preparation of unsaturated polyester resin composition (a-14))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1 and mixing well, after confirming the appearance, Polyflow WS as a component (C) (Manufactured by Kyoeisha Chemical Co., Ltd.) 15 parts as component (D) 10 parts of t-butylperoxybenzoate and 0.05 parts of hydroquinone as other materials are mixed well and mixed to obtain unsaturated polyester resin composition a-14. Obtained.

  About the resin composition of an above-described Example and a comparative example, the viscosity measurement, the gelation time measurement, the odor test, the volatilization amount measurement, the surface drying property, the hardness of the cured product, and the adhesion strength test were carried out as follows.

(1) Appearance measurement The appearance of the varnish when the unsaturated polyester (A) and the reactive diluent (B) were mixed was measured visually according to JIS C 2105.

(2) Viscosity measurement:
Based on JIS C 2105, it was measured by the Brookfield viscometer method.

(3) Gelation time measurement:
In accordance with JIS C 2105, gelation time was measured by a test tube method.

(4) Odor test 100 g of each of the resin compositions of Examples and Comparative Examples is placed in a polyvinyl beaker with 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 by a sensory test. evaluated. The sensory test for odor was performed in a four-step evaluation using the evaluation criteria shown in Table 1.

(5) Measurement of volatilization amount:
10 g of each of the resin compositions of Examples and Comparative Examples was 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.

(6) Shear adhesive strength:
As shown in FIGS. 1 (A) and 1 (B), a tester was prepared by preparing a tester test piece according to JIS C 2105, impregnating it with a resin composition for electrical insulation, and curing it under predetermined conditions. The shear adhesive strength at 23 ° C. was measured. In the figure, 1 denotes a polyester enameled copper wire having a diameter of 2.0 mm, and 2 denotes a polyester enameled copper wire having a diameter of 0.4 mm.

  The obtained results are shown in Tables 2 and 3.

  From the results of Tables 2 and 3, the resin composition for insulating electrical equipment according to the present invention has a good adhesion. Further, when a reactive diluent is selected, a good working environment can be provided because there is little odor, and it can be adapted to work on large equipment. Further, since the viscosity of the resin composition can be equal to that of the conventional product, in this case, it can be widely applied to the impregnation method. Furthermore, since the cured product characteristics such as electrical insulation and adhesion that are equal to or better than those of conventional liquid type resin compositions are possible and exhibit good stability, a highly reliable electrical device can be provided.

1 Polyester enameled copper wire with a diameter of 2.0 mm 2 Polyester enameled copper wire with a diameter of 0.4 mm

Claims (9)

An unsaturated polyester (A), a reactive diluent (B), a non-silicone surface conditioner (C), and an organic peroxide (D) that initiates a curing reaction at less than 80 ° C. as essential materials. Saturated polyester resin composition. The unsaturated polyester resin composition according to claim 1, wherein the acid value of the unsaturated polyester (A) is 15 or less. 3. The unsaturated polyester according to claim 1, wherein the reactive diluent (B) is a reactive diluent having a vapor pressure at 20 ° C. of 0.1 mmHg or less and having an unsaturated group. Resin composition. The unsaturated polyester resin composition according to any one of claims 1 to 3, comprising 25 to 400 parts by weight of the reactive diluent (B) with respect to 100 parts by weight of the unsaturated polyester (A). The unsaturated polyester resin composition according to any one of claims 1 to 4, wherein the non-silicon-based surface conditioner (C) is vinyl or acrylic. The non-silicon-based surface conditioner (C) is contained in an amount of 0.001 to 10.0 parts by weight with respect to 100 parts by weight of the total amount of unsaturated polyester (A) and reactive diluent (B). The unsaturated polyester resin composition in any one of -5. 0.1 to 5 parts by weight of organic peroxide (D) that initiates the curing reaction at less than 80 ° C. with respect to 100 parts by weight of the total amount of unsaturated polyester (A) and reactive diluent (B). The unsaturated polyester resin composition in any one of Claims 1-6. The resin composition for electrical insulation formed by containing the unsaturated polyester resin composition in any one of Claims 1-7. A method for producing an electrical equipment insulator, wherein the electrical insulation resin composition according to claim 8 is coated and cured.

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