JP2017203075A - Unsaturated polyester resin composition, rotor, resin composition for electric insulation, and method for manufacturing electric equipment insulator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which reduces a volatile substance and improves a working environment while improving a binding force in an operation in molding such as insulation processing such as impregnation and casting of electric equipment, particularly, a coil for electric equipment using an armature (rotor) of a power generator, an electric power tool and the like, and enables high life of a rotor because of having high binding force of a coating film and imparting flexibility; a rotor; a resin composition for electric insulation; and a method for manufacturing an electric equipment insulator.SOLUTION: An unsaturated polyester resin composition contains unsaturated polyester (A), a reactive diluent (B), an alkylbenzene-formaldehyde resin (C) and an organic peroxide (D) starting a curing reaction at lower than 80°C, as essential components.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an unsaturated polyester resin composition, a rotor, a resin composition for electrical insulation, and a method for producing an electrical equipment insulator.

  Furthermore, in particular, it improves the fixing force during work in molding such as impregnation of coils for electrical equipment that uses armatures (rotors) such as generators, electric tools, etc., and insulation treatment such as casting. While reducing the volatile substances, improving the working environment and providing flexibility with high adhesion of the coating film, the unsaturated polyester resin composition that provides a longer life of the rotor, the rotor, The present invention relates to a resin composition for electrical insulation and a method for producing an electrical equipment insulator.

  Conventionally, in order to fix an electric wire inserted in a rotor, varnish is generally applied. The main purpose of applying the varnish is to suppress vibrations and beats by moving the electric wires inside and outside due to centrifugal force and heat generated by the core when the motor rotates, and to cause damage to the insulation film caused by rubbing the wires. It is to prevent a decrease in insulation. Therefore, it is important for varnish application that the electric wires in the slot and the slot and the electric wire are sufficiently fixed.

  In particular, the rotor for the electric tool is driven at a high speed rotation of 2000 to 5000 revolutions / minute, the juicer mixer is 10,000 to 20000 revolutions / minute, and the vacuum cleaner is 100,000 revolutions / minute. A large centrifugal force is applied to the rotor wires. In particular, if there is a crossover floating in the air, the varnish may not adhere sufficiently and may break due to vibration or the like. Therefore, it is important to sufficiently fix the coil portion of the stator with the treatment varnish.

  In addition, the varnish treatment for this part is generally performed by raising the rotor temperature from room temperature to 100 to 150 ° C., sufficiently transferring the heat, removing moisture, repairing scratches on the coil wire, etc. Due to the dripping or dipping treatment, the surrounding temperature is raised by heat dissipation, and thinners such as xylene and toluene used in the varnish and reactive diluents such as styrene and vinyltoluene are volatilized, and the working environment is deteriorated by bad odor. doing.

  As for the varnish treatment method, the varnish penetrates between the commutator pieces of the rotor due to the capillary phenomenon to cause poor electrical conduction or sparks, or the varnish adheres to the core and may be shaken during rotation. It was difficult to fix the floating line in the air enough to the actual machine with varnish.

  For example, Patent Literatures 1, 2, and 3 have been proposed as methods for suppressing varnish penetration into the undercut portion. In Patent Document 1, the undercut of the commutator is shifted to the outer peripheral side of the commutator in the vicinity of the hook portion to prevent the varnish from penetrating. In patent document 2, it is a method of fixing a connecting wire by winding a connecting wire part in multiple times with a string, and preventing a varnish from penetrating into the undercut part of a commutator. Patent Document 3 describes a method of fixing an electric wire after varnish treatment, a method of increasing viscosity with a thixotropic agent, and a method of increasing viscosity using glass beads or saturated polyester.

JP-A-9-252564 JP 2008-160970 A JP 2014-138431 A

  In Patent Document 1 described above, the height of the rectifier is the same as the height of the rotor, and when a large amount of varnish with low viscosity and high permeability is applied, the varnish can penetrate beyond that height. There is a problem that sufficient effects cannot be obtained.

  Even in Patent Document 2, the varnish is absorbed to the string so that it is effective to some extent. However, when a lot of varnish is applied or when a highly permeable varnish is used, the varnish may penetrate and is sufficient. The effect is not obtained. Moreover, since the man-hour for winding the string increases, the production cost increases, for example, the number of steps during curing increases.

  Even in Patent Document 3, there is no description of the solvent used, there is no influence on the working environment, and when hollow glass is used, the heat dissipation of the varnish is hindered by the heat generated during coil rotation, and the varnish is thermally deteriorated. There was a problem of promoting the deterioration of the electric wire that was strongly and firmly fixed by heat. Also, when using a varnish with too high thixotropic properties for work, the varnish does not penetrate into the electric wire, increasing the amount of adhesion, as well as decreasing the viscosity and flakyness due to aging, even a little under As soon as it penetrates into the cut part, it spreads by capillary action. Furthermore, a problem that a cured varnish of the required coating thickness cannot be obtained occurs, increasing the defect rate, leading to an increase in production cost. For this reason, the methods of the above-mentioned patent documents are often insufficient.

In addition, when the varnish is applied thickly, the heat generated by an excessive load during operation tends to be stored without being dissipated and the temperature of the electrical equipment tends to rise, so that each material used is more resistant to heat and heat. The thing with high property has come to be demanded. 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. In addition, the generated heat may cause cracks in the varnish, causing defects, increasing the defect rate, and increasing production costs.
In addition, when the electrical equipment to be processed increases in size, it is often impossible to put the processed electrical equipment into a large drying facility, and processing at room temperature to low temperature has been required. Due to the problem of pot life, it is not used in general. Use a solvent-type varnish with a solvent that volatilizes at room temperature or use an organic peroxide. Only the repair method is used.

  In view of the above, the present invention is suitable for work in molding such as impregnation of coils for electrical equipment using an armature (rotor) such as a generator or electric tool, and insulation treatment such as casting. Unsaturated polyester resin composition that can increase the life of the rotor because it can improve the working environment, reduce the volatile substances, improve the working environment, and give the coating film high adhesive strength and flexibility to win. It is an object to provide a manufacturing method of a product, a rotor, a resin composition for electrical insulation, and an electrical equipment insulator. In addition, in the present invention, by applying a coil varnish with less odor prior to the coil treatment varnish, it is possible to suppress the penetration of the varnish into the rectifier portion of the stator, and to impart heat dissipation and improve reliability. It is an object to produce a rotor that has been made to move.

  The present invention contains an unsaturated polyester (A), a reactive diluent (B), an alkylbenzene / formaldehyde resin (C), and an organic peroxide (D) that initiates a curing reaction at less than 80 ° C. as essential materials. It is related with the unsaturated polyester resin composition which becomes.

  Furthermore, this invention relates to the unsaturated polyester resin composition in any one of said above whose acid value of unsaturated polyester (A) is 25 or less.

  Furthermore, the present invention provides the unsaturated polyester according to any one of the above, wherein the reactive diluent (B) has a vapor pressure at 20 ° C. of 0.1 mmHg or less and is a reactive diluent having an unsaturated group. The present invention relates to a resin composition.

  Furthermore, this invention mix | blends unsaturated polyester (A) and a reactive diluent (B), and the 25 degreeC viscosity of the unsaturated polyester resin composition obtained is 3000-8000 mPa * s in any one of the above It relates to the unsaturated polyester resin composition described.

  Furthermore, this invention is described in any one of the above which contains 0.1-20 mass parts of alkylbenzene formaldehyde resin (C) with respect to 100 mass parts of total amounts of unsaturated polyester (A) and a reactive diluent (B). It relates to an unsaturated polyester resin composition.

  Furthermore, the present invention provides 0.5 to 4 organic peroxides (D) that initiate a curing reaction at less than 80 ° C. with respect to 100 parts by mass of the total amount of unsaturated polyester (A) and reactive diluent (B). The unsaturated polyester resin composition according to any one of the above, wherein the unsaturated polyester resin composition contains 2 parts by mass and has a gelation time of 2 to 6 minutes at 120 ° C. according to a high temperature curing property measurement method of JIS C 2105.

  Further, the present invention uses the unsaturated polyester resin composition described above, and coats and cures at least a connecting wire portion under the commutator of the rotor before the treatment by dipping and so on. About.

  Furthermore, this invention relates to the resin composition for electrical insulation formed by further containing a polymerization initiator, a stabilizer, and a filler in the unsaturated polyester resin composition described above.

  The present invention relates to a method for producing an electrical equipment insulator, wherein the electrical equipment is coated with the resin composition for electrical insulation described above and cured.

  According to the present invention, the adhesion force is improved in the molding work such as the impregnation of the coil for the electric equipment, particularly the electric equipment using the armature (rotor) such as the generator and the electric tool, and the insulation treatment such as casting. While reducing the volatile substances, improving the working environment, and providing high flexibility with excellent adhesion of the coating film, the unsaturated polyester resin composition that enables the rotor to have a long life, A child, a resin composition for electrical insulation, and a method for producing an electrical equipment insulator can be provided. Also, by applying a coil varnish with low odor, it is possible to suppress the penetration of the varnish in the stator rectifier part while improving the working environment, and by using a soft resin cured material with a soft coating, It is possible to produce and provide a rotor that reduces defects such as breakage due to heat and the like and has heat dissipation properties to prevent cracking of the varnish film and improve reliability.

The front view (A) and side view (B) of the test piece which were used for the measurement of shear adhesive force.

  Hereinafter, the present invention will be described in more detail. However, the present invention is not limited to the following embodiments.

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

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 unsaturated dibasic acid described above, a saturated acid and a diester of this saturated acid lower alkyl may 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, 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 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 set to 1000 to 10,000. 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, when α, β-unsaturated dibasic acid, which is an essential component, and only an alcohol having one or more hydroxyl groups, or a polybasic acid component and a polyhydric alcohol component are used together and subjected to a condensation reaction, and both components react. The process proceeds while removing the resulting condensed water out of 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 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 for the purpose of obtaining a low-odor resin composition. Those having a thickness of 1 mmHg (20 ° C.) or less and further dissolving the unsaturated polyester resin (A) and the alkylbenzene / formaldehyde resin (C) are selected.

  Specific examples of polymerizable monofunctional (meth) acrylates that satisfy this requirement include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenol ethylene oxide modified (meth) acrylate. Can be mentioned. Also, use (meth) acrylate having a hydroxyl group such as (poly) caprolactone monoethoxy (meth) acrylate such as 2-hydroxyethyl methacrylate, Plaxel FA1, FA2D, FA3, FM1D, FM2D, FM3 (Daicel). Can do. 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 adjusted so that the viscosity of the obtained unsaturated polyester resin composition at 25 ° C. is 3000 to 8000 mPa · s. The Specifically, the reactive diluent (B) having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less is 10 to 50 parts by mass with respect to 100 parts by mass of the unsaturated polyester (A). It is preferable that If the amount is less than 10 parts, the resulting resin composition has a viscosity exceeding 8000 mPa · s, so that it not only adheres to the actual machine surface thickly, but also deteriorates internal permeability, and heat is generated during use. Cracks, etc. may occur, causing dielectric breakdown and making the actual machine unusable.

  Further, if 50 parts or more of a reactive diluent having an unsaturated group whose vapor pressure at 20 ° C. is 0.1 mmHg or less is added, the appearance of the resin composition becomes cloudy and the varnish viscosity is too low, and the coating film Becomes thinner and penetrates into the interior, and a coating cannot be formed.

  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 Generalite 30, Generalite 50, Generalite 100 manufactured by General Petrochemical Industries, Ltd., Nikanol L, Nikanol LL, 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 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 amount of the diluent. Part. If the alkylbenzene / formaldehyde resin exceeds 50 parts by mass, the surface drying time and the curing time of the resin composition will be extended, making it difficult to cure. On the other hand, when the blending amount is less than 0.1 parts by mass, a problem that the cured film of the resin composition does not become flexible occurs.

  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 amount of the diluent. Part. If the alkylbenzene / formaldehyde resin exceeds 50 parts by mass, the surface drying time and the curing time of the resin composition will be extended, making it difficult to cure. On the other hand, when the blending amount is less than 0.1 parts by mass, a problem that the cured film of the resin composition does not become flexible occurs.

  Examples of the organic peroxide (D) that starts the curing reaction at less than 80 ° C. used in the present invention include bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-methoxyethylperoxydicarbonate, and di-3. -Peroxycarbonates such as methoxybutyl peroxydicarbonate, di-2-methylhexyl peroxydicarbonate, di-isopropyl peroxydicarbonate; 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumene peroxy Neodecanoate, t-butylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxypivalate, t-hexylperoxypivalate, 1,1,3,3-tetramethylbutylperoxydi 2-ethylhexanoate, t Hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxysobutyrate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane Alkyl peroxides such as t-amylperoxy 2-ethylhexanoate; organic peroxides such as diacyl peroxides such as isobutyroyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, lauroyl peroxide Can be mentioned. These organic peroxides may be used alone or in combination of two or more.

  As the polymerization inhibitor used as necessary when adjusting the high-temperature curing characteristics in the present invention, 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 Etc.

  The amount of the organic peroxide (D) that starts the curing reaction at less than 80 ° C. is 0.5 to 4 parts by mass with respect to 100 parts by mass of the total amount of the unsaturated polyester (A) and the reactive diluent (B). Is preferably 0.8 to 3 parts by mass, and more preferably 1.0 to 2.5 parts by mass. If it is less than 0.5 mass part, hardening will be slow and will inhibit sclerosis | hardenability. Moreover, even if it adds exceeding 4 mass parts, sclerosis | hardenability will not accelerate | stimulate and the malfunction that the adhering force with the hardened | cured part obtained will generate | occur | produce.

The amount of the organic peroxide (D) that initiates the curing reaction at less than 80 ° C. and the amount of the polymerization inhibitor that is used as required is gelation at 120 ° C. according to the high temperature curing property measurement method of JIS C 2105. The time is preferably 2 to 8 minutes, more preferably 3 to 7 minutes, and even more preferably 4 to 6 minutes. If it is less than 2 minutes, the coating film can be prepared, but the time until curing is too short, the workability is remarkably lowered, and the film thickness is too thick, causing a problem that cracks occur.
If it is 8 minutes or longer, the curability is not promoted, and the thickness of the resulting cured product becomes thin, which causes a problem that it penetrates into the interior. The blending amount of the polymerization inhibitor used as necessary is determined conveniently so that the curability of the resulting unsaturated polyester resin composition is within the above range, but the blending amount is the unsaturated polyester resin composition. 0.01-5 mass parts is preferable with respect to 100 mass parts, More preferably, it is 0.5-3 mass parts.

  As the polymerization inhibitor used as necessary in the present invention, p-benzoquinone, hydroquinone, naphthoquinone, p-toluquinone, 2,5-diphenyl-p-benzoquinone, 2,5 diacetoxy-p-benzoquinone, p-tert- Examples include butyl catechol, 2,5-di-tert-butylhydroquinone, 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 unsaturated polyester resin composition to be obtained, and the blending amount is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the unsaturated polyester resin composition, More preferably, it is 0.5-3 mass parts.

  Stabilizers used as needed in the invention 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. 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 by weight relative to 100 parts by mass of the total amount of the resin composition. 5 mass parts or less are preferable, More preferably, it is 0.01-0.1 mass part.

  As the inorganic filler used as necessary in the present invention, the average particle diameter measured by the X-ray transmission gravity sedimentation method is 1.0 to 10 μm, more preferably the average particle diameter is 1.5 to 8 μm, More preferably, it is not particularly limited as long as it is 3 to 7 μm of silicon dioxide. If this average particle size exceeds 10 μm, the viscosity will be low and the permeability will be improved, but the sedimentation of the filler will be severe, the stability will deteriorate, the insulation and appearance will deteriorate, and the resistance such as chemical resistance will deteriorate. Tend to. On the other hand, when the average particle size is less than 1 μm, the viscosity increases, workability deteriorates, and the film thickness becomes uneven.

  In order to obtain a higher thermal conductivity, in addition to the inorganic filler, a material having a thermal conductivity of 3 W / mK or more measured by a laser flash method can be mixed. Specific examples include aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, aluminum borate whisker, silicon nitride, boron nitride, crystalline silica, non-crystalline Examples thereof include crystalline silica and silicon carbide. In order to increase thermal conductivity, alumina, aluminum nitride, silicon nitride, boron nitride, crystalline silica, amorphous silica, and silicon carbide are preferable. These inorganic fillers may be used alone or in combination of two or more.

  The insulation treatment using the resin composition of the present invention is performed by a known method. After impregnating the resin composition of the present invention dropwise onto an electric device for 1 to 10 minutes, the insulation composition is 0.2 to 0.2 at 100 to 180 ° C. It is desirable to carry out by a method in which the resin composition is cured by heating for 5 hours.

  Since the resin composition of the present invention has less odor and good workability, the resulting varnish film has flexibility and high adhesiveness, so that electric devices such as motors are representative. Suitable for impregnation treatment. In particular, it is optimal for terminal insulation treatment of rotors for electric tools, shoe mixers, vacuum cleaners, and generators that rotate at high speed.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments. In the following examples, “part” means “part by mass” 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 10 mgKOH / g, the reaction was terminated by cooling. The number average molecular weight at this time was 3260.

(2) Synthesis of unsaturated polyester (B) 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, and inert. 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 and cooled when the acid value reached 2.4. After adding 20600 parts of maleic anhydride, the temperature was raised again to 215 ° C. in 6 hours. When the acid value reached 30 mgKOH / g, the reaction was terminated by cooling. The number average molecular weight at this time was 2670.

(3) Preparation of unsaturated polyester resin composition (A1) 30 parts of 2-hydroxyethyl methacrylate as component (B) is added to 100 parts of the above unsaturated polyester (A) to prepare an unsaturated polyester resin composition (A1). did.

(4) Preparation of unsaturated polyester resin composition (A2) 50 parts of 2-hydroxyethyl methacrylate as component (B) is added to 100 parts of the unsaturated polyester (A) to prepare an unsaturated polyester resin composition (A2). did.

(5) Preparation of unsaturated polyester resin composition (A3) 10 parts of 2-hydroxyethyl methacrylate as component (B) is added to 100 parts of the unsaturated polyester (A) to prepare an unsaturated polyester resin composition (A3). did.

(6) Preparation of unsaturated polyester resin composition (A4) 65 parts of 2-hydroxyethyl methacrylate as component (B) is added to 100 parts of the above unsaturated polyester (A) to prepare an unsaturated polyester resin composition (A4). did.

(7) Preparation of unsaturated polyester resin composition (A5) 30 parts of styrene was added as component (B) to 100 parts of the unsaturated polyester (A) to prepare an unsaturated polyester resin composition (A5).

(8) Preparation of unsaturated polyester resin composition (B1) 30 parts of 2-hydroxyethyl methacrylate as component (B) is added to 100 parts of the above unsaturated polyester (B) to prepare an unsaturated polyester resin composition (B1). did.

Example 1
(Preparation of unsaturated polyester resin composition (a-1))
In the unsaturated polyester resin composition (A1), 10 parts of a formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Nicanol LL) as the component (C), and t-butylperoxy 2-ethylhexa as the component (D) 1 part of noate (manufactured by NOF Corporation, perbutyl O) and 0.02 part of hydroquinone as other materials were blended and mixed well to obtain unsaturated polyester resin composition a-1.

(Example 2)
(Preparation of unsaturated polyester resin composition (a-2))
Except that the unsaturated polyester resin composition (A1) used in Example 1 was changed to the unsaturated polyester resin composition (A2), all were blended in the same composition, mixed well, and the unsaturated polyester resin composition a- 2 was obtained.

(Comparative Example 1)
(Preparation of unsaturated polyester resin composition (a-3))
The unsaturated polyester resin composition (A1) used in Example 1 was blended in the same composition except that the unsaturated polyester resin composition (A3) was changed, mixed well, and the unsaturated polyester resin composition a- 3 was obtained.

(Comparative Example 2)
(Preparation of unsaturated polyester resin composition (a-4))
The unsaturated polyester resin composition (A1) used in Example 1 was blended in the same composition except that the unsaturated polyester resin composition (A4) was changed, mixed well, and the unsaturated polyester resin composition a- 4 was obtained.

(Comparative Example 3)
(Preparation of unsaturated polyester resin composition (a-5))
Except that the unsaturated polyester resin composition (A1) used in Example 1 was changed to the unsaturated polyester resin composition (A5), all were blended in the same composition, mixed well, and the unsaturated polyester resin composition a- 2 was obtained.

(Comparative Example 4)
(Preparation of unsaturated polyester resin composition (b-1))
Except for changing the unsaturated polyester resin composition (A1) used in Example 1 to the unsaturated polyester resin composition (B1), they were all blended in the same composition, mixed well, and the unsaturated polyester resin composition b- 1 was obtained.

(Comparative Example 5)
(Preparation of unsaturated polyester resin composition (a-6))
In the unsaturated polyester resin composition (A1), (C) component is not used, and (D) component is t-butylperoxy 2-ethylhexanoate (manufactured by NOF Corporation, perbutyl O) 1 part, As other materials, 0.02 part of hydroquinone was blended and mixed well to obtain an unsaturated polyester resin composition a-6.

(Comparative Example 6)
(Preparation of unsaturated polyester resin composition (a-7))
Unsaturated polyester resin composition (A1), 40 parts of formaldehyde resin (trade name Nicanol LL, manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (C), t-butylperoxy 2-ethylhexanoate as component (D) 1 part of ate (manufactured by NOF Corporation, perbutyl O) and 0.02 part of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-7.

(Comparative Example 7)
(Preparation of unsaturated polyester resin composition (a-8))
To the unsaturated polyester resin composition (A1), 10 parts of a formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Nicanol LL) as the component (C), and t-butylperoxy 2-ethylhexano as the component (D) 0 parts of ate (manufactured by NOF Corporation, perbutyl O) and 0.02 part of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-8.

(Comparative Example 8)
(Preparation of unsaturated polyester resin composition (a-9))
To the unsaturated polyester resin composition (A1), 10 parts of a formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Nicanol LL) as the component (C), and t-butylperoxy 2-ethylhexano as the component (D) 5 parts of ate (manufactured by NOF Corporation, perbutyl O) and 0.02 part of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-9.

(Comparative Example 9)
(Preparation of unsaturated polyester resin composition (a-10))
To the unsaturated polyester resin composition (A1), 10 parts of a formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Nicanol LL) as the component (C), and t-butylperoxy 2-ethylhexano as the component (D) 5 parts of ate (manufactured by NOF Corporation, perbutyl O) and 0 part of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-10.

(Comparative Example 10)
(Preparation of unsaturated polyester resin composition (a-11))
To the unsaturated polyester resin composition (A1), 10 parts of a formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name Nicanol LL) as the component (C), and t-butylperoxy 2-ethylhexano as the component (D) 5 parts of ate (manufactured by NOF Corporation, perbutyl O) and 0.1 part of hydroquinone as other materials were mixed and mixed well to obtain unsaturated polyester resin composition a-11.

  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, the gelation time was measured by a test tube method.

(4) Pot life measurement:
φ18 mm (φ represents a diameter. The same applies hereinafter) The resin compositions of Examples and Comparative Examples are placed in a test tube from the bottom, sealed, and placed in a constant temperature bath at 40 ° C. The internal state was confirmed every 24 hours, and the time when a gelled product was formed was measured as the pot life.

(5) Odor test 100 g of the resin compositions of the examples and comparative examples were placed in a polyvinyl beaker with a diameter of 70 mm and a height of 140 mm, respectively, capped, and the odor after being left for 1 hour in a 25 ° C. constant temperature bath was measured 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.

(6) Measurement of volatilization amount:
10 g each of the resin compositions of Examples and Comparative Examples were placed in a φ60 mm metal petri dish and left in a thermostatic bath at 130 ° C. for 2 hours, and the volatilization amount was measured by mass change.

(7) Shear adhesion 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. Moreover, the preparation state of the coating film in the center part of the test piece after curing was also observed.

(8) Thickness of coating 1-AIW (manufactured by Hitachi Metals, Ltd.) having a diameter of 1 mm is cut to a length of 100 mm, and 20 bundles are used as test pieces. 0.5 g of each of the resin compositions of Examples and Comparative Examples was applied to the bundled test pieces and cured at 150 ° C./1 h (representing 1 hour at 150 ° C., the same applies hereinafter). The thickness of the film of the obtained cured product was visually observed.

(9) State of coating 10 g of each of the resin compositions of Examples and Comparative Examples was placed in a metal petri dish of φ60 mm and allowed to stand in a 130 ° C. constant temperature bath, and the time when the surface was not sticky was measured as the drying time. Moreover, the hardness of the dried coating film was measured by SoreD. The obtained results are shown in Table 2, Table 3, and Table 4.

注 ○；良好 ×；不具合有（臭気試験を除く）

Note ○: Good ×: Faulty (excluding odor test)

注 ○；良好 ×；不具合有（臭気試験を除く）

Note ○: Good ×: Faulty (excluding odor test)

注 ○；良好 ×；不具合有（臭気試験を除く）

Note ○: Good ×: Faulty (excluding odor test)

  From the results of Tables 2, 3 and 4, the resin composition for insulating electrical equipment according to the present invention has a low odor, so it can provide a good working environment and has a good fixing force. It can be adapted to improve characteristics. Moreover, a coating film can be produced uniformly by controlling the viscosity of the resin composition. Moreover, it can respond to a wide range of conventional impregnation methods. Furthermore, it is possible to have cured product characteristics such as electrical insulation and adhesion that are equivalent to or better than conventional liquid type resin compositions, and the film becomes flexible, so it is possible to suppress cutting of wires due to heat of the actual machine. Therefore, a highly reliable electric 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)

  Unsaturated polyester comprising unsaturated polyester (A), reactive diluent (B), alkylbenzene-formaldehyde resin (C), and organic peroxide (D) that initiates curing reaction at less than 80 ° C. as essential materials Resin composition.   2. The unsaturated polyester resin composition according to claim 1, wherein the acid value of the unsaturated polyester (A) is 25 or less.   The unsaturated polyester resin composition according to claim 1 or 2, wherein the reactive diluent (B) has a vapor pressure at 20 ° C of 0.1 mmHg or less and has an unsaturated group.   The unsaturated polyester resin composition obtained by blending the unsaturated polyester (A) and the reactive diluent (B) has a viscosity at 25 ° C of 3000 to 8000 mPa · s. Unsaturated polyester resin composition.   Item 5. The content according to any one of Items 1 to 4, comprising 0.1 to 20 parts by mass of an alkylbenzene / formaldehyde resin (C) with respect to 100 parts by mass of the total amount of the unsaturated polyester (A) and the reactive diluent (B). Saturated polyester resin composition.   0.5 to 4 parts by mass of organic peroxide (D) that initiates the curing reaction at less than 80 ° C. with respect to 100 parts by mass of the total amount of unsaturated polyester (A) and reactive diluent (B); Item 6. The unsaturated polyester resin composition according to any one of Items 1 to 5, wherein the gelation time at 120 ° C. is 2 to 6 minutes according to the high temperature curing property measurement method of JIS C 2105.   Using the unsaturated polyester resin composition according to any one of claims 1 to 6, at least a connecting wire part under a commutator of a rotor before treatment is covered by dipping and the like and cured. Rotor.   The resin composition for electrical insulation formed by containing a polymerization initiator, a stabilizer, and a filler in the resin composition in any one of Claims 1-6.   A method for producing an electrical equipment insulator, wherein the electrical equipment is coated with the resin composition for electrical insulation according to claim 8 and cured.

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