JP2017048329A - Unsaturated polyester resin composition, and method for manufacturing resin composition for electric insulation and electric equipment insulation using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin composition which emits little odor and improves working environment, can suppress infiltration of varnish, reduces failure such as breakage of a crossover portion due to a resin cured product having a soft film, and has improved reliability to which heat dissipation is imparted, and to provide a method for manufacturing a resin composition for electric insulation and an electric equipment insulation using the same.SOLUTION: There is provided an unsaturated polyester resin composition which contains an unsaturated polyester resin (A), a reactive diluent (B), a non-silicon based surface conditioner (C), an alkylbenzene-formaldehyde resin (D), an inorganic filler (E), and an organic peroxide (F) that starts a curing reaction at lower than 80°C, as essential materials, where a vapor pressure at 20°C of the (B) component is 0.1 mmHg or less, and 25-400 pts.mass of the (B) component is contained with respect to 100 pts.mass of the (A) component, and 0.001-10.0 pts.mass of the (C) component, 0.1-20 pts.mass of the (D) component, 20-100 pts.mass of the (E) component, and 0.1-4.5 pts.mass of the (F) component are contained with respect to 100 pts.mass of the total amount of the (A) and (B) components.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 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 and improving the working environment, the coating film has a high adhesive force and can be provided with flexibility, so that the unsaturated polyester resin composition providing a longer life of the rotor and the same 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 on this portion is generally performed after the rotor is heated from room temperature (25 ° C.) to 100 to 150 ° C. and heat is sufficiently transferred to remove moisture, repair the wound of the coil wire, etc. Since the varnish is dripped or dipped without any change, the ambient temperature increases due to heat dissipation, and thinners such as xylene / toluene used in the varnish and reactive diluents such as styrene / vinyltoluene volatilize and work with bad odor. The environment is getting worse.

  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 causes shaking 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, increasing the viscosity with a thixotropic agent, and increasing the viscosity using glass beads or a saturated polyester resin.

Japanese Patent Laid-Open No. 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, if a varnish with too high thixotropy is used in the work, the varnish does not penetrate into the electric wire as described above, and not only increases the amount of adhesion, but also the viscosity and thixotropy decrease with the passage of time. 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 having 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 electric equipment to be processed is enlarged, it is often impossible to put the processed electric equipment into a large drying facility, and processing at room temperature (20 ° C.) to low temperature has been required. Due to problems with pot life and pot life, it is not generally used. Use a solvent-type varnish with a solvent that volatilizes at room temperature or use an organic peroxide. Because of the problem, only a partial repair method is used.

  From the above, in the present invention, by applying the coil fixing varnish with less odor, it is possible to suppress the penetration of the varnish of the rectifier portion into the stator while improving the working environment, and further, the resin cured product with a soft film It is an object of the present invention to produce a rotor that has improved reliability by reducing defects such as crossover breakage due to high-speed rotation, heat, etc., and imparting heat dissipation.

  The present invention provides: [1] Unsaturated polyester resin (A), reactive diluent (B), non-silicone surface conditioner (C), alkylbenzene / formaldehyde resin (D), inorganic filler (E), 80 ° C. An unsaturated polyester resin composition comprising an organic peroxide (F) that initiates a curing reaction at less than an essential material, wherein the vapor pressure at 20 ° C. of the component (B) is 0.1 mmHg or less, (C) component is 0.001-10 mass with respect to 100 mass parts of (A) component with respect to 100 mass parts of (B) component 25-400 mass parts and (A) component and the total amount of (B) component, respectively. Part, (D) component relates to an unsaturated polyester resin composition containing 0.1 to 20 parts by mass, (E) component to 20 to 100 parts by mass, and (F) component to 0.1 to 4.5 parts by mass.

  Moreover, this invention relates to the unsaturated polyester resin composition as described in said [1] whose acid value of [2] unsaturated polyester resin (A) is 30 mgKOH / g or less.

  Moreover, this invention relates to the unsaturated polyester resin composition as described in said [1] or [2] whose [3] reactive diluent (B) is a reactive diluent which has an unsaturated group.

  Moreover, this invention is [4] unsaturated polyester resin composition as described in any one of said [1]-[3] whose non-silicon-type surface conditioning agent (C) is a vinyl type compound or an acryl-type compound. Related to things.

  Moreover, this invention is [5] unsaturated polyester as described in any one of said [1]-[4] whose average particle diameter of an inorganic filler (E) is 1.0-10 micrometers silicon dioxide. The present invention relates to a resin composition.

  Moreover, this invention relates to the unsaturated polyester resin composition as described in any one of said [1]-[5] containing [6] and a stabilizer (G) further.

  Furthermore, the present invention relates to [7] an electrically insulating resin composition comprising the unsaturated polyester resin composition according to any one of [1] to [6].

  Moreover, this invention relates to the manufacturing method of the electrical equipment insulator characterized by coat | covering with the resin composition for electrical insulation as described in [8] said [7], and hardening | curing.

  By using the unsaturated polyester resin composition of the present invention as a resin composition for electrical insulation, it is possible to suppress the penetration of varnish in the stator rectifier portion while reducing the odor and improving the working environment, and further the resin curing of the film is soft By using the product, it is possible to reduce the defects such as crossover breakage due to high-speed rotation, heat, etc., and to produce and provide a rotor that has improved heat reliability by preventing cracking of the varnish film. be able to.

It is the front view (A) and side view (B) of the test piece used for the measurement (shearer method) of the shearing | fixing force.

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

((A) component: unsaturated polyester resin)
The unsaturated polyester resin (A) used in the present invention comprises an α, β-unsaturated dibasic acid and an alcohol having one or more hydroxyl groups as essential components, and an acid component and an alcohol component, and further a modifying component as necessary. Obtained by reaction.

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. A terephthalic acid diester such as monomethyl terephthalate or a lower alkyl diester of terephthalic acid, for example, dimethyl terephthalate is used. Further, isophthalic acid, adipic acid, phthalic acid, sebacic acid and the like can also be used. Examples of 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. It is done. For example, dimethyl terephthalate is used as the diester of the lower alkyl saturated acid. These may be used alone or in combination.
Furthermore, edible oil fatty acids such as soybean oil fatty acid, linseed oil fatty acid, 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, cyclopentadiene and the like.
The number average molecular weight of the unsaturated polyester resin (A) used in 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.
From the viewpoint of compatibility with the reactive diluent (B), the acid value of the unsaturated polyester resin (A) used in the present invention is preferably 30 mgKOH / g or less, and more preferably 15 mgKOH / g or less. When the acid value of the unsaturated polyester resin (A) of the present invention exceeds 30 mgKOH / g, 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 resin (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.

((B) component: reactive diluent)
The reactive diluent (B) used in the present invention has a vapor pressure of 0.1 mmHg (20 ° C.) or less for the purpose of obtaining a low-odor resin composition, and further contains an unsaturated polyester resin (A ), A non-silicon-based surface conditioner (C), and an alkylbenzene / formaldehyde resin (D) are selected.

Specific examples of the polymerizable monofunctional (meth) acrylate that satisfies this requirement include dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and phenol ethylene oxide-modified (meth) acrylate. . Further, 2-hydroxyethyl methacrylate, Plaxel FA1 (unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, CH ₂ ═CHCOO (CH ₂ ) ₂ O [CO (CH ₂ ) ₅ O] _n H, molecular weight 230), FA2D ( Unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, CH ₂ ═CHCOO (CH ₂ ) ₂ O [CO (CH ₂ ) ₅ O] _n H, molecular weight 344), FA3 (unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ O [CO (CH ₂ ) ₅ O] _n H, molecular weight 473), FM1D (unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ O [CO (CH ₂ ) ₅ O] _n H, molecular weight 358), FM2D (unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone, CH ₂ = CHCOO (CH ₂ ) ₂ O [CO _{(CH 2) 5 O] n} H, molecular weight 344), FM3 (unsaturated fatty acid hydroxyalkyl Kill ester modifications ε- _{caprolactone, CH 2 = C (CH 3} ) COO (CH 2) 2 O [CO (CH 2) 5 O] n H, molecular weight 473) (manufactured by Daicel), etc. (poly) caprolactone mono A (meth) acrylate having a hydroxyl group such as ethoxy (meth) 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.
In addition, (meth) acrylate means an acrylate or a methacrylate.

The use amount of the unsaturated polyester resin (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 mass of the unsaturated polyester resin (A). It is preferable that the reactive diluent (B) having an unsaturated group is 25 to 400 parts by mass. When the amount is less than 25 parts by mass, the resulting resin composition has too high a viscosity, and not only thickly adheres to the transformer surface but also deteriorates internal permeability.
Moreover, when the reactive diluent having an unsaturated group having a vapor pressure at 20 ° C. of 0.1 mmHg or less exceeds 400 parts by mass, 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.

((C): non-silicon-based surface conditioner)
The non-silicon-based surface conditioner (C) used in the present invention is a method for improving the adhesion, and can be selected from vinyl compounds, acrylic compounds and fluorine compounds. Moreover, this surface conditioner can be used individually or in combination of 2 or more types. Examples of such commercially available surface conditioners include acrylic compound surface conditioners BYK-350, BYK-352, BYK-354, BYK-355, BYK-356, BYK-358N, BYK-361N, and BYK. -381, BYK-392, BYK-394, BYK-3440, BYK-399 of silicon-free surface conditioner, BYK-UV3535 of surface conditioner having a crosslinkable functional group (above, manufactured by BYK Japan Co., Ltd., trade name) ), OX-880EF, OX-881, OX-883, OX-77EF, OX-710, 1970, 230, LF-1980, LF-1982, LF-1983, LF-1984, surface modifiers of acrylic compounds LF-1985, vinyl polymer surface modifier LHP-90, LHP-96, P- 10EF (or more, Kusumoto Kasei Co., Ltd., trade name), Polyflow No. of surface modifier of the acrylic compound 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 (manufactured by Kyoeisha Chemical Co., Ltd., trade name) and the like. These may be used alone or in combination of two or more.

  The amount of the non-silicon-based surface conditioner (C) used is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the reactive diluent (B). It is more preferable to set it as -5 mass parts, and it is still more preferable to set it as 0.05-3 mass parts. If the amount is less than 0.001 part by mass, the resulting fixing force is reduced. Moreover, even if it adds exceeding 10 mass parts, the adhering force will not improve, and the malfunction which adhering force with the hardened | cured material obtained will fall conversely will generate | occur | produce.

((D) component: alkylbenzene / formaldehyde resin)
The (D) component alkylbenzene / formaldehyde resin used in the present invention is a resol type obtained by reacting alkylbenzene such as toluene or xylene with formaldehyde in the presence of an alkali catalyst such as sodium hydroxide, ammonia or trieramine. Resin. Examples of commercially available xylene / formaldehyde resins include Generalite 30, Generalite 50, Generalite 100, General Petrochemical Co., Ltd., Nikanol L, Nikanol LL, Nikanol LLL manufactured by Mitsubishi Gas Chemical Co., Ltd.

  The amount of the component (D) alkylbenzene / formaldehyde resin used in the present invention is 100 parts by weight of the total amount of the unsaturated polyester (A) and the reactive diluent (B). D) It is preferable that it is 0.1-20 mass parts, It is more preferable that it is 1-15 mass parts, More preferably, it is 5-10 mass parts. If the alkylbenzene / formaldehyde resin exceeds 20 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.

((E) inorganic filler)
The inorganic filler (E) used in the present invention has a thermal conductivity measured by a laser flash method of 3 W / mK or more in order to give higher thermal conductivity. As a specific example, 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, amorphous silica or silicon carbide It is done. In order to increase thermal conductivity, alumina, aluminum nitride, silicon nitride, boron nitride, crystalline silica, amorphous silica, and silicon carbide are preferable. As the inorganic filler (E), silicon dioxide is more preferable. These inorganic fillers may be used alone or in combination of two or more.
The inorganic filler (E) used in the present invention has an average particle size of 1.0 to 10 μm, more preferably an average particle size of 1.5 to 8 μm, as measured by an X-ray transmission gravity sedimentation method. Preferably, it is 3-7 micrometers. When this average particle diameter exceeds 10 μm, the viscosity is lowered and the workability is improved, but the sedimentation of the filler is severe, the stability is deteriorated, the insulation property and the appearance are deteriorated, and the coating thickness tends to be thinned. is there. 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. The amount of the inorganic filler (E) used is preferably 20 to 100 parts by mass and more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (A) and (B). Preferably, it is more preferable to set it as 50-70 mass parts. If it is less than 20 parts by mass, it is difficult to obtain a heat dissipation effect, and if it exceeds 100 parts by mass, the viscosity of the resin composition is excessively increased, workability is deteriorated, and the varnish film becomes non-uniform.

((F) component: organic peroxide that initiates curing reaction at less than 80 ° C.)
Examples of the organic peroxide (F) 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-butylperoxyisobutyrate, 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.

  The amount of the organic peroxide (F) that initiates the curing reaction at less than 80 ° C. is 0.1 to 4.4 relative to 100 parts by mass of the total amount of the unsaturated polyester resin (A) and the reactive diluent (B). 5 mass parts is preferable, it is more preferable to set it as 0.2-4 mass parts, and it is still more preferable to set it as 0.5-3 mass parts. If it is less than 0.1 mass part, hardening will be slow and will inhibit sclerosis | hardenability. Moreover, even if it adds exceeding 4.5 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.

  In this invention, a stabilizer (G) (polymerization inhibitor) is contained as needed. As stabilizer (G) to be used, 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 by the storage stability of the resulting unsaturated polyester resin composition, the curing temperature and the curing time during actual processing, and is usually 0.5% relative to 100 parts by weight of the total amount of the resin composition. The amount is preferably not more than part by mass, more preferably 0.01 to 0.1 part by mass.

  Moreover, it is preferable to add well-known various commercially available additives etc. which have the air barrier effect of the hardened | cured material surface as needed to the unsaturated polyester resin composition of this invention. By blending these additives, the surface curing (surface drying) time can be shortened. As an example of the additive for shortening the surface curability, paraffin waxes having various melting points, low volatility agents such as BYK-S740 and BYK-S750 (manufactured by BYK Japan) are listed. As a compounding quantity of wax, it is 0.05-1 mass part with respect to 100 mass parts of unsaturated polyester resin compositions, Preferably it is 0.1-0.5 mass part.

  The insulation treatment using the unsaturated polyester resin composition of the present invention is performed by a known method, and the electrical insulation resin composition containing the unsaturated polyester resin composition of the present invention is applied to an electrical device. Desirably, the impregnation is carried out by dripping and impregnating for 10 minutes, followed by heating at 80 to 180 ° C. for 0.2 to 5 hours to cure the resin composition for electrical insulation.

  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. It is particularly suitable for the insulation treatment of rotors for electric tools, juicer mixers, vacuum cleaners, and generators that rotate at high speed.

  Examples of the present invention will be described below. In addition, this invention is not limited by this Example. In the following examples, “part” means “part by mass” unless otherwise specified.

(1) Synthesis of unsaturated polyester resin (A) 1107 parts of isophthalic acid and 760 parts of propylene glycol were charged into a reaction vessel equipped with a thermometer, a nitrogen blowing tube, a rectifying tower and a stirring device, and an inert air current ( In nitrogen) with a mantle heater and heated to 230 ° C. over 8 hours. Thereafter, the mixture was kept warm and cooled when the acid value reached 2.4 mgKOH / g, 19600 parts of maleic anhydride was added, and the temperature was raised again to 215 ° C. in 6 hours. When the acid value reached 11 mgKOH / g, the reaction was terminated by cooling. The number average molecular weight at this time was 2980.

(2) Synthesis of unsaturated polyester resin (B) Into an inert gas stream, 1107 parts of isophthalic acid and 760 parts of propylene glycol were charged into a reaction vessel equipped with a thermometer, a nitrogen blowing tube, a rectifying tower and a stirring device. The mixture was heated with a mantle heater and heated to 230 ° C. over 8 hours. Thereafter, the mixture was kept warm and cooled when the acid value reached 2.4 mgKOH / g. After adding 20600 parts of maleic anhydride, the temperature was raised again to 215 ° C. in 6 hours. When the acid value reached 43 mgKOH / g, the reaction was terminated by cooling. The number average molecular weight at this time was 2650.

Example 1
(Preparation of unsaturated polyester resin composition (a-1))
After adding 50 parts of 2-hydroxyethyl methacrylate (vapor pressure 0.01 mmHg at 25 ° C.) as component (B) to 50 parts of the unsaturated polyester resin (A) synthesized above, after thoroughly mixing and confirming the appearance As the component (C), 0.5 parts of Polyflow WS (carboxyl group-containing acrylic polymer, manufactured by Kyoeisha Chemical Co., Ltd.), as the component (D), xylene / formaldehyde resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd.)), product (Nicanol LL) 10 parts, 50 parts of silicon dioxide having an average particle size of 5 μm as component (E), 1 part of t-butylperoxybenzoate as component (F), hydroquinone 0. 05 parts was blended and mixed well to obtain an unsaturated polyester resin composition (a-1).

(Example 2)
(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 resin (A) obtained in Example 1, and thoroughly mixing and confirming the appearance, BYK is used as the component (C). -350 (polyacrylate-based surface conditioner, manufactured by Big Chemie Japan Co., Ltd.) 0.5 parts, (D) component as xylene-formaldehyde resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd.), trade name Nicanol LL ) 10 parts, 50 parts of silicon dioxide with an average particle size of 5 μm as component (E), 1 part of t-butylperoxybenzoate as component (F), and 0.05 part of hydroquinone as stabilizer (G) And mixed well to obtain an unsaturated polyester resin composition (a-2).

(Comparative Example 1)
(Preparation of unsaturated polyester resin composition (a-3))
After adding 50 parts of styrene (vapor pressure 5 mmHg at 20 ° C.) as the component (B) to 50 parts of the unsaturated polyester (A) obtained in Example 1, and after mixing well, (C) As a component, 0.5 part of Polyflow WS (manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts of xylene-formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), E) 50 parts silicon dioxide having an average particle size of 5 μm as component, 1 part t-butylperoxybenzoate as component (F), 0.05 part hydroquinone as stabilizer (G), and mixed well, An unsaturated polyester resin composition (a-3) was obtained.

(Comparative Example 2)
(Preparation of unsaturated polyester resin composition (b-1))
After adding 50 parts of 2-hydroxyethyl methacrylate as a component (B) to 50 parts of the unsaturated polyester (B) obtained in Example 1, mixing well, and confirming the appearance, Polyflow WS as a component (C) 0.5 parts (manufactured by Kyoeisha Chemical Co., Ltd.), xylene formaldehyde resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) 10 parts as component (D), 50 parts of silicon dioxide having an average particle size of 5 μm, 1 part of t-butylperoxybenzoate as component (F), 0.05 part of hydroquinone as stabilizer (G), mixed well, and unsaturated polyester resin composition A product (b-1) was obtained.

(Comparative Example 3)
(Preparation of unsaturated polyester resin composition (a-4))
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) 0.5 parts (manufactured by Kyoeisha Chemical Co., Ltd.), xylene formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), (E) 50 parts of silicon dioxide having an average particle size of 5 μm, 1 part of t-butylperoxybenzoate as component (F), 0.05 part of hydroquinone as stabilizer (G), mixed well, and unsaturated polyester resin composition A product (a-4) was obtained.

(Comparative Example 4)
(Preparation of unsaturated polyester resin composition (a-5))
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) 0.5 parts (manufactured by Kyoeisha Chemical Co., Ltd.), xylene formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), (E) 50 parts of silicon dioxide having an average particle size of 5 μm, 1 part of t-butyl peroxybenzoate as component (F) and 0.05 part of hydroquinone as stabilizer (G), mixed well, and unsaturated polyester resin composition A product (a-5) was obtained.

(Comparative Example 5)
(Preparation of unsaturated polyester resin composition (a-6))
50 parts of the unsaturated polyester (A) obtained in Example 1 was added with 50 parts of 2-hydroxyethyl methacrylate as the component (B), mixed well, and after confirming the appearance, the component (D) was xylene / formaldehyde. Resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) 10 parts, (E) component, 50 parts of silicon dioxide with an average particle size of 5 μm, (F) component t-butyl 1 part of peroxybenzoate and 0.05 part of hydroquinone as a stabilizer (G) were blended and mixed well to obtain an unsaturated polyester resin composition (a-6).

(Comparative Example 6)
(Preparation of unsaturated polyester resin composition (a-7))
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) 15 parts (manufactured by Kyoeisha Chemical Co., Ltd.), 10 parts of xylene / formaldehyde resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), average particle size as component (E) 50 parts of silicon dioxide having a diameter of 5 μm, 1 part of t-butylperoxybenzoate as component (F), and 0.05 part of hydroquinone as stabilizer (G), mixed well, and unsaturated polyester resin composition ( a-7) was obtained.

(Comparative Example 7)
(Preparation of unsaturated polyester resin composition (a-8))
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.), (E) component, 50 parts of silicon dioxide having an average particle size of 5 μm, (F) component, t-butyl peroxybenzoate 1 part, stabilizer (G), 0.05 part of hydroquinone was blended and mixed well to obtain an unsaturated polyester resin composition (a-8).

(Comparative Example 8)
(Preparation of unsaturated polyester resin composition (a-9))
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.), xylene / formaldehyde resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) 25 parts as component (D), 50 parts of silicon dioxide having an average particle size of 5 μm, 1 part of t-butyl peroxybenzoate as component (F), and 0.05 part of hydroquinone as other materials were mixed and mixed well to obtain an unsaturated polyester resin composition (a- 9) was obtained.

(Comparative Example 9)
(Preparation of unsaturated polyester resin composition (a-10))
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.), 10 parts of xylene / formaldehyde resin (Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), As 1 part of t-butylperoxybenzoate and 0.05 part of hydroquinone as a stabilizer (G), they were mixed well to obtain an unsaturated polyester resin composition (a-10).

(Comparative Example 10)
(Preparation of unsaturated polyester resin composition (a-11))
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.), xylene formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), (E) 150 parts of silicon dioxide having an average particle diameter of 5 μm, 1 part of t-butylperoxybenzoate as component (F), 0.05 part of hydroquinone as stabilizer (G), and mixed well, unsaturated polyester resin composition (A-11) was obtained.

(Comparative Example 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) 0.5 parts (manufactured by Kyoeisha Chemical Co., Ltd.), xylene formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), (E) 50 parts of silicon dioxide having an average particle diameter of 5 μm and 0.05 part of hydroquinone as other materials were blended and mixed well to obtain an unsaturated polyester resin composition (a-12).

(Comparative Example 12)
(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.), xylene formaldehyde resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. (Fudo Co., Ltd., trade name Nicanol LL) as component (D), (E) 50 parts of silicon dioxide having an average particle size of 5 μm, 5 parts of t-butyl peroxybenzoate as component (F), and 0.05 parts of hydroquinone as stabilizer (G), mixed well, and unsaturated polyester resin composition (A-13) was obtained.

  About the unsaturated polyester resin compositions of Examples 1-2 and Comparative Examples 1-12 described above, appearance measurement, viscosity measurement, gelation time measurement, odor test, volatilization measurement, tendon adhesion, adhesion amount test, A crack resistance test of the film was performed as follows.

(1) Appearance measurement In accordance with JIS C 2105 (Test method for solvent-free liquid resin for electrical insulation), the varnish appearance when the unsaturated polyester resin (A) and the reactive diluent (B) are mixed is used. Measured visually. The case where the varnish was transparent was evaluated as “◯”, and the case where it was cloudy was evaluated as “×”.

(2) Measurement of varnish viscosity Based on JIS C2105, it measured at 25 degreeC using the Brookfield type | mold viscosity meter.

(3) Gelation time measurement 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 polybeaker having a diameter of 70 mm and a height of 140 mm, covered, and the odor after being left for 1 hour in a 25 ° C. constant temperature bath was organoleptic. The test was 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 Each 10 g of the resin compositions of Examples and Comparative Examples were put in a metal petri dish having 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 mass change.

(6) Shear Adhesive Force As shown in FIGS. 1 (A) and 1 (B), a Stracker test piece was prepared in accordance with JIS C 2105, impregnated with a resin composition for electrical insulation, and 150 ° C., 60 ° C. What was hardened in minutes was used as a test piece, and the shear adhesive strength at 23 ° C. was measured. In FIG. 1, 1 indicates a polyester enameled copper wire having a diameter of 2.0 mm, and 2 indicates a polyester enameled copper wire having a diameter of 0.4 mm.

(7) Adhesion amount test A test piece was prepared by springing 30 polyester enameled copper wires having a diameter of 2.0 mm and a length of 100 mm, and stopped with a polyester enameled copper wire having a diameter of 0.4 mm. A test piece was prepared by dripping and impregnating one side with the resin composition for electrical insulation and curing at 150 ° C. for 60 minutes. The film thickness remaining on the electric wire was measured.
The film thickness of 3 μm or more was evaluated as “◯”, and the film thickness of less than 3 μm was evaluated as “x”.

(8) Crack resistance of film 15 g of the resin compositions of Examples and Comparative Examples were placed in a metal petri dish having a diameter of 60 mm, and allowed to stand in a thermostat at 140 ° C. for 2 hours. After curing, it was allowed to stand in a high-temperature bath at 150 ° C. for 200 hours, and after returning to room temperature (25 ° C.), the state of the varnish cured product was confirmed.
The case where no crack was observed was evaluated as “◯”, and the case where a crack was observed was evaluated as “×”.

  The results of observation, measurement, and evaluation obtained are shown in Tables 2 and 3.

By using a reactive diluent (B) having a vapor pressure of 0.1 mmHg or less at 20 ° C. from Comparative Example 1 in Table 2 and Examples 1 and 2 and Comparative Examples 2 to 12 in Tables 2 and 3, the odor is generated. It can be seen that it is improved. In Comparative Example 2, an unsaturated polyester resin having an acid value of 43 mgKOH / g was used, and when mixed with the reactive diluent (B), a slight turbidity was generated and the amount of adhesion was slightly reduced. When 11 mgKOH / g having an acid value of 30 mgKOH / g or less is used, a slightly yellow transparent composition is obtained. In Comparative Examples 3 and 4, the blending amounts of the components (A) and (B) were changed, and the component (B) was 566 parts (Comparative Example 3) and 100 parts by mass of the component (A). When the blending amount of 6 parts (Comparative Example 4) and the component (B) is deviated from 25 to 400 parts by mass, the varnish viscosity, gelation time, fixing force, adhesion amount, and crack resistance are inferior.
Comparative Examples 5 and 6 are cases in which 0.001 to 10 parts by mass of the blending amount of the non-silicon-based surface conditioner as the component (C) is deviated and affect the varnish viscosity, the adhesion amount, and the crack resistance.
Comparative Examples 7 and 8 are cases in which 0.1 to 20 parts by mass of the blending amount of the alkylbenzene / formaldehyde resin as the component (D) is deviated, and affect the volatilization amount, adhesion, adhesion amount, and crack resistance.
Comparative Examples 9 and 10 are cases where the blending amount of the inorganic filler of the component (E) is out of 20 to 100 parts by mass, and affect varnish viscosity, adhesion amount, and crack resistance.
Comparative Examples 11 and 12 are cases in which 0.1 to 4.5 parts by mass of the blended amount of the organic peroxide that starts the curing reaction at less than 80 ° C. of the component (F), gelation time, volatilization amount Affects adhesion, adhesion amount.
From the results of Tables 2 and 3, since the resin composition for electrical insulation according to the present invention has little odor, it can provide a good working environment and has a good fixing force, so that it can be used for processing a rotor rotating at high speed. Can adapt. In addition, since the viscosity of the resin composition is optimized, it can be used in a wide range of impregnation methods using conventional impregnation equipment. Moreover, the penetration of the varnish of the rectifier part to the stator can be suppressed, and further, the use of a resin-cured resin with a soft film reduces defects such as high-speed rotation, breakage of the connecting wire due to heat, etc. Although the cured film has the same or better cured product characteristics as the type of resin composition, the film becomes flexible, so that it is possible to suppress film cracking due to heat and the like, and thus 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 (8)

  Unsaturated polyester resin (A), reactive diluent (B), non-silicone surface conditioner (C), alkylbenzene / formaldehyde resin (D), inorganic filler (E), and curing reaction started at less than 80 ° C An unsaturated polyester resin composition containing an organic peroxide (F) as an essential material, wherein the vapor pressure at 20 ° C. of component (B) is 0.1 mmHg or less, and 100 of component (A) (C) component is 0.001-10 mass parts, (D) component with respect to 100 mass parts of (B) component 25-400 mass parts and (A) component and (B) component total amount with respect to mass parts, respectively. 0.1 to 20 parts by mass, (E) 20 to 100 parts by mass, and (F) 0.1 to 4.5 parts by mass of an unsaturated polyester resin composition.   The unsaturated polyester resin composition according to claim 1, wherein the acid value of the unsaturated polyester (A) is 30 mgKOH / g or less.   The unsaturated polyester resin composition according to claim 1 or 2, wherein the reactive diluent (B) is a reactive diluent having an unsaturated group.   The unsaturated polyester resin composition according to any one of claims 1 to 3, wherein the non-silicon-based surface conditioner (C) is a vinyl compound or an acrylic compound.   The unsaturated polyester resin composition according to any one of claims 1 to 4, wherein the inorganic filler (E) is silicon dioxide having an average particle size of 1.0 to 10 µm.   Furthermore, the unsaturated polyester resin composition as described in any one of Claims 1-5 containing a stabilizer (G).   The resin composition for electrical insulation formed by containing the unsaturated polyester resin composition in any one of Claims 1-6.   A method for producing an electrical equipment insulator comprising coating and curing with the resin composition for electrical insulation according to claim 7.

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