JP5674026B2 - Thixotropic liquid insulating varnish and electrical equipment insulator and electric motor using the same - Google Patents

Description

  The present invention relates to a thixotropic liquid insulating varnish, an electrical equipment insulator using the same, and an electric motor.

  With the growing awareness of reducing environmental impact, electric motors are required to have high efficiency. In Japan, standards such as JIS C 4212 “High-efficiency low-pressure three-phase squirrel-cage induction motor” and NEMA MG 1 in the United States have been established. It has come to be. In order to increase the efficiency of an electric motor, it is effective to increase the product of the current and the number of turns called an ampere turn, but the ampere turn per unit cross-sectional area is the proportion of the conductor in the coil cross section, that is, the space The higher the rate, the higher it can be. Therefore, the application of a rectangular wire that can increase the space factor to the winding used for the electric motor has been widely studied from the conventional round wire. The problem here is how to make the coil ends of rectangular wires arranged neatly on the motor core in order to increase the space factor. A flat wire generally has a large cross-sectional area and is difficult to be bent or twisted from a square shape. There is a problem in that the insulating enamel film is broken if it is forcibly deformed. In order to avoid this, if the flat wire is deformed loosely at the coil end, the volume is wasted, and the motor is not downsized. In order to solve these problems, Patent Document 1 (Japanese Patent Laid-Open No. 2008-199751) and the like disclose a method of joining the ends of rectangular wires in a welding process. As disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 2004-137903), a powder epoxy resin has been used for insulating the coil end joint.

  As described above, powder epoxy resin has been used to insulate the coil end joint, but since the powder epoxy resin is solid at room temperature, the coil is heated to a temperature at which the powder epoxy resin melts. It is necessary to heat the end so that this portion is brought into contact with the powdered epoxy resin and melted to adhere. For this reason, there is a problem that the permeability to a narrow portion is not sufficient, and in the case of a highly efficient motor such as a motor for driving an automobile, the insulation reliability is inferior. Further, when the powder epoxy resin is adhered to the coil end, it is necessary to make it flow with air or the like so that the powder epoxy resin does not become fooled. The powder epoxy resin generally contains an inorganic filler in order to make it easier to flow like a powder fluid and to improve adhesion. Such a powder epoxy resin has reduced permeability to a narrower portion.

  On the other hand, when trying to insulate the rectangular coil end joint using a conventional liquid insulating varnish, the adhesion of the rectangular wire edge portion was insufficient. For this reason, for example, when a material having a high melt viscosity is used, it is necessary to dissolve in an organic solvent in order to liquefy it. When the adhesion treatment is performed, it is necessary to volatilize the solvent used, and the working environment is poor. In addition, there was a problem that the yield of the varnish material that was volatilized was poor.

  Further, a highly efficient automobile drive motor often employs a system cooled by ATF (abbreviation of automatic transmission fluid) in order to process heat generated during operation. ATF degrades and becomes acidic when used at high temperatures for a long period of time. For this reason, the insulating material for the joint portion of the coil end is required to have a property that the deterioration does not easily proceed even in this acidic environment.

JP 2008-199751 A JP 2004-137903 A

  The present invention achieves both adhesiveness to a flat wire edge part and sufficient permeability even in a narrow part such as a joint part, and is excellent in adhesiveness, storage stability, heat deterioration resistance, acid resistance, and ATF resistance resistance. Furthermore, the present invention provides a thixotropic liquid insulating varnish, an electrical equipment insulator and an electric motor using the same, which have less volatile components, protect the working environment, have a better yield, and have fewer residual bubbles and can be attached.

The present invention relates to the following.
1. (A) polybasic acid or anhydride-modified vinyl ester resin thereof, (b) dicyclopentenyloxyalkyl methacrylate or dicyclopentenyloxyalkyl acrylate, (c) trifunctional acrylate or trifunctional methacrylate, (D) Metal soap, (e) Hydroxyl-terminated liquid polybutadiene and (f) fumed silica, 25 ° C. change rate 2.0 to 8.0 and 25 ° C. viscosity 5.0 Pa · s A thixotropic liquid insulating varnish that is in the range of 50 Pa · s or less.
2. (F) The thixotropic liquid insulating varnish according to Item 1, wherein fumed silica is blended within a range of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of other components.
3. Item 3. The thixotropic liquid insulating varnish according to Item 1 or 2, wherein the polybasic acid or its anhydride-modified vinyl ester resin is a bisphenol-type epoxy resin having a weight average molecular weight of 1000 to 7000.
4). Item 4. The thixotropic liquid insulating varnish according to any one of Items 1 to 3, wherein the glass transition temperature after curing is 90 ° C or higher.
5. Item 5. The thixotropic liquid insulating varnish according to any one of Items 1 to 4, wherein the dispersity measured with a particle gauge is 70 µm or less.
6). Item 6. An electrical equipment insulator obtained by electrical insulation coating with a cured product of the thixotropic liquid insulating varnish according to any one of Items 1 to 5.
7). An electric motor comprising a cured product of the thixotropic liquid insulating varnish according to any one of Items 1 to 5, and covering an end portion of a welded rectangular enameled wire.

  The thixotropic liquid insulating varnish according to the present invention achieves both adhesion to a flat wire edge portion and sufficient permeability even in a narrow part such as a joint, adhesiveness, storage stability, heat deterioration resistance, acid resistance Excellent resistance to ATF deterioration. Furthermore, there are few volatile components, the working environment is protected, the yield is good, the remaining bubbles are few, and adhesion treatment is possible, and the electrical equipment insulation and electric motor obtained by using this thixotropic liquid insulating varnish have the corresponding excellent effects. It is what you play.

The components used in the thixotropic liquid insulating varnish according to the present invention will be described.
The polybasic acid used in the thixotropic liquid insulating varnish according to the present invention or its anhydride-modified vinyl ester resin is a polybasic acid or a vinyl ester resin obtained by reacting an epoxy resin with an unsaturated monobasic acid. An acid anhydride is added and reacted (modified).

  Examples of the epoxy resin used in this synthesis include bisphenol A type epoxy resins, bisphenol AF type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AD type epoxy resins, and bisphenol A alkylene oxide adducts. Bisphenol type epoxy resins such as diglycidyl ether, phenol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthalene novolac type epoxy resins, cresol novolac type epoxy resins and other novolak type epoxy resins, 1,3-diglycidyl-5,5- Heterocyclic epoxy resins such as dimethylhydantoin and triglycidyl isocyanurate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6 Cycloaliphatic epoxy resins such as methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, dipropylene glycol diglycidyl ether, trimethylol Glycidyl esters of polyhydric alcohols such as propane triglycidyl ether, naphthalene diol diglycidyl ether, glycidyl ethers of phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl p-oxybenzoic acid, dimer acid glycidyl ester , Tetraglycidyldiaminodiphenylmethane, tetraglycidyl m-xylenediamine, triglycidyl p-aminophenol, N, N-diglycidyl Glycidylamines such as niline, 2,2 ′, 4,4′-tetraglycidoxybiphenyl, dimethylbisphenol C diglycidyl ether, bis-β-trifluoromethyldiglycidyl bisphenol A, glycidyl methacrylate, aliphatic epoxy resins Epoxidized polybutadiene resin, silicone-modified epoxy resin, etc., which are generally known, and these alkyl-substituted products, halides, hydrogenated products, etc. can also be used in combination, and one or more of these may be used in combination You can also The epoxy resin is preferably a compound having two or more epoxy groups in one molecule.

  Such epoxy resins are commercially available, for example, jER807, jER815, jER825, jER825, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1004AF, jER1007, jER1009, jER1003F, jER1004F (and above, Mitsubishi). Chemical Co., Ltd., trade name), DER-330, DER-331, DER-301, DER-361, DER-661, DER-662, DER-663U, DER-664, DER-664U, DER-667, DER-642U, DER-672U, DER-673MF, DER-668, DER-669 (above, manufactured by The Dow Chemical Company, trade name), Epototo YD8125 Bisphenol A type epoxy resin such as Epototo YDF8170 (trade name, manufactured by Toto Kasei Co., Ltd.), Bisphenol F type epoxy resin such as Epototo YDF-2004 (trade name, manufactured by Toto Kasei Co., Ltd.), jER152, jER154 ( As described above, phenol novolac type such as Mitsubishi Chemical Corporation, trade name), EPPN-201 (Nippon Kayaku Co., Ltd., trade name), DEN-438 (The Dow Chemical Company, trade name), etc. Epoxy resin, jER180S65 (Mitsubishi Chemical Co., Ltd., trade name), Araldite ECN1273, Araldite ECN1280, Araldite ECN1299 (above, Huntsman Advanced Materials (Switzerland) Gezelshaft Mit Beschlenktel Huffung, trade name), Epot YDCN-701, Epototo YDCN-702, Epotot YDCN-703, Epototo YDCN-704 (above, manufactured by Toto Kasei Co., Ltd., trade name), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1012, EOCN -1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd., trade name), ESCN-195X, ESCN-200L, ESCN-220 (above, Sumitomo Chemical Co., Ltd., trade name) Cresol novolac type epoxy resin such as Epon 1031S (manufactured by Shell Chemical Corporation), jER1032H60, jER157S70 (manufactured by Mitsubishi Chemical Corporation, trade name), Araldite 0163 (Huntsman Advanced Materials (Switzerland)) Zellshaft Mit Beschlenktel Huffung, trade name), Denacol EX-611, Denacol EX-614, Denacol EX-614B, Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-421, Denacol EX-411 , Denacol EX-321 (above, Nagase Kasei Co., Ltd., trade name), EPPN501H, EPPN502H (above, Nippon Kayaku Co., Ltd., trade name), etc., polyfunctional epoxy resin, jER604 (Japan Epoxy Resin Co., Ltd.) ), Trade name), YH-434 (manufactured by Toto Kasei Co., Ltd., trade name), TETRAD-X, TETRAD-C (above, trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), ELM-120 (Sumitomo Chemical) Amine-type epoxy resin such as product name), Araldite Heterocyclic epoxy resins such as T810 (Huntsman Advanced Materials (Switzerland) Gesellshaft Mitt Beschlenktel Huffung, trade name), and cycloaliphatic epoxy resins such as Celoxide 2021P (Daicel Chemical Industries, trade name) Etc. are exemplified.

  Examples of the unsaturated monobasic acid used in this synthesis include methacrylic acid, acrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, Examples thereof include hydroxypropyl acrylate malate, monomethyl malate, monopropyl malate, monobutyl malate, mono (2-ethylhexyl) malate, and acrylic acid dimer. These can be used alone or in combination of two or more. .

  From the viewpoint of excellent adhesiveness and heat deterioration resistance of the thixotropic liquid insulating varnish according to the present invention, a bisphenol type epoxy resin is particularly preferable as the epoxy resin, and methacrylic acid is particularly preferable as the unsaturated monobasic acid.

  Although there is no restriction | limiting in particular in the compounding ratio of an epoxy resin and unsaturated monobasic acid, From the point which gives suitable curability to thixotropic liquid insulation varnish, it is unsaturated monobasic acid with respect to 1.0 equivalent of epoxy groups of an epoxy resin. The carboxyl group is preferably in the range of 0.70 to 0.99 equivalents. If it is less than 0.70 equivalent, curability may be reduced, and if it exceeds 0.99 equivalent, gelation tends to occur during synthesis. In this sense, the range of the unsaturated monobasic acid is preferably 0.75 to 0.95 equivalent, and more preferably the unsaturated monobasic acid is 0.80 to 0.90 equivalent, relative to 1.0 equivalent of the epoxy group. It is said.

  The temperature at which the epoxy resin reacts with the unsaturated monobasic acid is not particularly limited, but is preferably in the range of 60 to 160 ° C. If the temperature is lower than 60 ° C., the reaction proceeds remarkably slowly. Conversely, if the temperature exceeds 150 ° C., the reaction tends to be fast and easily gelled. In this sense, the reaction temperature is more preferably in the range of 70 to 150 ° C, still more preferably 90 to 130 ° C.

  In the reaction between the epoxy resin and the unsaturated monobasic acid, it is also preferable to use an esterification reaction catalyst in order to facilitate the esterification reaction and reduce side reactions of the esterification. The reaction catalyst is not particularly limited, and examples thereof include ammonium salts such as trimethylbenzylammonium chloride and pyridinium chloride, tertiary amines such as triethylamine and dimethylaniline, phosphines such as triphenylphosphine, ferric chloride, and lithium chloride. One or more known reaction catalysts such as metal salts such as stannic chloride and hydroxides such as lithium hydroxide can be used.

  When the epoxy resin and the unsaturated monobasic acid are reacted, it is also preferable that a polymerization inhibitor is present in order to prevent gelation. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone, trihydroquinone, monotertiarybutylhydroquinone, and 2,5-ditertiarybutylhydroquinone, parabenzoquinone, tolquinone, naphthoquinone, phenanthraquinone, and 2,5-diphenyl. Quinones such as parabenzoquinone, catechols such as tertiary butyl catechol, 2,6-ditertiarybutylphenol, 2,4-dimethyl-6-tertiarybutylphenol, 2,6-ditertiarybutyl-4-methylphenol, etc. 1 type, or 2 or more types of well-known polymerization inhibitors, such as phenols and organic copper salts, such as copper naphthenate, can be used.

Examples of such polybasic acids or acid anhydrides used for the modification of vinyl ester resins include unsaturated aliphatic dibasic acids such as maleic acid, fumaric acid, and itaconic acid, and saturated aliphatic acids such as adipic acid and pyromellitic acid. There are aromatic saturated polybasic acids such as dibasic acid, phthalic acid, and isophthalic acid, and among these, acid anhydrides can be used.
By using a polybasic acid or its anhydride-modified vinyl ester resin, the adhesiveness of the thixotropic liquid insulating varnish can be effectively improved. From such a viewpoint, maleic acid, fumaric acid, and maleic anhydride are particularly preferable as the polybasic acid or acid anhydride thereof.
Although the thixotropic liquid insulating varnish according to the present invention is used in a state containing substantially no inorganic filler (although in that case, the adhesion generally tends to decrease), the polybasic acid or its acid anhydride-modified vinyl ester resin is used. Good adhesion is obtained by using

  Although there is no restriction | limiting in particular in the compounding ratio of a polybasic acid or its acid anhydride, In the meaning which expresses the outstanding adhesiveness, a carboxyl group conversion (one acid anhydride group is 1 equivalent) with respect to 1.0 equivalent of epoxy groups of an epoxy resin. It is preferable that the amount be in the range of 0.05 to 0.50 equivalent in terms of two carboxyl groups). If it is less than 0.05 equivalent, the adhesion tends to be low, and if it exceeds 0.50 equivalent, the storage stability tends to decrease. In this sense, the polybasic acid or acid anhydride thereof is more preferably in the range of 0.06 to 0.20 equivalent, more preferably 0.07 to 0.15 equivalent, relative to 1.0 equivalent of epoxy group. The

  The temperature at which the polybasic acid or acid anhydride is added and reacted is not particularly limited, but is preferably in the range of 60 to 160 ° C. If the temperature is lower than 60 ° C., the reaction proceeds remarkably slowly. Conversely, if the temperature exceeds 150 ° C., the reaction tends to be fast and easily gelled. In this sense, the reaction temperature is more preferably in the range of 70 to 150 ° C, still more preferably 90 to 130 ° C. The reaction can be carried out in an air atmosphere.

  The weight average molecular weight of the polybasic acid or acid anhydride-modified vinyl ester resin used in the thixotropic liquid insulating varnish according to the present invention is in the range of 1000 to 7000 while maintaining adhesiveness and heat deterioration resistance. The varnish is preferable because it is easy to handle, adheres to the edge of a flat wire, and has sufficient permeability even in a narrow part such as a joint. The weight average molecular weight in the present invention is a polystyrene conversion value using a calibration curve with standard polystyrene by gel permeation chromatography. If the weight average molecular weight of the polybasic acid or acid anhydride-modified vinyl ester resin is less than 1000, the adhesiveness and the heat deterioration resistance may decrease, and if it exceeds 7000, sufficient permeability tends not to be obtained. . In this sense, the weight average molecular weight is more preferably 1500 to 6500, and still more preferably 2000 to 6000.

  The acid value of the polybasic acid or acid anhydride-modified vinyl ester resin used in the thixotropic liquid insulating varnish according to the present invention is not particularly limited, but is preferably in the range of 1 to 20 KOHmg / g.

  The thixotropic liquid insulating varnish according to the present invention includes dicyclopentenyloxyalkylene methacrylate or dicyclopentenyloxyalkylene acrylate as a reactive diluent for polybasic acid or its anhydride-modified vinyl ester resin. And trifunctional acrylates are used.

  By using dicyclopentenyloxyalkylene methacrylate or dicyclopentenyloxyalkylene acrylate, good curability and good yield without deteriorating the work environment with a volatile content of 5% or less until the completion of curing. A processable thixotropic liquid insulating varnish can be obtained. As the alkylene group of dicyclopentenyloxyalkyl methacrylate or dicyclopentenyloxyalkyl acrylate, there are ethylene group, propylene group, butylene group, etc., and the compound is dicyclopentenyloxyethyl methacrylate. Particularly preferred.

  Further, by using trifunctional acrylate or trifunctional methacrylate, the glass transition temperature of the cured product of the thixotropic liquid insulating varnish according to the present invention can be easily increased. For example, the glass transition temperature can be easily increased to 90 ° C. As a result, a thixotropic liquid insulating varnish excellent in heat-resistant deterioration as a result can be easily obtained.

  The glass transition temperature in the present invention is a peak top temperature of loss tangent (tan δ) measured by changing the temperature with a dynamic viscoelastic property measuring apparatus. The dynamic viscoelastic property measuring apparatus is described in T.W. A. Instruments such as RSAIII manufactured by Instruments are commercially available.

  The trifunctional acrylate or trifunctional methacrylate used in the thixotropic liquid insulating varnish according to the present invention is a compound having three acrylolyl groups or methacryloyl groups in one molecule, specifically, trimethylolmethane triacrylate, Methylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, pentaerythritol triacrylate, glycerin propoxytriacrylate, tris (2-acryloyloxyethyl) isocyanurate, trimethylolmethane trimethacrylate, Trimethylolpropane trimethacrylate, trimethylolpropane ethylene oxide modified trimethacrylate, trimethylolpropane Chi trimethylolpropane propylene oxide-modified trimethacrylate, pentaerythritol trimethacrylate, glycerol propoxy trimethacrylate, tris (2-methacryloyloxyethyl) isocyanurate and the like, may be used in combination one or more of these.

（ただし、式中ｋ、ｍ及びｎは、それぞれ独立に１〜２０の整数である）で表される化合物である。
また、トリメチロールプロパンプロピレンオキサイド変性トリアクリレートは、上記構造式（Ｉ）において、すべてのエチレンオキシ基のエチレン基を、プロピレン基、例えば、構造式（ＩＩ）

で表される基で置換した化合物である。 The trimethylolpropane ethylene oxide-modified triacrylate has the following structural formula (I)

(Wherein, k, m and n are each independently an integer of 1 to 20).
Further, the trimethylolpropane propylene oxide-modified triacrylate is the above-mentioned structural formula (I) wherein all ethyleneoxy groups are converted to propylene groups such as structural formula (II).

It is a compound substituted by group represented by these.

  In addition, trimethylolpropane ethylene oxide modified trimethacrylate and trimethylolpropane propylene oxide modified trimethacrylate are all acryloyl groups of the above trimethylolpropane ethylene oxide modified triacrylate and trimethylolpropane propylene oxide modified triacrylate, respectively. Is a compound substituted with

Trimethylolpropane ethylene oxide-modified triacrylate is a product name of Miramer M3130, Miramer M3160, Miramer M3190 as trimethylolpropane EO-modified triacrylate from Toyo Chemicals Co., Ltd. It is marketed under the trade name TMPEOTA under the trade name V # 360 as trimethylolpropane ethoxytriacrylate by Daicel Cytec Co., Ltd.
In addition, Sartomer Yuesuei LLC (Sartomer USA, LLC) from, SR9035 [ETHOXYLATED (15) TRIMETHYLOLPROPANE TRIACRYLATE], SR454 [ETHOXYLATED (3) TRIMETHYLOLPROPANE TRIACRYLATE], SR454HP [ETHOXYLATED (3) TRIMETHYLOLPROPANE TRIACRYLATE], SR499 [ETHOXYLATED ( 6) TRIMETHYLOLPROPANE TRIACRYLATE], SR502 [ETHOXYLATED (9) TRIMETHYLOLPROPANE TRIACRYLATE], SR415 [ETHOXYLATED (20) TRIMET YLOLPROPANE TRIACRYLATE] and trimethylolpropane propylene oxide modified triacrylate are commercially available from Toyo Chemicals as trimethylolpropane PO modified triacrylate under the product name Miramer M360. Can be used.

  The amount of dicyclopentenyloxyalkyl methacrylate or dicyclopentenyloxyalkyl acrylate (referred to as “component (b)”), trifunctional acrylate or trifunctional methacrylate (referred to as “component (c)”) is particularly Although there is no limitation, Preferably, (b) component 100-300 weight part, (c) component with respect to 100 weight part of polybasic acid or its acid anhydride modified vinyl ester resin [referred to as "(a) component"] The range is 20 to 120 parts by weight. There is a tendency that good curability cannot be obtained in any case of less than 100 parts by weight or more than 300 parts by weight of component (b) with respect to 100 parts by weight of component (a). In this sense, component (b) Is more preferably 115 to 280 parts by weight, and still more preferably 130 to 240 parts by weight. Further, when the component (c) is less than 20 parts by weight relative to 100 parts by weight of the component (a), the glass transition point temperature tends to be low and the required heat resistance tends not to be obtained. The elastic modulus tends to be too high and tends to be hard and brittle. In this sense, the component (c) is more preferably in the range of 25 to 115 parts by weight, still more preferably 30 to 110 parts by weight.

  In the thixotropic liquid insulating varnish according to the present invention, a metal soap such as cobalt octenoate, cobalt naphthenate, potassium octenoate, manganese naphthenate, copper naphthenate, etc. is used as a curing accelerator (referred to as “(d) component”). Can be blended. By using metal soap, curability can be improved. From this viewpoint, manganese-containing metal soaps such as manganese naphthenate are particularly preferable. The blending amount of the metal soap is determined by the metal content and the pot life required for the curing process, and is not particularly limited. However, the total amount of the component (a), the component (b) and the component (c) is 100% by weight. The metal content is preferably in the range of 0.004 to 0.4 parts by weight with respect to parts. If the amount of metal soap is small, sufficient curability cannot be improved. If the amount is too large, gelation is too fast and the pot life required for the curing process may not be obtained. In this sense, the metal soap has a metal content of more preferably 0.008 to 0.16 parts by weight, more preferably 100 parts by weight of the total amount of the components (a), (b) and (c). 0.016 to 0.08 parts by weight are used. Here, the pot life required for the curing step is the time from the addition of the curing agent to the gelation of the thixotropic liquid insulating varnish, and generally 1 to 30 minutes at 120 ° C. Range. Metal soap is often used after being dissolved in a solvent such as a hydrocarbon solvent such as mineral spirit, and such a solution may be used for blending. When making a solution, the concentration of the metal soap is preferably, for example, 3 to 50% by weight in terms of metal content.

  The thixotropic liquid insulating varnish according to the present invention may contain a hydroxyl-terminated liquid polybutadiene [referred to as “(e) component”] as an antifoaming agent. In particular, when the thixotropic liquid insulating varnish according to the present invention does not substantially contain an inorganic filler, the defoaming property is lowered, and if used as it is, residual bubbles are formed, and there is a possibility that sufficient insulating performance cannot be exhibited. It is preferable to blend a hydroxyl-terminated liquid polybutadiene as an antifoaming agent.

  (E) Although the compounding quantity of a component does not have a restriction | limiting in particular, It uses in the range of 0.05-5.0 weight part with respect to 100 weight part of total amounts of (a) component, (b) component, and (c) component. It is preferable to do. (A) Component, (b) component and (c) 100 parts by weight of the total amount of component (e) Component is defoaming in any case less than 0.05 parts by weight or more than 0.5 parts by weight The improvement effect tends to decrease. In this sense, the component (e) is more preferably in the range of 0.1 to 2.0 parts by weight, and still more preferably in the range of 0.2 to 1.0 parts by weight.

  The thixotropic liquid insulating varnish according to the present invention uses fumed silica (referred to as “component (f)”) as a thixotropic agent. By using fumed silica, a thixotropic liquid insulating varnish is set to a grade suitable for adhesion treatment with a 25 ° C. variation of 2.0 to 8.0 and a 25 ° C. viscosity of 5.0 to 50 Pa · s. it can. The throttling degree and the viscosity in the present invention are measured by a BH type rotary viscometer according to JIS K 6901.

  The thixotropic liquid insulating varnish according to the present invention is set to a grade suitable for adhesion treatment with a 25 ° C. variation of 2.0 to 8.0 and a 25 ° C. viscosity of 5.0 to 50 Pa · s. It is necessary. A fluctuation degree at 25 ° C. of less than 2.0 or a viscosity at 25 ° C. of less than 5.0 Pa · s is a factor that sufficient adhesion cannot be obtained. For example, an edge portion of a rectangular wire ( The flat wire has a rectangular cross-section, but the film thickness becomes extremely thin at the corners), and sufficient insulation reliability cannot be obtained. On the other hand, if the degree of change at 25 ° C. exceeds 8.0 or the viscosity at 25 ° C. exceeds 50 Pa · s, sufficient defoaming properties cannot be obtained and residual bubbles remain. Sufficient insulation reliability cannot be obtained. In this sense, the thixotropic liquid insulating varnish according to the present invention is more preferably that the degree of change at 25 ° C. is 3.0 to 7.0 and the viscosity at 25 ° C. is 10 to 30 Pa · s, It is more preferable that the degree of change is 3.5 to 6.5 and the viscosity at 25 ° C. is 12 to 28 Pa · s.

  (F) Component may be blended in the range of 3 to 20 parts by mass with respect to 100 parts by mass of the total amount of component (a), component (b), (c), (d) and (e). , Grade suitable for adhesion treatment to thixotropic liquid insulating varnish, that is, effective to set the degree of change at 25 ° C to 2.0-8.0 and the viscosity at 25 ° C to 5.0-50 Pa · s It is. In this sense, the component (f) is added in an amount of 3.5 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (a), (b), (c), (d) and (e). More preferably, it is blended in the range of 4 to 10 parts by mass.

It is particularly effective that the average diameter of the primary particles of the fumed silica [component (f)] is in the range of 5 to 50 nm. If it is less than 5 nm, the fumed silica tends to aggregate, and if it exceeds 50 nm, the necessary thixotropy tends not to be obtained. In this sense, the average diameter of the fumed silica primary particles is more preferably in the range of 7 to 30 μm, and even more preferably in the range of 10 to 20 nm. By doing in the above way, the effect of using fumed silica can be made more reliable.
The average diameter of the primary particles in the present invention is measured by observation with a scanning electron microscope.

  Fumed silica is surface treated with fatty acids, rosin acid, various coupling agents, etc. to avoid agglomeration and to improve dispersibility when producing the thixotropic liquid insulating varnish according to the present invention. May be used.

Other examples of the thixotropic agent include colloidal calcium carbonate. However, calcium carbonate including heavy calcium carbonate and light calcium carbonate has a drawback that it is easily deteriorated in an acidic atmosphere. When the above quality is set using colloidal calcium carbonate, the filling amount increases. For example, when a system cooled by ATF, such as a high-efficiency automobile drive motor, is used, the ATF can be used under a long-term high temperature. Since it deteriorates and becomes acidic by use, deterioration is feared, which is not preferable. For this reason, it is indispensable to use fumed silica having high thixotropic properties with a small amount of filling and excellent acid resistance in the thixotropic liquid insulating varnish of the present invention.
In the thixotropic liquid insulating varnish according to the present invention, in addition to fumed silica and calcium carbonate, crystalline silica, amorphous silica, molten, as thixotropic agent, as long as the effects of the invention described above are not impaired. Silica, magnesium oxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, aluminum borate whisker, nitride One or more known thixotropic agents such as boron, clay, talc and barium sulfate may be used in combination.

  Concealing the electrical insulation part of the electrical equipment means, for example, that not only the appearance where the conductor metal is exposed is not seen to improve the appearance, but also that the electrical insulation is ensured visually. This is an important function for the insulating material to be confirmed. In order to impart this concealing property, for example, titanium oxide having a high refractive index of 2.5 or higher can be raised, but there is also a drawback that the specific gravity is as high as 4 and tends to settle.

  Although calcium carbonate has a refractive index of 1.6, it has a sufficient concealing property as long as it is a level for visually confirming that electrical insulation is reliably performed, and has a specific gravity of 2.6 and dispersion stability. Also excellent. However, since calcium carbonate has the disadvantage of poor acid resistance as described above, when used in combination, the total amount of component (a), component (b), component (c), component (d) and component (e) Calcium carbonate is made into the range of 1-25 mass parts with respect to 100 mass parts. If the amount is less than 1 part by weight, the concealability may be insufficient. If the amount exceeds 25 parts by weight, the acid resistance of the thixotropic liquid insulating varnish tends to be reduced. In this sense, the calcium carbonate has a range of 2 to 20 parts by mass with respect to 100 parts by mass of the total amount of the components (a), (b), (c), (d) and (e). The range of 3 to 15 parts by mass is more preferable.

  In addition, the thixotropic liquid insulating varnish according to the present invention has an epoxy resin, a polyimide resin, a polyamideimide resin, a triazine resin, and a phenol resin in addition to the above-described essential components as long as the effects of the above-described invention are not impaired. , One or more of thermosetting resins such as melamine resin, urea resin, urethane resin, unsaturated polyester resin, alkyd resin, silicone resin, cyanate ester resin, and modified resins of these resins are used as essential components. Can be used.

  In the thixotropic liquid insulating varnish according to the present invention, an acrylic random copolymer such as polymethyl methacrylate, a thermoplastic plastic such as polystyrene, polyvinyl acetate, and saturated polyester, as long as the effects of the present invention are not impaired. In addition, one or more kinds such as a cross-linked reaction rubber, a thermoplastic elastomer, and a phenoxy resin can be used in combination with essential components.

  The thixotropic liquid insulating varnish according to the present invention can be used in combination with reactive diluents other than the component (b) and the component (c) as long as the effects of the invention described above are not impaired. Other examples of volatile components up to 5% or less that can be processed with good yield without deteriorating the working environment include orthodiallyl phthalate and isodiallyl phthalate, but the curability tends to decrease. Therefore, care must be taken when blending. In any case, the reactive diluent used in the thixotropic liquid insulating varnish according to the present invention has a curing temperature, that is, a flash point of 160 ° C. or more, and curing of a polybasic acid or its anhydride-modified vinyl ester resin. It will be excellent.

  In the thixotropic liquid insulating varnish according to the present invention, as long as it does not inhibit the effects of the above-described invention, one or more kinds such as tertiary amines such as dimethylaniline and diethylaniline are used as a curing accelerator. Can be used in combination with essential ingredients.

  In the thixotropic liquid insulating varnish according to the present invention, as long as the effect of the invention described above is not impaired, as an antifoaming agent, in addition to the hydroxyl-terminated liquid polybutadiene, an alkyl vinyl ether copolymer system, an acrylic polymer system, One or more known antifoaming agents such as polysiloxane, polydimethylsiloxane, and silicon can be used in combination as essential components.

  Furthermore, various coupling agents can be added to the thixotropic liquid insulating varnish according to the present invention within a range that does not impair the effects of the present invention in order to improve the bonding and wettability of the interface between the materials. There is no restriction | limiting in particular as a coupling agent, A silane type, a titanium type, an aluminum type etc. are mentioned, These 1 type (s) or 2 or more types can also be used together.

  Examples of the silane coupling agent include vinyl silanes such as vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxy. Methacryloylsilanes such as propylmethyldimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, methyltri (methacryloyloxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltri Epoxy group-containing silanes such as methoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and methyltri (glycidyloxy) silane N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, N-β- Aminoethyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl-tris (2-methoxy) -Ethoxy-ethoxy) silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3- (4,5-dihydroimidazol-1-yl) -propyltrimethoxysilane, amyltrichlorosilane Aminosilanes such as , Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercaptosilanes such as 3-mercaptopropyl-methyldimethoxysilane, urea linkages such as 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane -Containing silanes, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxysilane isocyanate and other isocyanate group-containing silanes, 3-chloropropyl-methyldimethoxysilane, 3 -Chloropropyl-dimethoxysilane, 3-cyanopropyl-triethoxysilane, hexamethyldisilazane, N, N- Bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, γ- And chloropropylmethyldiethoxysilane. As for the silane coupling agent, γ-glycidoxypropyltrimethoxysilane is NUC A-187, γ-mercaptopropyltrimethoxysilane is NUC A-189, γ-aminopropyltriethoxysilane is NUC A-1100, γ-ureido. Propyltriethoxysilane is commercially available from Nippon Unicar Co., Ltd. under the trade names NUC A-1160 and N-β-aminoethyl-γ-aminopropyltrimethoxysilane as NUC A-1120.

  Titanium coupling agents include, for example, isopropyl trioctanoyl titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate , Isopropyltris (dioctylpyrophosphate) titanate, isopropyltris (n-aminoethyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl) -1-butyl) bis (ditridecyl) phosphite titanate, dicumylf Nyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, polytitanium acetylacetonate, titanium octyl Len glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium triethanolamate, polyhydroxy titanium stearate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate , Cresyl titanate monomer, cresyl titanate polymer Diisopropoxy-bis (2,4-pentadionate) titanium (IV), diisopropyl-bis-triethanolamino titanate, octylene glycol titanate, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate Examples thereof include polymers and tri-n-butoxy titanium monostearate.

  Examples of the aluminum coupling agent include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetyl acetate bis (ethyl acetoacetate), aluminum tris (acetylacetate). Nate), aluminum monoisopropoxy mono-oroxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethyl acetoacetate, aluminum chelate compounds such as aluminum-di-iso-propoxide-mono-ethyl acetoacetate, aluminum isopropiate Rate, mono-sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate, al Aluminum alcoholate such as iodonium ethylate and the like.

  Furthermore, in the thixotropic liquid insulating varnish according to the present invention, various ion scavengers are added within a range that does not impair the effects of the above-mentioned invention in order to adsorb or adhere ionic impurities and improve the insulation reliability at the time of moisture absorption. It can also be added. The ion scavenger is not particularly limited, and is a compound known as a copper damage inhibitor to prevent copper from being ionized and dissolved, for example, triazine thiol compound, bisphenol-based reducing agent, zirconium-based, antimony bismuth, and the like. And inorganic ion adsorbents such as magnesium aluminum compounds can be used, and one or more of these can be used in combination.

  Furthermore, the thixotropic liquid insulating varnish according to the present invention includes flame retardants such as bromotoluene, hexabromobenzene, antimony trioxide, chlorinated paraffin, carbon black, bengara, titanate, and the like within the range not impairing the effects of the present invention. Various additives such as a colorant and a flow modifier can also be added.

The thixotropic liquid insulating varnish according to the present invention preferably has a dispersity measured by a particle gauge of 70 μm or less. The degree of dispersion in the present invention is measured by a particle gauge according to JIS K 5600-2-5. If the degree of dispersion exceeds 70 μm, thixotropy may not be sufficient, or grains may be raised on the surface of the cured product and the appearance may be impaired. The degree of dispersion can be adjusted by uniformly stirring and mixing the components used in the thixotropic liquid insulating varnish according to the present invention. The method for uniformly stirring and mixing the components of the thixotropic liquid insulating varnish according to the present invention is not particularly limited, for example, a dissolver, a static mixer, a homogenizer, an ultrasonic homogenizer, a paint shaker, a ball mill, a planetary mixer, Examples include a method of using a kneading apparatus such as a revolving and revolving stirrer such as a mixed rotor or a universal stirrer, a reiki machine, or a three roll. After stirring and mixing, it is preferable to remove bubbles in the thixotropic liquid insulating varnish. In this sense, the rotation and revolution type stirrer is preferably used because it can perform mixing, dissolution and removal of bubbles at the same time.
It is preferable that a physical shearing force is applied by a reika machine, a three-roller, a ball mill, a bead mill, or the like and sufficiently dispersed so that there are no aggregated particles. These dispersion methods can also be performed in combination. At this time, when a material having low hardness and easily crushed is used, care should be taken because a desired viscosity may not be obtained if the material is crushed and crushed by a shearing force.
According to such an adjustment method, the lower limit of the degree of dispersion is usually 10 μm.

Next, a method for using the thixotropic liquid insulating varnish according to the present invention will be described.
The thixotropic liquid insulating varnish according to the present invention can be cured using an organic peroxide as a curing agent. The organic peroxide is not particularly limited. For example, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide and cyclohexanone peroxide, diacyl peroxides such as benzoyl peroxide and isobutyl peroxide, cumene Hydroperoxides such as hydroperoxide and t-butyl hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, 1,1-di-t-butylperoxy-cyclohexane, 1,1-di-t-butylperoxy-2-methylcyclohexane, 1,1-di-t-hexylperoxy-cyclohexane, 1,1-di-t-hexylperoxy-3,3,5-trimethyl Cyclohexane, 2,2-di-4,4-di Peroxyketals such as t-butylperoxy-cyclohexyl-propane, 2,2-di- (t-butylperoxy) -butane, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexa No alkylates such as noate, t-amylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 2,4,4-trimethylpentylperoxy-2-ethylhexanoate Examples thereof include parkers such as esters, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butylperoxyisobutylcarbonate, and the like, and heat curing can be performed using these. These organic peroxides can be used alone or in combination of two or more.

The thixotropic liquid insulating varnish according to the present invention is suitably cured in the range of 80 to 160 ° C. from the viewpoint of processing efficiency, safety, and work environment. In this sense, the above-mentioned known organic peroxidation is used. Of these, peroxyketals are preferably used. 1,1-di-t-butylperoxy-cyclohexane is particularly preferred.
The thixotropic liquid insulating varnish according to the present invention is preferably used by being mixed with a curing agent immediately before application to an application because of its usable life.

  The compounding amount of the organic peroxide is determined by the concentration of the organic peroxide and the required pot life, and is not particularly limited. However, the component (a), the component (b), the component (c), ( The range of 0.35 to 3.5 parts by weight is preferable with respect to 100 parts by weight of the total amount of component d) and component (e). If the amount of organic peroxide is too small, sufficient curability cannot be obtained, and if it is too large, gelation is too fast and sufficient pot life cannot be obtained. In this sense, the organic peroxide is more preferably in the range of 0.49 to 2.1 parts by weight, further preferably 0.7 to 1.4 parts by weight.

  In view of storage stability, the organic peroxide is preferably stored and used by mixing with an inert substance such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate. Care is taken not to use too much inert material so as not to inhibit the activity of the organic peroxide. The amount of inert material used varies depending on the type of organic peroxide, so it cannot be generally stated. From this point of view, the inert material is 25 to 35% by weight based on the total amount of the organic peroxide and the inert material. It is preferable that

  The electrical equipment insulator according to the present invention can be manufactured by coating at least an insulating portion with the thixotropic liquid insulating varnish according to the present invention and curing. The thixotropic liquid insulating varnish according to the present invention is attached to electrical and electronic parts by any method such as casting, impregnation, lamination, coating, molding, etc., and cured by the above-described method to be used as a cured product. In particular, the electric motor according to the present invention can be manufactured by coating at least the exposed portion of the end portion of the welded rectangular enameled wire with the thixotropic liquid insulating varnish according to the present invention and curing.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the following mixing | blending and evaluation were performed in the air | atmosphere of room temperature 18-25 degreeC, when there is no description in particular.

  Into a 2 liter four-necked flask equipped with a heating device, a thermometer, and a stirrer was charged 1665 g of jER1001 (bisphenol A-based epoxy resin, Japan Epoxy Resin Co., Ltd., epoxy equivalent 475), and the temperature was raised to 100 ° C. Thereafter, 0.8 g of hydroquinone was added, and 260 g of methacrylic acid was subsequently added and stirred well, then 5.0 g of trimethylbenzylammonium chloride was added, and the temperature was further raised to 120 ° C. to react to an acid value of 10 KOH mg / g. To this was added 19 g of maleic anhydride to obtain a maleic anhydride-modified vinyl ester resin V1 having an acid value of 13 KOH mg / g. The reaction was performed in an air atmosphere.

  In a cylindrical container, 30 parts by weight of V1, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, 10 parts by weight of trimethylolpropane EO-modified triacrylate (using Toyo Chemicals trade name Miramer M3130), 8 parts of manganese 0.5% by weight of manganese naphthenate (a solution of manganese naphthenate dissolved in a hydrocarbon solvent so that the amount of manganese is 8% by weight; the same applies hereinafter), poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd. ) Product name) Add 0.5 parts by weight, and stir at 300 rpm for 5 minutes with a stirrer equipped with a Disper type stirring blade. AEROSIL R972CF (fumed silica, product name of Nippon Aerosil Co., Ltd.) 6 Gradually add part by weight so as not to be fooled, stir at 300 rpm for 30 minutes, then reduce And defoamed to obtain a thixotropic liquid insulating varnish J1.

  In a cylindrical container, 100 parts by weight of J1 and 70% by weight of 1,1-di-t-butylperoxy-cyclohexane (70% by weight of 1,1-di-t-butylperoxy-cyclohexane and 2,2,4 -Use a mixture of 30% by weight of trimethyl-1,3-pentanediol diisobutyrate; the same applies below), stir well with an ointment spatula for 3 minutes, degassed under reduced pressure, and contains a curing agent A thixotropic liquid insulating varnish JP1 was obtained.

In a cylindrical container, 30 parts by weight of V1 obtained in Example 1, 40 parts by weight of dicyclopentenyloxyethyl methacrylate, trimethylolpropane EO-modified triacrylate (using the product name Miramer M3130, Toyo Chemicals Co., Ltd.) 30 parts by weight, manganese 8% by weight manganese naphthenate 0.5 part by weight, Poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd.) 0.5 part by weight, and a stirrer equipped with a Disper type stirring blade At 300 rpm for 5 minutes, gradually add 6 parts by weight of AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd.) to the material being stirred, and stir at 300 rpm for 30 minutes. By defoaming, a thixotropic liquid insulating varnish J2 was obtained.
Take 100 parts by weight of J1 and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane in a cylindrical container, stir well with an ointment spatula for 3 minutes, and then degas under reduced pressure. A thixotropic liquid insulating varnish JP2 containing a curing agent was obtained.

A 2-liter four-necked flask equipped with a heating device, a thermometer, and a stirrer was mixed with 952 g of EPOMIC R140 (bisphenol A epoxy resin, trade name of Mitsui Petrochemical Co., Ltd., epoxy equivalent 189) and jER1001 (bisphenol A epoxy resin, 514 g of Japan Epoxy Resin Co., Ltd. trade name) is charged and heated to 100 ° C. Thereafter, 0.8 g of hydroquinone was charged, and subsequently 455 g of methacrylic acid was charged and stirred well. Then, 5.0 g of trimethylbenzylammonium chloride was charged, and the temperature was raised to 120 ° C. to react to an acid value of 10 KOH mg / g. To this was added 31 g of maleic anhydride to obtain a maleic anhydride-modified vinyl ester resin V2 having an acid value of 13 KOH mg / g. The reaction was performed in an air atmosphere.
In a cylindrical container, 30 parts by weight of V2, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, 10 parts by weight of trimethylolpropane EO-modified triacrylate (using the trade name Miramer M3130, Toyo Chemicals), manganese 8 Add 0.5% by weight of manganese naphthenate by weight, 0.5 part by weight of poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd.), and stir at 300 rpm for 5 minutes with a stirrer equipped with a Disper type stirring blade. Then, gradually add 6 parts by weight of AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd.) to the stirring material so that it does not become confused, stir at 300 rpm for 30 minutes, degassed under reduced pressure, and shaken. A modified liquid insulating varnish J3 was obtained.
Take 100 parts by weight of J3 and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane in a cylindrical container, stir well with an ointment spatula for 3 minutes, and then degas the vacuum. A thixotropic liquid insulating varnish JP3 containing a curing agent was obtained.

In a cylindrical container, 30 parts by weight of V1 obtained in Example 1, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, trimethylolpropane EO-modified triacrylate (using the product name Miramer M3130, Toyo Chemicals Co., Ltd.) 10 parts by weight, manganese 8% by weight manganese naphthenate 0.5 part by weight, Poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd.) 0.5 part by weight, and a stirrer equipped with a Disper type stirring blade 5 minutes by weight of AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd. trade name), Calfine 200M (colloidal calcium carbonate, Maruo calcium trade name) 5 weight Gradually add part so as not to be fooled, stir at 300 rpm for 30 minutes, Degassing under reduced pressure gave thixotropic liquid insulating varnish J4.
Take 100 parts by weight of J4 and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane in a cylindrical container, stir well with an ointment spatula for 3 minutes, and then degas under reduced pressure. A thixotropic liquid insulating varnish JP4 containing a curing agent was obtained.

(Comparative Example 1)
In a cylindrical container, 30 parts by weight of V1 obtained in Example 1, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, trimethylolpropane EO-modified triacrylate (using the product name Miramer M3130, Toyo Chemicals Co., Ltd.) 10 parts by weight, manganese 8% by weight manganese naphthenate 0.5 part by weight, Poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd.) 0.5 part by weight, and a stirrer equipped with a Disper type stirring blade After stirring at 300 rpm for 5 minutes, gradually adding 40 parts by weight of Calfine 200M (colloidal calcium carbonate, trade name of Maruo Calcium Co., Ltd.) to the material being stirred, and stirring at 300 rpm for 30 minutes, Degassing under reduced pressure gave thixotropic liquid insulating varnish H1.

  Take 100 parts by weight of H1 in a cylindrical container and 1.1 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane, stir well with an ointment spatula for 3 minutes, and then degas under reduced pressure. A thixotropic liquid insulating varnish HP1 containing a curing agent was obtained.

(Comparative Example 2)
To a 2 liter four-necked flask equipped with a heating device, a thermometer and a stirrer, 1665 g of jER1001 (bisphenol A epoxy resin, trade name of Japan Epoxy Resin Co., Ltd.) was charged, and the temperature was raised to 100 ° C. Thereafter, 0.8 g of hydroquinone was added, and 260 g of methacrylic acid was added and stirred well. Then, 5.0 g of trimethylbenzylammonium chloride was added, and the mixture was further heated to 120 ° C. to react to an acid value of 9 KOH mg / g. V3 was obtained. The reaction was performed in an air atmosphere.
In a cylindrical container, 30 parts by weight of V3, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, 10 parts by weight of trimethylolpropane EO-modified triacrylate (using Toyo Chemicals trade name Miramer M3130), manganese 8 Add 0.5% by weight of manganese naphthenate by weight, 0.5 part by weight of poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd.), and stir at 300 rpm for 5 minutes with a stirrer equipped with a Disper type stirring blade. Then, gradually add 6 parts by weight of AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd.) to the stirring material so that it does not become confused, stir at 300 rpm for 30 minutes, degassed under reduced pressure, and shaken. A modified liquid insulating varnish H2 was obtained.

  Take 100 parts by weight of H2 in a cylindrical container and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane, stir well with an ointment spatula for 3 minutes, and then degas under reduced pressure. A thixotropic liquid insulating varnish HP2 containing a curing agent was obtained.

(Comparative Example 3)
In a cylindrical container, 30 parts by weight of V1 obtained in Example 1, 70 parts by weight of styrene, 0.5 parts by weight of manganese 8% by weight manganese naphthenate, Poly bd (hydroxyl-terminated liquid polybutadiene, Idemitsu Kosan Co., Ltd., trade name) ) Add 0.5 parts by weight, and stir at 300 rpm for 5 minutes with a stirrer equipped with a disperser-type stirring blade. Add 6 parts by weight of AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd. trade name) to the material being stirred. The mixture was gradually added so as not to be confused, stirred at 300 rpm for 30 minutes, and then degassed under reduced pressure to obtain a thixotropic liquid insulating varnish H3.

  Take 100 parts by weight of H3 and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane in a cylindrical container and stir well with an ointment spatula for 3 minutes, then degassed under reduced pressure. A thixotropic liquid insulating varnish HP3 containing a curing agent was obtained.

(Comparative Example 4)
30 parts by weight of V1 obtained in Example 1, 70 parts by weight of dicyclopentenyloxyethyl methacrylate, 0.5 parts by weight of manganese 8% by weight manganese naphthenate, Poly bd (hydroxyl-terminated liquid polybutadiene) , Idemitsu Kosan Co., Ltd. (trade name) 0.5 parts by weight was added and stirred at 300 rpm for 5 minutes with a stirrer equipped with a Disper-type stirring blade. AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd.) was used as the stirring material. ) Product name) 6 parts by weight were gradually added so as not to be confused, stirred at 300 rpm for 30 minutes, and then degassed under reduced pressure to obtain thixotropic liquid insulating varnish H4.

  Take 100 parts by weight of H4 in a cylindrical container and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane, stir well with an ointment spatula for 3 minutes, and then degas under reduced pressure. A thixotropic liquid insulating varnish HP4 containing a curing agent was obtained.

(Comparative Example 5)
In a cylindrical container, 30 parts by weight of V1 obtained in Example 1, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, trimethylolpropane EO-modified triacrylate (using the product name Miramer M3130, Toyo Chemicals Co., Ltd.) Add 10 parts by weight, 0.5 parts by weight of Poly bd (hydroxyl-terminated liquid polybutadiene, trade name of Idemitsu Kosan Co., Ltd.), and stir at 300 rpm for 5 minutes with a stirrer equipped with a disperser type stirring blade. 6 parts by weight of AEROSIL R972CF (fumed silica, Nippon Aerosil Co., Ltd.) is gradually added so as not to be fooled, stirred at 300 rpm for 30 minutes and then degassed under reduced pressure to obtain thixotropic liquid insulating varnish H5 It was.

  Take 100 parts by weight of H5 in a cylindrical container and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane, stir well with an ointment spatula for 3 minutes, and degas the vacuum. A thixotropic liquid insulating varnish HP5 containing a curing agent was obtained.

(Comparative Example 6)
In a cylindrical container, 30 parts by weight of V1 obtained in Example 1, 60 parts by weight of dicyclopentenyloxyethyl methacrylate, trimethylolpropane EO-modified triacrylate (using the product name Miramer M3130, Toyo Chemicals Co., Ltd.) Add 10 parts by weight and 0.5 parts by weight of manganese 8% by weight manganese naphthenate and stir at 300 rpm for 5 minutes with a stirrer equipped with a disperser type stirring blade. AEROSIL R972CF (fumed silica, Nippon Aerosil) (Trade name) 6 parts by weight were gradually added so as not to be fooled, stirred at 300 rpm for 30 minutes, and then degassed under reduced pressure to obtain thixotropic liquid insulating varnish H6.

  Take 100 parts by weight of H6 in a cylindrical container and 1.4 parts by weight of 70% by weight of 1,1-di-t-butylperoxy-cyclohexane, stir well with an ointment spatula for 3 minutes, and then degas under reduced pressure. A thixotropic liquid insulating varnish HP6 containing a curing agent was obtained.

The maleic anhydride-modified vinyl ester resin was evaluated by the following method. The results are shown in Table 1.
The acid value was measured by an indicator titration method according to JIS K 6901.
The weight average molecular weight was calculated by a polystyrene conversion value using a standard polystyrene calibration curve by gel permeation chromatography.

The thixotropic liquid insulating varnish was evaluated by the following method. The results are shown in Table 1.
The degree of dispersion was measured with a grain gauge according to JIS K 5600-2-5.
The throttling degree and the viscosity were measured with a BH type rotary viscometer according to JIS K 6901.
For storage stability, 30 g of thixotropic liquid insulating varnish was sealed in a 50 cc glass sample bottle. This was stored in a constant temperature room at 23 ° C. without moving for 3 months, then tilted and evaluated as ◯ when the thixotropic liquid insulating varnish did not flow, and ◯ when it flowed.

  The gelation time of the thixotropic liquid insulating varnish containing the curing agent was measured by a test tube method in accordance with JIS C 2105.

  Volatile matter was obtained by taking 1.5 g of a thixotropic liquid insulating varnish containing a hardener in a 60φ metal petri dish, stretching the varnish to the bottom of the petri dish with a gem clip, and measuring the mass. This was cured on a hot plate heated to 190 ° C. for 10 minutes, and then the mass was measured again to calculate the mass reduction rate before and after curing of the thixotropic liquid insulating varnish containing the curing agent.

  The glass transition temperature is determined by T. C., a cured product obtained by curing a thixotropic liquid insulating varnish containing a curing agent at 80 ° C. for 1 hour, further at 100 ° C. for 1 hour, and further at 130 ° C. for 16 hours. A. Loss tangent (tan δ) was measured at a frequency of 10 Hz while increasing the temperature from −50 ° C. to 250 ° C. at a rate of 5 ° C./min using a dynamic viscoelastic property measuring apparatus RSAIII manufactured by Instruments Co., Ltd., and the peak top temperature was examined.

The appearance of the cured product was evaluated by the following method.
[Preparation of test cured product]
The end of the 3 mm × 2 mm AIW rectangular wire was 1 cm, the center was 4 cm, and the enamel was separated with a metal file. An AIW rectangular wire test piece simulating welding was prepared by bending 180 ° C. from the center of the center where the enamel was peeled off and pressing the tip with a vise. From the bent tip, it was immersed once in a thixotropic liquid insulating varnish containing a curing agent (room temperature 22 ° C.) up to 3 cm and slowly pulled up. This was hung on a jig so that the adhesion portion with the thixotropic liquid insulating varnish containing the curing agent was placed, placed in a thermostatic bath at 130 ° C., and cured for 1 hour to prepare a bent AIW rectangular wire adhered cured product.
[Evaluation]
The concealability was evaluated by visually observing the cured product when the enamel peeling portion was clearly visible as x, when slightly visible as Δ, and when hardly visible as ○.
The presence or absence of crushing was evaluated by observing the surface of the cured product with a stereomicroscope, and indicating that there was a particle having a particle size of 30 μm or more as x and not having it.
The presence or absence of bubbles was evaluated by observing the surface of the cured product with a stereomicroscope as in the case of the presence or absence of crumbs.

  Narrow part penetrability is obtained by embedding the hardened material side of the bent AIW flat wire attached hardened material produced with the appearance of the hardened material with epoxy resin, and cutting the hardened part 1 cm from the tip perpendicular to the longitudinal direction of the flat wire. Then, after this cut surface was polished with an abrasive, it was observed with a stereomicroscope, and the presence or absence of bubbles of 5 μm or more was observed between AIW rectangular wires pressed by a vise. Five of these tests were performed, and evaluation was made with “x” when there was one or more bubbles of 5 μm or more, and “good” when there were no bubbles.

  Edge adhesion was determined by measuring the thickness of the cured product at the four edge portions of the AIW rectangular wire by the method observed with narrow portion permeability, and was taken as the value of the thinnest portion.

  The tester was prepared using Hitachi KM Wire Co., Ltd. KMK-22A enameled wire, impregnated with a thixotropic liquid insulating varnish containing a curing agent, and then the temperature was maintained at 130 ° C. The solution was put into a tank and cured for 1 hour, and measured according to JIS C2103.

  The heat-resistant deterioration property is determined by observing the surface of the cured product with a stereomicroscope after putting the cured product side of the bent AIW rectangular wire-attached cured product prepared in the cured product appearance into a thermostat at 150 ° C. for 500 hours. The presence or absence of cracks was observed. Five of these tests were performed, and evaluation was made with x indicating one or more cracks of 30 μm or more and ◯ indicating no crack at all.

The dielectric breakdown voltage is determined by applying the 50Hz AC voltage from the end where the enamel is peeled off from the end of the enamel peeled off. The voltage that causes
The ATF deterioration resistance was measured by measuring the water content of Aisin Wide Range ATF4020 (ATF, Aisin Seiki Co., Ltd.) by the Karl Fischer method and adjusting the water content to 0.3 wt%. After that, a cured AIW flat wire attached cured product produced in the appearance of a cured product so as to be completely immersed in ATF adjusted to a moisture content of 0.3 wt% is put into a pressure vessel that can be sealed, and the pressure vessel is tightly sealed. Then, a 1500 h ATF degradation test was conducted at 150 ° C.
The bent AIW rectangular wire adhered cured product after the deterioration test was evaluated by measuring the dielectric breakdown voltage by the above-described method, and the retention rate calculated by the following formula was evaluated as 0 when less than 30% and x when less than 30%. Table 1 shows the evaluation results.
Retention rate (%) = (dielectric breakdown voltage after ATF degradation test (V) × 100) / dielectric breakdown voltage before ATF degradation test (V)

  As shown in Table 1, the thixotropic liquid insulating varnishes of Examples 1 to 4 have a storage stability of 3 months or more, sufficient adhesion to the edge of a rectangular wire, and sufficient permeability to a narrow part. In curing, since the volatile content is small, not only can a good work environment be maintained, but it can be expected to produce an electrical device insulator with high yield without wasting varnish. Furthermore, this cured product is excellent in adhesiveness, heat deterioration resistance, and ATF deterioration resistance, has no bubbles, and exhibits a high dielectric breakdown voltage. Therefore, it can be said that it is a highly reliable insulating material.

The thixotropic liquid insulating varnish of Comparative Example 1 cannot be said to have high insulation reliability because bubbles remain, the permeability to a narrow portion is insufficient, and the ATF deterioration resistance is poor.
The thixotropic liquid insulating varnish of Comparative Example 2 has insufficient storage stability and is inferior in adhesiveness and heat deterioration resistance.
Since the thixotropic liquid insulating varnish of Comparative Example 3 has high volatility, not only does the working environment worsen, but the varnish volatilizes unnecessarily, resulting in poor yield in the manufacture of electrical equipment insulators.
The thixotropic liquid insulating varnish of Comparative Example 4 has a low glass transition temperature and poor heat resistance.
The thixotropic liquid insulating varnish of Comparative Example 5 has a long gelation time, so that the production efficiency during the production of the container insulator is poor and the heat deterioration resistance is poor.
The thixotropic liquid insulating varnish of Comparative Example 6 cannot be said to have high insulation reliability because bubbles remain and the permeability to a narrow portion is insufficient.

Claims (7)

(A) 100 parts by weight of a polybasic acid or its anhydride-modified vinyl ester resin, (b) 100 to 300 parts by weight of dicyclopentenyloxyalkyl methacrylate or dicyclopentenyloxyalkyl acrylate and (C) containing 20 to 120 parts by weight of trifunctional acrylate or trifunctional methacrylate , and (d) metal soap 0.004 with respect to 100 parts by weight of the total amount of component (a), component (b) and component (c) -4 parts by weight (however, metal) and (e) 0.05 to 5.0 parts by weight of hydroxyl-terminated liquid polybutadiene , and further (f) fumed silica, with a degree of change at 25 ° C of 2 A thixotropic liquid insulating varnish having a viscosity of from 0.0 to 8.0 and a viscosity at 25 ° C. of from 5.0 Pa · s to 50 Pa · s.
  (F) The thixotropic liquid insulating varnish according to claim 1, wherein fumed silica is blended within a range of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of other components.   The thixotropic liquid insulating varnish according to claim 1 or 2, wherein the polybasic acid or its anhydride-modified vinyl ester resin is a bisphenol-type epoxy resin having a weight average molecular weight of 1000 to 7000.   The thixotropic liquid insulating varnish according to any one of claims 1 to 3, wherein the glass transition temperature after curing is 90 ° C or higher.   The thixotropic liquid insulating varnish according to any one of claims 1 to 4, wherein the dispersity measured with a particle gauge is 70 µm or less.   The electrical equipment insulator formed by carrying out electrical insulation coating with the hardened | cured material of the thixotropic liquid insulation varnish in any one of Claims 1-5.   An electric motor comprising a cured product of the thixotropic liquid insulating varnish according to any one of claims 1 to 5 and covering an end portion of a welded rectangular enameled wire.