JPS628884B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing insulated electrical equipment, including polyester copper wire (hereinafter abbreviated as PEW),
Polyester imide copper wire (hereinafter abbreviated as EIW)
Or improve the reliability and performance of electrical equipment using polyurethane copper wire (hereinafter abbreviated as UEW),
Another object of the present invention is to provide a method for manufacturing electrical equipment subjected to insulation treatment, which can perform insulation treatment in a short time. Recently, electrical equipment has become increasingly smaller and lighter, has harsher usage conditions, and has become more reliable.As a result, insulating varnishes have improved heat resistance, adhesive strength, chemical resistance, and crack resistance. improvement, also
From the viewpoint of productivity, there has been a strong desire to shorten the processing time of insulating varnishes, and unsaturated polyester resins are being used to replace the conventionally widely used solvent-based varnishes. Epoxy ester resin, which is made by reacting polyepoxide with α/β-unsaturated basic acid and has excellent adhesive strength, crack resistance, and chemical resistance, is used for insulating rotating equipment such as stators and armatures. It has been. Rotating equipment requires high reliability, and the insulating varnish must be compatible with the enamelled wire being used, but conventional unsaturated epoxy esters usually have a resin acid value of about 10 to 20. Among the insulating varnishes in which this is dissolved in α/β-unsaturated ethylenic monomers, when PEW, EIW, or UEW is used as enamelled copper wire and the baking conditions are not particularly appropriate, heating of the insulating varnish may cause When cured, the PEW, EIW, or UEW film may crack or blister, resulting in a decrease in electrical insulation properties, resulting in poor reliability. Furthermore, when metallic soaps such as cobalt naphthenate, cobalt octenoate, manganese naphthenate, and lead naphthenate are added to these insulating varnishes as hardening accelerators, there are also drawbacks such as precipitation occurring over time. Furthermore, when insulating rotating equipment with these insulating varnishes, it is generally
A better insulation treatment method has been desired since it requires heating and curing for a period of time, the processing time is relatively long, and the crosslinkable monomer volatilizes during heating and curing, so there is a need for a better insulation treatment method from the viewpoint of resource saving and pollution. The present invention provides an electrical wire treated with an insulating varnish that is highly compatible with enamelled wires used in equipment, improves the reliability and performance of electrical equipment, and enables shortening of insulation processing time. The present invention provides a method for manufacturing equipment, and the present invention provides (1) an unsaturated epoxy ester having a resin acid value of 5 or less obtained by reacting a polyepoxide with an α/β-unsaturated basic acid; α/β-unsaturated ethylenic monomer and
(3) A method for manufacturing an electrical device subjected to insulation treatment, characterized in that the insulation treatment is performed using a photo- and thermosetting resin composition containing a photosensitizer and a peroxide, and (1) polyepoxide and α. A reaction product having a resin acid value of 5 or less obtained by reacting a monoepoxide with an unsaturated epoxy ester having a resin acid value of more than 5 obtained by reacting with a β-unsaturated basic acid, (2) α・Insulated electrical equipment characterized by being insulated using a photo- and thermosetting resin composition containing a β-unsaturated ethylenic monomer and (3) a photosensitizer and a peroxide. Regarding manufacturing methods. The photo and thermosetting resin composition used in the present invention will be explained below. Unsaturated epoxy esters with resin oxidation of 5 or less and more than 5 have approximately equivalent amount of α・
It is obtained by reacting β-unsaturated basic acids, and there are no particular restrictions on the production conditions. For example, it can be synthesized by reacting with a catalyst at 100 to 130°C for 5 to 10 hours. Unsaturated epoxy esters with a resin acid value of 5 or less are synthesized by reacting for a longer time than unsaturated epoxy esters with a resin acid value of more than 5 at the same reaction temperature. The resin acid value of the above reaction product is also adjusted by the reaction time. The resin acid value is measured by taking out a part of the resin during the reaction and using a known method. In the present invention, if an unsaturated epoxy ester with a resin acid value exceeding 5 is used, compatibility with the enameled wire will deteriorate, so the resin acid value of the unsaturated epoxy ester resin is set to be 5 or less. . The resin acid value of the reaction product obtained by reacting an unsaturated epoxy ester with a monoepoxide is also set to 5 or less for the same reason. Polyepoxide is a compound having one or more epoxy groups per molecule, including glycidyl polyether of polyhydric alcohol or polyphenol, epoxidized fatty acid or epoxidized drying oil fatty acid, epoxidized diolefin, epoxidized ester of unsaturated acid, epoxy Ester of saturated acid, epoxidized saturated polyester, etc. are used. As the α/β-unsaturated basic acid, methacrylic acid, acrylic acid, crotonic acid, etc. are used, and these may be used in combination. Catalysts include halides such as zinc chloride and lithium chloride, sulfides such as dimethyl sulfide and methyl phenyl sulfide, sulfoxides such as dimethyl sulfoxide, methyl sulfoxide and methyl ethyl sulfoxide, N・N-dimethylaniline, pyridine, triethylamine, hexamethylene diamine, etc.
amines, their hydrochlorides or oxalic acid, quaternary ammonium salts such as tetramethylammonium chloride and trimethyldodecylbenzylammonium chloride, sulfonic acids such as para-toluenesulfonic acid, mercaptans such as ethyl mercaptan and propyl mercaptan, etc. used. In addition, there are no particular restrictions on the monoepoxides to be reacted with the unsaturated epoxy ester having a resin acid value of more than 5, such as glycidyl ethers such as phenyl glycidyl ether and butyl glycidyl ether, glycidyl ester of parathyabutyl benzoic acid, and fatty acids. Glycidyl esters such as monoglycidyl esters can be used. Although there are no particular restrictions on the reaction conditions, the amount added is such that the resin acid value of the reaction product is 5 or less, and the amount added varies depending on the molecular weight of the monoepoxide. For example, Cardiura E, which is a glycidyl ether or a monoglycidyl ester of a fatty acid, is added to 100 parts by weight of an unsaturated epoxy ester with an acid value of around 15.
(manufactured by Ciel Chemical Co., Ltd., epoxy equivalent: 240-250), 2.5-6 parts by weight for phenyl glycidyl ether, 4 parts by weight for Cardiura E.
~10 parts by weight is added, and the reaction is carried out at 110 to 120°C for 2 to 3 hours so that the resin acid value becomes 5 or less. Examples of α/β-unsaturated ethylenic monomers include styrene, vinyltoluene, ethylvinylbenzene, divinylbenzene, diallylphthalate, α
- methylstyrene, 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, 1,6-hexanediol diacrylate or 1,6-hexanediol dimethacrylate,
Acrylic acid esters or methacrylic acid esters such as trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, tris-(hydroxyethyl-isocyanuric acid) triacrylate or trimethacrylate, polyethylene glycol diacrylate or polyethylene glycol dimethacrylate, etc. Used alone or in combination of two or more, preferably an unsaturated epoxy ester or a reaction product of an unsaturated epoxy ester and a monoepoxide.
70 parts by weight, the α,β-unsaturated ethylenically monomer ranges from 70 to 30 parts by weight. Examples of photosensitizers include benzoin, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2,2-dimethoxy-2-phenylacetophenone.
Acetophenones such as diethoxy-2-phenylacetophenone, benzoin-Michler ketone,
Benzointhioethers, benzophenones, anthraquinones, decyl chloride, etc. can be used.
The amount of the photosensitizer added is 0.1 to 3% by weight based on the total amount of the unsaturated epoxy ester or the reaction product of the unsaturated epoxy ester and monoepoxide and the α/β-unsaturated ethylenic monomer. A range is preferred. Examples of peroxides include acyl peroxides such as benzoyl peroxide and acetyl peroxide, hydroperoxides such as tertiary butyl peroxide and kyumene hydroperoxide, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, Dialkyl peroxides such as tertiary butyl peroxide and dicumyl peroxide, and oxyperoxides such as tertiary butyl peroxy acetate are used. The amount added is preferably 0.5 to 3% by weight based on the total amount of the unsaturated epoxy ester or the reaction product of the unsaturated epoxy ester and the monoepoxide and the α/β-unsaturated ethylenic monomer. as needed,
Metal soaps such as manganese naphthenate, lead naphthenate, cobalt naphthenate, and cobalt octenoate are used as accelerators, and amines and the like may be used as necessary. Hydroquinone, tertiarybutylcatechol, p-
Benzoquinone, 2,5-dithyabutylhydroquinone, etc. are used. There are no particular limitations on the method for insulating electrical equipment with photo- and thermosetting resin compositions, and as is generally done, electrical equipment is dipped in insulating varnish, then pulled up, and the surface of the equipment is irradiated with light. Alternatively, you can drip insulating varnish onto a rotating electrical device to impregnate it, irradiate the surface of the device with light to cure it, and then heat it. There are methods of hardening the unhardened interior. At this time, the equipment before being impregnated with the insulating varnish is usually preheated, but there are no particular limitations on whether or not to preheat and the conditions. Moreover, the heating method after curing by light irradiation is not particularly limited, and hot air, electricity, high frequency, far infrared rays, etc. can be used. Electrical equipment to which the present invention is applied include stators, armatures, and the like. Also, to explain one example of the present invention, a stator for a motor with an output of 125W used at 100V (coil-wound, core dimensions 140 x 110 x 35 mm)
The photo- and heat-curable resin composition used in the present invention is pre-dried at 110-130°C for 30-60 minutes, left in the air for 10-30 minutes, and has a viscosity of about 0.5-2.0 poise at 25°C. Soak in the material for 2-5 minutes.
Then, after raising the stator and leaving it in the air for 10 to 30 minutes, the stator was exposed to ultraviolet light (high-pressure mercury lamp) for 15 minutes.
An insulated stator can be manufactured by irradiating from a distance of ~40 cm for about 1 to 4 hours to harden the surface, and then heat curing at 110 to 130°C for 15 to 30 minutes. Examples of the present invention will be described below. Parts are by weight. Comparative Example 1 376 parts of diglycidyl ether of 4,4'-isopropylidene diphenol (Ciel Chemical, Ep-828, epoxy equivalent 188), 172 parts of methacrylic acid, 2 parts of benzyldimethylamine, 0.05 parts of hydroquinone
A portion of the mixture was charged and reacted at 115°C to synthesize an unsaturated epoxy ester [A] having a resin acid value of 16.
A resin composition [A-1] was prepared using 45 parts of [A], 55 parts of styrene, 0.3 parts of 6% cobalt octenoate, and 1 part of tertiary butyl perbenzoate. Further, 2 parts of benzoin isopropyl ether was dissolved in 100 parts of the resin composition [A-1] to prepare a photocurable resin composition [A-2]. [A-
1] and [A-2] were processed under the test piece preparation conditions and actual machine curing conditions shown in Table 1, and evaluated on the characteristic items shown in Table 1. Comparative Example 2 An unsaturated epoxy ester [B] having a resin acid value of 7.6 was synthesized using the same formulation and temperature conditions as Comparative Example 1, but with different reaction times. [B] 45 parts, styrene 55
%, cobalt octenoate 6%, 0.3 part, and tertiary butyl perbenzoate 1 part. A resin composition [B-1] was prepared. In addition, 2 parts of benzoin isopropyl ether was dissolved in 100 parts of [B-1],
A photocurable resin composition [B-2] was prepared. [B-1] and [B-2] were processed under the test piece preparation conditions shown in Table 1 and the curing conditions of the actual machine, and the characteristic items shown in Table 1 were evaluated. Comparative Example 3 An unsaturated epoxy ester [C] with a resin acid value of 4.9 and an unsaturated epoxy ester [D] with a resin acid value of 3.1 were synthesized using the same formulation and temperature conditions as in Comparative Example 1, but with different reaction times. 45 each of [C] and [D]
parts, 55 parts of styrene, 6% of cobalt octenoate,
Resin compositions [C-1] and [D-1] containing 0.3 parts of tertiary butyl perbenzoate and 1 part of tertiary butyl perbenzoate were prepared. [C-1] and [D-1] were processed under the test piece preparation conditions shown in Table 1 and the curing conditions of the actual machine, and the characteristic items shown in Table 1 were evaluated. Example 1 2 parts of benzoin isopropyl ether was added to 100 parts each of [C-1] and [D-1] of Comparative Example 3,
Resin compositions [C-2] and [D-2] were prepared.
[C-2] and [D-2] were processed under the test piece preparation conditions shown in Table 1 and the curing conditions of the actual machine, and the characteristic items shown in Table 1 were evaluated. Comparative Example 4 [D-2] of Example 1 was treated under the test piece preparation conditions shown in Table 1 and the curing conditions of the actual machine.
The characteristic items shown in are evaluated. Comparative Example 5 When synthesized under the same formulation and temperature conditions as Comparative Example 1, and when the resin acid value reached 17.0, Cardiura E35
The reaction was continued at 115℃ until the resin acid value was 9.0.
product [E], product [F] with a resin acid value of 6.2,
A product [G] with a resin acid value of 4.6 was synthesized. [E]
~ Resin composition [E-1] containing 45 parts each of [G], 55 parts of styrene, 0.3 parts of 6% cobalt octenoate, and 1 part of tertiary butyl perbenzoate ~
[G-1] was created. Also [E-1], [F-
1] Add 2 parts of benzoin isopropyl ether to 100 parts of each resin composition [E-2], [F-
2]. [E-1], [F-1], [G-1],
[E-2] and [F-2] were processed under the test piece preparation conditions shown in Table 1 and the curing conditions of the actual machine, and the characteristic items shown in Table 1 were evaluated. Example 2 Resin composition [G-
2] was created. [G-2] was treated under the test piece preparation conditions shown in Table 1 and the curing conditions of the actual machine,
The characteristic items shown in Table 1 were evaluated. The actual machine characteristics are a single-phase, 125W stator using 1PEW with a diameter of 0.6mm (core dimensions 140 x 110 x 35
mm) was preheated at 120°C for 30 minutes, left at room temperature for 15 minutes, and then immersed in the resin compositions obtained in the above Examples and Comparative Examples for 1 minute, pulled out, and left at room temperature for 5 minutes. It was then cured under the conditions shown in the column of actual curing conditions in Table 1, and evaluated for curing time, compatibility with enameled wire after curing, and crack resistance. <Light irradiation conditions> Lamp: Manufactured by Oak Seisakusho, ORC・AHH-1000
1KW/high pressure mercury lamp, 2 lights Irradiation distance: 20cm

【table】

【table】

[Table] Test method (1) Compatibility with styrene A resin composition was placed in an 18φ test tube to a height of 180 mm, sealed, and left at 0°C for 5 days, and then the appearance of the resin composition was observed. 〇: No change in appearance, good compatibility, △: Appearance,
Opaque, compatibility is slightly poor, ×: Phase separation occurs, compatibility is poor. (2) Stability of varnish over time 300g of the resin composition was placed in a 300cc round tin can, and after being left at 40°C for 10 days, the appearance of the resin composition was observed. 〇: No change in appearance, △: Slight occurrence of sediment. (3) Surface hardening property After applying the resin composition to a tin plate of 18 x 5 x 0.25 tmm, the resin composition was irradiated with ultraviolet rays or heated at 120°C, and the time until the surface hardened was measured. (4) Amount of monomer dissipation: Apply the resin composition to a 60φ x 12mm metal shear tray.
The amount of monomer dissipated was determined from the difference in mass before and after curing when 10 g was poured and heated at 120°C for 2 hours, and when it was irradiated with ultraviolet rays for 3 minutes and then heated at 120°C for 20 minutes. (5) 2.0φ shown in Figure 1 according to JIS C 2105
(Diameter 2.0 mm) 1PEW-1 impregnated with a resin composition and heated at 120℃ for 2 hours, and after 3 minutes of ultraviolet irradiation at 120℃
The shear adhesive strength was measured at 23°C when heated for 20 minutes. In Fig. 1, 2 is a butting part, 3 is an enameled wire (wire diameter 0.29 mm), and the units of numbers are mm. ) (6) Compatibility with enamelled wire in the model coil By using a vertical furnace (furnace length 4.5 m, passed through the die 7 times, temperature: 300°C at the bottom, 350°C at the center, 400°C at the top) and changing the baking speed. Test-fired 0.8φ (diameter 0.8mm)
PEW-1 (linear speed 9 m/min), PEW-2 (linear speed
As shown in Figure 2, the resin composition was applied to a model coil that was turned 30 times using a winding speed of 11 m/min. The appearance of the PEW film was observed when heated at ℃ for 20 minutes, and the dielectric breakdown voltage (abbreviated as BDV) between the lines was measured. 〇: No abnormality in appearance, BDV10~12KV, 〇~
△: Slight swelling in 1 part, BDV10~
12KV, △: Blistering, BDV7~10KV, ×:
The degree of swelling is large, BDV2-5KV In Figure 2, 4 is 0.8φ1 PEW, 5 is cotton thread, and the unit of number is mm. (7) Curing time 125W stator is impregnated with resin composition and heated at 120℃
The curability of the resin composition was determined from the insulation resistance between the wires of the stator when heated at 120°C and after 3 minutes of ultraviolet irradiation and then heated at 120°C. The time when the insulation resistance was saturated was defined as the curing time. (8) Compatibility with enameled wire after curing A 125W stator is impregnated with a resin composition and heated at 120°C.
After heating for 2 hours and after irradiating with ultraviolet rays for 3 minutes
Observation of PEW film after heating at 120℃ for 20 minutes,
The BDV between the lines was measured. (Appearance) 〇: No peeling or blistering, △: Slightly slight bulging, ×: Blistering (BDV) 〇: 10~12KV, △: 7~10KV, ×: 2~
5KV (9) Cracking resistance Using a 125W stator cured in the same manner as in (8), heat cycle 5 times at 25°C/1 hour ← → Low temperature/1 hour, and no cracks should occur in the cured varnish. For example, we lowered the low temperature side by 10°C and conducted a heat cycle in the same way to confirm the temperature at which cracks occurred. From the results in Table 1, it can be seen that by using the photo- and thermosetting resin composition of the present invention, irradiating it with light and curing it with heat, the curing time for insulation treatment is approximately 1/3 of that in the case of heat curing. Furthermore, since the compatibility with enameled wire is improved, it becomes possible to manufacture electrical equipment with excellent reliability.

[Brief explanation of the drawing]

FIG. 1 shows a test piece used in the shear adhesive strength measurement conducted in the example, and FIG. 2 shows a model coil used in the compatibility test with enamelled wire in the example. Explanation of symbols, 1...2.0φ1PEW, 2...Butting part, 3...Enameled wire, 4...0.8φ
1PEW, 5...cotton thread.

Claims (1)

[Claims] 1 (1) unsaturated epoxy ester with a resin acid value of 5 or less obtained by reacting polyepoxide with an α/β-unsaturated basic acid, (2) α/β-unsaturated ethylene 1. A method for producing an electrical device subjected to insulation treatment, characterized in that the insulation treatment is performed using a photo- and thermosetting resin composition containing a photosensitive monomer and (3) a photosensitizer and a peroxide. 2 (1) A reaction in which the resin acid value obtained by reacting a monoepoxide with an unsaturated epoxy ester obtained by reacting a polyepoxide with an α/β-unsaturated basic acid and whose resin acid value exceeds 5 product, (2)
An insulated electrical device characterized by being insulated using a photo- and thermosetting resin composition containing an α/β-unsaturated ethylenic monomer and (3) a photosensitizer and a peroxide. Method of manufacturing equipment.