JPS5937285B2 - Photo and thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photo- and thermosetting resin composition,
Polyester copper wire (hereinafter abbreviated as PEW) is used for insulating and fixing electrical equipment, and is particularly used as an enamelled copper wire.

) or urethane copper wire (hereinafter abbreviated as UEW) provides excellent compatibility, improves the reliability and performance of electrical equipment, and shortens the time for insulation processing of electrical equipment. The present invention relates to possible photo- and thermosetting resin compositions. Recently, there has been a growing trend toward smaller and lighter electrical equipment, harsher operating conditions, and improved reliability, and insulating varnishes are desired to have improved adhesive strength, crack resistance, heat resistance, chemical resistance, etc. In order to replace the conventionally widely used solvent-based varnishes, unsaturated polyester resins, which have excellent properties, have improved adhesive strength, crack resistance, chemical resistance, etc. than unsaturated polyester resins. Unsaturated epoxy ester resins with excellent properties have been used as insulating varnishes for rotating equipment.

Rotating equipment requires high reliability, and insulating varnish is
A material that is compatible with the enameled wire being used is required, and conventional unsaturated epoxy esters usually have an acid value of 1.
0 to 20, and among insulating varnishes in which these are dissolved in α and β = unsaturated ethylenic monomers, PEW and UEW with poor solvent resistance or with inappropriate baking conditions may be used. In some cases, the PEW and UEW films peeled or blistered during heat curing, resulting in significantly poor electrical insulation properties.

Furthermore, when metal soaps such as cobalt naphthenate, cobalt octenoate, manganese naphthenate, and lead naphthenate are added as accelerators, there are also drawbacks such as the formation of sediment over time. In addition, heat curing of these insulating varnishes
Generally, it is necessary to heat at 100 to 140°C for 2 to 5 hours, and the processing time is relatively long. Further, the crosslinking monomer volatilizes during curing, which poses problems from the viewpoint of resource saving and pollution. As a result of various studies, the present inventors found that (1)
A reaction product with an acid value of 5 or less obtained by reacting a monoepoxide of an unsaturated epoxy ester with an acid value of more than 5 obtained by reacting a polyepoxide with an α/β monounsaturated monobasic acid, (2) Impregnating electrical equipment such as motor stators and armatures with a photo- and thermosetting resin composition containing an α/β monounsaturated ethylenic monomer and (3) a photosensitizer and a peroxide, It has been found that these defects can be improved by curing the surface by irradiating it with light and then heating it with heat current, high frequency, far infrared rays, etc.

The present invention provides (1) an unsaturated epoxy ester with an acid value of more than 5 obtained by reacting a polyepoxide with an α/β monounsaturated monobasic acid and an unsaturated epoxy ester with an acid value of 5 or less obtained by reacting a monoepoxide with an The present invention relates to a photo- and thermosetting resin composition comprising a reaction product, (2) an α/β monounsaturated ethylenic monomer, and (3) a photosensitizer and a peroxide.

In the present invention, acid value refers to JISC21O5-1979
(the number of potassium hydroxide required to neutralize the acid in sample 1V) measured by

The unsaturated epoxy ester of the present invention having an acid value exceeding 5 is obtained by reacting polyepoxide with approximately equivalent amount of α/β unsaturated monobasic acid, and there are no particular restrictions on the manufacturing conditions, such as catalyst 5~ at 100~130℃ using
It is synthesized by reacting for 10 hours.

The acid value of the reaction product obtained by reacting an unsaturated epoxy ester with a monoepoxide is set to be 5 or less for compatibility with enameled wire.

The polyepoxide used in the present invention is a compound having one or more epoxy groups per molecule, such as glycidyl polyether of polyhydric alcohol or polyphenol, epoxidized fatty acid or epoxidized drying oil fatty acid, epoxidized diolefin, and epoxidized diolefin. Saturated acid esters, epoxidized saturated acid esters, epoxidized saturated polyesters, etc. are used.

As the α/β monounsaturated monobasic 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 - Tertiary amines such as N-dimethylaniline, pyridine, triethylamine, hexamethylene diamine and their hydrochlorides or oxalates, quaternary ammonium salts such as tetramethylammonium chloride, trimethyldodecylbenzylammonium chloride, para-toluene Sulfonic acids such as sulfonic acid, mercaptans such as ethyl mercaptan and propyl mercaptan, and the like are used.

In addition, there are no particular restrictions on the monoepoxides to be reacted with unsaturated epoxy esters having an acid value of more than 5, including glycidyl ethers such as phenyl glycidyl ether and butyl glycidyl ether, glycidyl esters of paratertiary butyl 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 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, unsaturated epoxy ester 10 with an acid value of around 15
When reacting phenyl glycidyl ether or a monoglycidyl ester of fatty acid Cardiura E (manufactured by Ciel Chemical Co., Ltd., epoxy equivalent: 240 to 250) to 0 parts by weight, in the case of phenyl glycidyl ether, 2.5 to 6
parts by weight, in the case of Cardiura E, add 4 to 10 parts by weight,
2-3 at 110-120℃ so that the acid value is 5 or less
Allow time to react.

Examples of α/β monounsaturated ethylenic monomers include styrene,
Vinyltoluene, ethylvinylbenzene, divinylbenzene, diallyl phthalate, α-methylstyrene, 2-
Hydroxyethyl acrylate or 2-hydroxyethyl methacrylate, 1,6-hexanediol diacrylate or 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, polyethylene glycol diacrylate or polyethylene glycol dimethacrylate, etc. Acrylic esters or methacrylic esters are used alone or in combination of two or more, preferably based on 30 to 70 parts by weight of an unsaturated epoxy ester or a reaction product of an unsaturated epoxy ester and a monoepoxide. The amount of α/β monounsaturated ethylenic monomer is in the range of 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-diethoxy-2- Acetophenones such as phenylacetophenone, benzoin-Michler-ketone, benzinthioethers, benzophenone, anthraquinones, decyl chloride, and the like can be used.

The amount of the photosensitizer added is preferably in the range of 0.1 to 3% by weight based on the total amount of the reaction product of the unsaturated epoxy ester and monoepoxide and the α/β monounsaturated ethylenic monomer. . 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, and dither. Dialkyl peroxides such as shalybutyl peroxide and dicumyl peroxide, oxyperoxides such as tertiary butyl peroxy acetate, etc. are used.

The amount added is preferably 0.5 to 3% by weight based on the total amount of the reaction product of the unsaturated epoxy ester and monoepoxide and the α/β monounsaturated ethylenic monomer. If necessary, a metal soap such as manganese naphthenate, lead naphthenate, cobalt naphthenate, cobalt octenoate, etc. may be used as an accelerator, and an amine or the like may be used if necessary. Hydroquinone, tert-butylcatechol, p-benzoquinone, 2,5-ditertibutylhydroquinone, etc. are used as the polymerization inhibitor. The photo- and thermosetting resin composition of the present invention is suitable for insulating and fixing electrical equipment such as motor stators and armatures.

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 (manufactured by Ciel Chemical, Ep-828, epoxy equivalent 188), 172 parts of methacrylic acid, 2 parts of benzyldimethylamine, and 0.05 part of hydroquinone were charged. , the reaction was carried out at 115°C while measuring the acid value, and the acid value was 16.
unsaturated epoxy ester [A] and unsaturated epoxy ester [B] with an acid value of 7.6 were synthesized, [A], [B]
45 parts each of L styrene 55 parts, cobalt octenoate 6 parts
% and 1 part of benzoyl peroxide were prepared.

Comparative Example 2 [A-1] and [B-1] of Comparative Example 1, 1 each
00 parts and 2 parts of benzoin isopropyl ether were added to prepare resin compositions [A-2] and [B-2].

Comparative Example 3 Synthesis was carried out using the same formulation and synthesis steps as in Comparative Example 1. When the acid value reached 17, 35 parts of Cardiura E was added and the reaction was continued while measuring the acid value at 115°C until the acid value reached 9. A reaction product [C] with an acid value of 0, a reaction product [D] with an acid value of 6.2, and a reaction product [E] with an acid value of 4.6 were synthesized.

Resin compositions [C-1] and [D-1] containing 45 parts each of [C], [D], and [E], 55 parts of styrene, 0.3 parts of 6% cobalt octenoate, and 1 part of benzoyl peroxide. ]
, [E-1] was created. Comparative Example 4 2 parts of benzoin isopropyl ether was added to 100 parts each of [C-1] and [D-1] obtained in Comparative Example 3 to prepare J resin compositions [C-2] and [D-2]. .

Example 1 2 parts of benzoin isopropyl ether was added to 100 parts of [E-1] obtained in Comparative Example 3 to prepare a resin composition [E-2].

Comparative Example 5 Synthesized using the same formulation and synthesis process as Comparative Example 1, and when the acid value reached 15, 16 parts of butyl glycidyl ether was added,
The reaction continued at 115°C while measuring the acid value, and the acid value reached 8.
5 reaction product [F], reaction product with acid value 6.0 [G
], a reaction product [H] with an acid value of 4.2 was synthesized.

Resin compositions [F-1], [G-1] containing 45 parts each of CF], [G], and [H], 55 parts of styrene, 0.3 parts of 6% cobalt octenoate, and 1 part of benzoyl peroxide.
, [H1] was created. Comparative Example 6 2 parts of benzoin isopropyl ether was added to 100 parts each of the resin compositions [F-1] and [G1] obtained in Comparative Example 5 to form resin compositions [F-2] and [G-2]. did.

Example 2 2 parts of benzoin isopropyl ether was added to 100 parts of the resin composition [H-1] obtained in Comparative Example 5, and the resin composition [H-1] was added.
H-2].

After irradiating the resin compositions obtained in Comparative Example 2, Comparative Example 4, Comparative Example 6, and Examples 1 to 2 for 3 minutes with ultraviolet rays,
The resin compositions obtained in Comparative Example 1, Comparative Example 3, and Comparative Example 5 were heated at 120° C. for 2 hours to prepare cured products, and their properties were compared.

The results are shown in Table 1. In addition, a single-phase, 125W stator (core dimensions 140 x 110 x 35 mm) using 0.6φ (diameter 0.6 yam) IPEW was treated with the resin composition obtained in the above examples and comparative examples. Table 1 shows a comparison of hardenability, compatibility with enameled copper wire, crack resistance, etc. when heated at 120° C. and when heated at 120° C. after irradiation with ultraviolet rays.

<Ultraviolet irradiation conditions> Lamprie Oak Manufacturing Co., Ltd., 0RC-AHH-1000,
1 is a high-pressure mercury lamp, 2 lamps Irradiation distance: 20 (V7L Irradiation time: 3 minutes Test method (1) Compatibility with styrene Put the resin composition in an 18φ test tube to a height of 180n, seal it, and heat it to 50°C. After standing for a day, the appearance of the resin composition was observed.

○: No change in appearance, good compatibility; △: Appearance, opaque, slightly poor compatibility; ×: Phase separation, poor compatibility.

(2) Varnish stability over time Pour 300V of the resin composition into a 300CC round tin can,
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 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 required for the surface to harden was measured.

(4) Monomer loss amount When the resin composition is placed in an IOV of a 60φ x 12 mwL metal petri dish and heated at 120°C for 2 hours, and after irradiated with ultraviolet rays for 3 minutes, it is heated at 120°C for 20 minutes. The amount of dispersion was determined from the difference in mass before and after curing.

(5) Shear adhesive strength A Strucker test piece made of 2.0φ (diameter 2.0 mwL) IPEW-1 shown in Figure 1 was impregnated with a resin composition in accordance with JISC21O5 and heated at 120°C for 2 hours.
The shear adhesive strength was measured at 23° C. when heated for a certain period of time and when heated at 120° C. for 20 minutes after irradiation with ultraviolet rays for 3 minutes.

In FIG. 1, 2 is an abutting portion, 3 is an enameled wire (wire diameter 0.29 mm), and the unit of numbers is 7 nm.

(6) Compatibility with PEW in model coil Rigid trial furnace (
Furnace length: 4.5 m) Pass through the die 7 times, Furnace temperature: 300°C at the bottom,
0.8φ (diameter 0.8m7n) PEW-1 (350°C in the center, 400°C in the upper part) with different baking speeds
Linear speed 9m/wl) and PEW-2 (Linear speed 11m/M
m), the resin composition was applied to a model coil that had been turned 30 times in a para-wound manner as shown in Figure 2.
120°C when heated for 2 hours and after 3 minutes of ultraviolet irradiation
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, V on BDVIO ~ 12, ○ ~ △: 1
There is a slight bulge on the part, V on BDVIO to 12, △: There is a bulge, V on BDV 7 to 10) ×: The degree of bulge is large, V on BDV 2 to 5 In Fig. 2, 4 is 0.8φ
IPEW, 5 is cotton thread, and the unit of number is mrei.

(7) Curing time: 125W stator impregnated with resin composition and heated at 120℃ for 50 minutes, and 125W stator heated at 120℃ for 3 minutes after irradiation with ultraviolet rays.
The curability of the resin composition when heated for 7 minutes was determined from the insulation resistance between the wires of the stator.

The time when the insulation resistance was saturated was defined as the curing time. (8) Compatibility with enameled wire after curing A case in which a 125W stator is impregnated with a resin composition and heated at 120℃ for 2 hours, and a case in which it is heated at 120℃ for 3 minutes after irradiation with ultraviolet rays.
Observation of appearance of PEW film after heating for 0 minutes and B between lines
DV was measured.

(Appearance) 〇: No peeling or blistering, △: Some slight bulging, × Bulging (BDV) ○: V on 10-12) △: V on 7-10 KV) x 2-5 (9) Cracking resistance Using a 125W stator hardened in the same manner as in (8), heat cycles of Θ low temperature/1 hour at 25°C/1 hour were carried out for 5
The heat cycle was repeated, and if no cracks were generated in the cured varnish, the temperature was lowered by 10° C., and the heat cycle was repeated in the same manner to confirm the temperature at which cracks occurred.

From the results in Table 1, it can be seen that the curing time of insulation treatment using the photo- and thermosetting resin composition of the present invention by light irradiation and heat curing is approximately 1/2 that of heat curing. 5, and the compatibility with the enamelled wire is improved, making it possible to manufacture electrical equipment with excellent reliability.

[Brief explanation of drawings]

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 PEW conducted in the example. Explanation of symbols, 1...20φIPEW, 2...
...Butting part, 3...Enameled wire, 4
...0.8φ1PEW, 5...cotton thread.

Claims (1)

[Claims] 1 (1) The acid value obtained by reacting a polyepoxide with an α/β-unsaturated monobasic acid is more than 5. The acid value obtained by reacting an unsaturated epoxy ester with a monoepoxide is 5.
A photo- and thermosetting resin composition comprising the following reaction product, (2) an α/β-unsaturated ethylenically monomer, and (3) a photosensitizer and a peroxide.