JPS59129224A - Resin composition - Google Patents

Abstract

PURPOSE:A resin composition having a controlled amount of carbon dioxide gas formed during heat curing and forming an electrical insulated winding low in varnish bleeding and void content, comprising an epoxy resin, methylhexahydrophthalic anhydride, water, and an imidazole derivative. CONSTITUTION:A resin composition comprising an epoxy resin (A), methylhexahydrophthalic anhydride (B), 0.01-5.0wt%, based on the sum of components A and B, water (C), and at least 0.3wt%, based on the sum of components A and B, imidazole derivative (D). To apply the above composition to an electrical insulated winding, a thermosetting resin composition comprising components A, B, and C is infiltrated into the insulation layer, allowed to gel at a temperature <=120 deg.C in the presence of component D, and cured. It is possible to allow, for example, component D to absorb component C instead of adding component C to the varnish later.

Description

[Detailed description of the invention] [Field of application of the invention] The invention relates to resin compositions.

[Advanced technology]

Epoxy resin has excellent chemical resistance, mechanical properties, heat resistance, and adhesive properties, so it is used in paints, electrical insulation, civil engineering, etc.
It is widely used in various fields such as architecture, and as a resin that meets the recent demands for higher performance in plastic materials, its application fields are being expanded and its quantitative development is progressing.

Epoxy resins are rarely used alone; they are amines.

By combining it with a curing agent such as an acid anhydride, its performance is fully demonstrated. Amine-based hardeners have relatively high toxicity, which poses health management problems for workers who handle them.Acid anhydride hardeners with low toxicity, especially acid anhydrides that are liquid at room temperature and easy to work with, are recommended. Attention is now being paid to

Liquid acid anhydride curing agents currently used industrially are obtained by isomerizing the double bonds of methyltetrahydrophthalic anhydride obtained by Teils-Alder reaction with isogrene or piperylene maleic anhydride. Liquid acid anhydride (for example, H manufactured by Hitachi Chemical KK)
N-2200゜Evicron B-570 manufactured by Dainippon Ink and Chemicals KK), methylhexahydrophthalic anhydride obtained by hydrogenating methyltetrahydrophthalic anhydride (e.g. HN-550 manufactured by Hitachi Chemical KK)
0, Dainippon Ink Chemical Industry K Ebikuron B-65
0, Rikashido MH-700 manufactured by Shinnihon Rika Kogyo KK, manufactured by Bayer) (arter M-hereinafter IVIHH, PA
It is abbreviated as ), or methylendomethylenetetrahydrophthalic anhydride obtained by the Diels-Alder reaction of methylcyclopentadiene and maleic anhydride (e.g., methyl-imitsic anhydride manufactured by Hitachi Chemical KK, Kayahard MC0 manufactured by Nippon Kayaku Kogyo KK), etc. can be given.

In particular, i-type MHHP A is relatively inexpensive and has good heat resistance and electrical properties, so it is mainly used for casting, embedding, tip coating, and insulating sources for electrical and electronic components.
Used as an electrical layer. Curing of epoxy resin with such MH and HPA was disclosed in Japanese Patent Publication No. 39-1452.
It is known as shown in Publication No. 1' and 2% Publication No. 57-9741.

On the other hand, MI-IHPA absorbs moisture in the air, converts it into free carboxylic acid, and precipitates crystals, which may cause poor casting, impregnation, or hardening.

4-Methylhexahydrophthalic anhydride (I) and 3
-Methylhexahydrophthalic anhydride (2) 75/25
MHHPA, which is contained in a ratio such that the ratio is ~25/75 (weight ratio), and in which 4-methyl-Δ3-tetrahydrophthalic anhydride (2) is 0.1 H amount % or less in the acid anhydride.
is known from Japanese Patent Publication No. 57-9741. An example of such a MHHPA is the aforementioned HN-5500.

By the way, when an epoxy resin composition using MHHPA as a curing agent is blended with a curing accelerator and cured immediately by heat, carbon dioxide gas is generated. Therefore, when the epoxy resin composition is used as an impregnating varnish, the varnish may run out or voids may occur during heat curing, resulting in poor electrical properties and moisture resistance. Therefore, in order to suppress the generation of carbon dioxide gas, we investigated the cause of the generation of carbon dioxide scum and found that it was based on equation (1).

Next, as a result of various studies on the carbon dioxide gas generation conditions in formula (1), the amount of carbon dioxide gas generated depends on the type and amount of the curing accelerator, and the gelation rate.
It was found that it depends on the degree of correction and water content.

[Purpose of the invention]

The present invention was made in view of the circumstances described above, and its purpose is to provide an electrical insulating winding wire that suppresses the amount of carbon dioxide gas generated during heat curing and prevents varnish from flowing out and voids from occurring. There is a particular thing.

[Summary of the invention]

To summarize the present invention, (A) epoxy resin, (]3
31MI-1'L-]p A, O and (Q, (
AJ CB + (IJ) A thermosetting resin composition containing 0.01 to 5.0% by weight of water based on the total amount of (IJ) is impregnated into the continuous layer, and (B) and (Q) 0.3 relative to the total amount
It is characterized in that it is gelled in the presence of more than % by weight of an imiguzole derivative at a degree of sleep of 120 C or less, and then post-cured.

Examples of epoxy resins in non-inventions include vias, 7
Diglycidyl ether of xnol A, phthalene dieboxide, 3,4-epoxycyclohexylmethyl-
(3,4-epoxy)cyclohexane lupoxylate, vinylcyclohexene dioxide, 4,4'-di(
l,2-epoxyethyl)diphenyl ether, 4.4
'-(1,2-epoxyethyl)biphenyl, 2.2-
Bis(3,4-epoxycyclohexyl)propa/, diglycidyl ether of resorcin, phlorogrunnocyclidyl ether, diglycidyl ether of methyl 70rogrun/, bis(2,3-epoxycyclopeethyl) ether, 2- (3,4-Epoxy)cyclohexane-5,5-spiro(3,4-Epoxy7)-cyclohexa/-n]-dioxa/, bis-(3,4-epoxy-6
-methyl/chlorohequinyl)adipate, N, N'
n]-722lenebis(4,5-epoxy-1,2
-7 2-giryu epoxy resins such as hexanedicarboquinimide, triglycidyl ether of aminophenol, polyallyl grindyl ether, 1.3.5-
1-li(1,2-epoxyethyl)benzene, 2.2'
, 4'-tetragrindquin benzophenone, tetragridqui7tetraphenylethane, polyglycidyl ether of phenol formaldehyde novolac,
Tri- or higher functional epoxy resins such as glycerin triglycidether and trimethylolpropane triglycidether are used.

Among the above epoxy resins, diglycidyl ether of bisphenol A is particularly useful. Also, MI-1
)] PA includes the above-mentioned HN-5500, Ebicuron B-650, Rikajid MH-700,1 (ar
There are ter M and so on. Of these, H, N-55
Even if 00 absorbs moisture, the amount of conversion to free carboxylic acid is small, crystal precipitation is also small, and the heat distortion temperature IW is good, so it is preferable.

Further, as imidazole derivatives, 2-methylimidazole, 2-ethylimidazole, 2-u/decylimidazole, 2-heptadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, l-propyl-2- Methylictasol, 1-benzyl-2-methylimidazole, 1-dianoethyl-2-
Methylimidazole, ■-Cyanethyl-2-undecylimitasol, 1-cyanethyl-2-phenylimidazole, 1. -(4,,6-diamitsu-triazinyl-2-ethyl)-2-'7te/limidazole,
Imidazole derivatives such as 1-(4,6-diamitsu-)realenyl-2-ethyl)-2-methylimidazole are useful. Salts of the above imidazole derivatives (such as limellitic acid) and adducts with octane and instant lead are also useful. In order to reduce the amount of carbon dioxide gas generated during curing, 0.3% by weight or more is required.In particular, the range of 1.0 to 3.0mm% is suitable.The method for blending the catalyst is as follows: It does not necessarily need to be blended into the thermosetting resin composition composed of the epoxy resin and MHHPA, but may be attached to the insulating base material in advance.

Furthermore, the moisture in the present invention does not need to be added to the varnish afterwards; for example, moisture absorbed by M or HHP A can be used. When the moisture content is 0.01% or less, the amount of carbon dioxide gas generated tends to increase. When the moisture content is high, the amount of carbon dioxide gas generated decreases, but when the water content exceeds 5.0% by weight, the amount of negative 7 of the free acid increases, which tends to cause poor curing.

[Embodiments of the invention]

Next, examples of the present invention will be shown and specifically explained. The MHf-IPA and epoxy resin used in the examples are as follows.

DEW-332: Dow Chemical Co., Ltd. glass sphere 7-A
Diglycidyl ether, equivalent weight 174 HN-55Q Q: Hitachi Chemical K K MHH
PA Examples 1-9. Comparative Examples 1 to 4 Dll-33247, 6-fold leaf part, HN-5500, 52
, 4 parts by weight, 7J < 0.1 parts by weight, and the amine and imidazole curing catalysts listed in Table 1, respectively.
Stir well. The obtained thermosetting resin composition was heated to 120C.
/1 hour+1601T/4 hours of heating to obtain a cured product.

The amount of carbon dioxide gas generated during the curing process was measured and is shown in 1 below.

Table 1 Carbon dioxide gas measurement was carried out using Daikin Electric KK 701FPSS.
This was carried out using a CI type pyrolysis gas chromatograph. In other words, it has an inner diameter of 2 that accommodates the varnish.

A quartz glass sample bottle with a depth of 8 holes was placed in an electric furnace,
The predetermined temperature was maintained at ±2c for 2 to 3 seconds. Next, the gas generated from the sample is sent to a gas chromatograph at predetermined intervals and passed through a 150C separation column packed with activated carbon.
The carbonate scum was separated. Thereafter, carbon dioxide gas was reduced with methane and identified and quantified using a %FID detector.

As can be seen from Table 1, the examples in which 0.3 portions or more of the imidazole inducer were blended had little carbon dioxide scum generation.

Example 10 DER33250 parts, HN-550050 parts by weight, 0.5 parts by weight of water, and 1 part by weight of 1-(4,6-diamitsu-triazinyl-2-ethyl)-2-undezolimidazole were blended. , room temperature 0.5 +trm
A thermosetting resin composition was prepared by degassing under Hg for 2 hours.

On the other hand, a glass cloth tape (manufactured by Nittobo, 0.1
3 crucian carp thickness, 25w1]) once in a half wrap, on top of which NOMXE-410 tape (25mm width) is wrapped in a half wrap three times, and on top of that, the above glass cloth tape is wrapped once in a half wrap, and this is 80C. , 0,5 cylinder i (g) After holding for 3 hours, the above thermosetting resin!J
After impregnating with ifjX material, 120C/1 hour +16
It was thermally cured at 0C/4 hours to obtain an insulated winding wire for electrical machinery. The electrical properties of this product are shown in Table 2.

Table 2 Note that no voids were observed in the insulating layer of this product.

Comparative Example 5 Insulating winding for electrical machinery was prepared in the same manner as Example 0 except that the amount of l-(4,d-diamino-8-triazinyl-2-ethyl)-2-undecylimidazole was 0.2 parts by weight. Got the line. Voids were observed in the insulating layer of this product. The electrical properties of this product are also listed in Table 2.

Example] 1 Fibrid mica (A mica manufactured by Nippon Aroma Co., Ltd.) and glass woven cloth were coated with a silicone resin binder (12% by weight) on a conductor.
), the insulating tape (0.13m thick) is bonded with
It was wrapped three times in a half wrap.

In addition, along with the above binder, 1-<4 which is a curing accelerator
．． 6-diamitsu-triazinyl-2-ethyl)-2
- One decyl imidazole per 1 m3 of insulating tape p 1
．． It was attached at a rate of 5 g.

1 m3 of the above-mentioned curing accelerator was placed on the above-mentioned fibrid mica tape wound layer. Glass woven fabric (Nittobo Co., Ltd., alkali-free tape ET05052) attached at a ratio of Og
mi] thickness) was wound once to obtain an insulated conductor.

On the other hand, DER-33250 parts by weight, l-lN-5500
A thermosetting resin composition comprising 60 parts by weight and 03 parts by weight of water was added to the insulated conductor at room temperature, 0, ], rra
After inducing pressure under n Hg for 1 hour, 120
It was cured by hDOIh at 160C for 1 hour and then 4 hours at 160C. The electric properties of this material are shown in Table 2. There is a void in the optimal layer of this material.

In addition, 1. ．． 5g, 2.0
The adhesion amount of g is 1.8% by weight and 25% by weight, respectively, based on the impregnated thermosetting resin composition.

Example 12 Completely the same as Example 11 except that fibrid mica (Mica A manufactured by Nippon Aroma Co., Ltd.), an insulating tape (0.13 mm thick) made by binding glass woven cloth and Mylar with an evogynoester binder were used. In the same way, we obtained a complete insulation material for electrical machinery. Table 2 shows the electrical properties of this material. In addition, no voids were observed in the bone layer.

Disaster Example 13 Example 1 except that a supine tape (0.13 mm thick) made by binding fibrid mica (A mica manufactured by Nippon Aroma Co., Ltd.) and Nomex with an epoxy ester binder was used.
] An insulated winding wire for electrical machinery was obtained in exactly the same manner. The electrical properties of this product are shown in Table 2. Matazetsu #IKI? No voids were observed in =.

〔Effect of the invention〕

Claims (1)

[Claims] 1. Epoxy resin, methylhexahydrophthalic anhydride, 0.01 to 5.0% water by weight based on b"jJ1' of the epoxy resin and methylhexahydrophthalic anhydride, and epoxy resin, methylhexahydrophthalic anhydride acid,
A resin composition comprising an imidacene derivative in an amount of 0.3% by weight or more based on the total amount of an epoxy resin, a resin, and methylhexahedrophthalic anhydride.