JPH093143A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermosetting resin compsn. which can reduce the odor of a cured varnish or the amt. of stryene evaporated without lowering the productivity. CONSTITUTION: This resin compsn. contains 100 pts.wt. unsatd. polyester obtd. by the condensation reaction of a hydrogenated bisphennol A (A). an alcohol component (B) contg. a 6C or lower alkylene or alkenylene dialcohol, and an acid component (C) contg. maleic acid or anhydride or fumaric acid, 50-500 pts.wt. hydroxyethyl methacrylate, and an org. peroxide in an amt. of 0.5-2.0wt.% of the sum of components A, B, and C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition, and more particularly to a thermosetting resin composition which produces a small amount of odor and volatilizes styrene.

[0002]

2. Description of the Related Art Conventionally, phthalic acid or its derivative has been used for an insulating varnish such as an air conditioner fan, a closed type rotating machine such as a washing machine, and a closed type transformer such as a small adapter transformer.
A varnish in which an unsaturated polyester resin containing an acid or alcohol containing a benzene ring such as bisphenol A in the molecule as a raw material is dissolved in styrene and / or a styrene derivative is often used. In recent years, these electric appliances are required to reduce the odor of cured varnish more than ever before. The operating temperature (70 to 90
There is a problem such as generation of an offensive odor component in the fuse temperature range (about 140 ° C.). Further, in a sealed transformer such as a small adapter transformer, since a thermoplastic resin such as Noryl resin is used for the housing, there is a problem that cracks are generated due to styrene monomer dissipated from the cured varnish. On the other hand, in order to reduce the odorous components generated from the cured varnish and the volatilized styrene monomer, measures such as lengthening the curing time are taken, but there is a problem of reduced productivity.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and can reduce the odor generation and styrene volatilization amount of a cured varnish product without lowering the productivity. A resin composition is provided.

[0004]

Means for Solving the Problems The present invention comprises (I) (a) hydrogenated bisphenol A and (b) an alcohol component containing an alkylene dialcohol or alkenylene dialcohol having 6 or less carbon atoms and (c) maleic acid. , 100 parts by weight of an unsaturated polyester obtained by condensation reaction of an acid component containing maleic anhydride or fumaric acid, (II) 50-500 parts by weight of 2-hydroxyethyl methacrylate and (II)
I) A thermosetting resin composition containing 0.5 to 2.0% by weight of the organic peroxide based on the total weight of (a), (b) and (c), and the unsaturated polyester. , (A) 1 to 3 mol of hydrogenated bisphenol A, (b) 7 to 11 mol of alkylene dialcohol or alkenylene dialcohol having 6 or less carbon atoms, and (c) maleic acid, maleic anhydride or fumaric acid 8
The present invention relates to a thermosetting resin composition obtained by condensation reaction of 11 mol.

The unsaturated polyester (I) used in the present invention comprises (a) 1 to 3 mol of hydrogenated bisphenol A and (b)
7 to 11 mol (particularly preferably 9) of alkylene dialcohol or alkenylene dialcohol having 6 or less carbon atoms
~ 11 mol) and (c) maleic acid, maleic anhydride or fumaric acid 8 to 11 mol (particularly preferably 10 to 1 mol).
It is preferable to mix it in the range of 1 mol), and it is preferable to adjust it to a condensate having an acid value of 30 or less by reacting at 210 ° C. for 7 to 15 hours by a known condensation reaction.

When the amount of (a) hydrogenated bisphenol A and (b) alkylene dialcohol having 6 or less carbon atoms or alkenylene dialcohol used as the alcohol component in the unsaturated polyester is outside the above range, the odor and flexibility The sexual balance is impaired. When the alkylene dialcohol or alkenylene dialcohol has more than 6 carbon atoms, problems such as deterioration of compatibility occur. As the alkylene dialcohol, ethylene glycol, propylene glycol, neopentyl glycol or the like is used, and as the alkenylene dialcohol, butene-2-diol-1,4 or the like is used.

When the amount of maleic acid, maleic anhydride or fumaric acid (c) used as an acid component in the unsaturated polyester is out of the above range, the amount of unreacted monomer remaining increases and the odor component increases. The problem of occurs. It is preferable to mix these acid components in a range of 0.83 to 1.0 mol per 1 mol of the alcohol component. 2-Hydroxyethyl methacrylate (II) is added to the thermosetting resin composition of the present invention. From the viewpoint of viscosity balance, the amount used is 50 to 500 parts by weight, preferably 200 to 500 parts by weight, relative to 100 parts by weight of the (I) unsaturated polyester.

Examples of the organic peroxide (III) used in the present invention include acyl peroxides such as benzoyl peroxide and acetyl peroxide, hydroperoxides such as tertiary butyl peroxide, cumene hydroperoxide, and methyl ethyl ketone peroxide. , Ketones such as cyclohexanone peroxide, dicumyl peroxide, tertiary butyl perbenzoate, and the like. The usage is
From the viewpoint of the balance between curability and pot life of the resin composition, components (a) and (b) when synthesizing the unsaturated polyester.
And 0.5 to 2.0% by weight based on the total weight of (c).

If necessary, generally used polymerization inhibitors such as hydroquinone, pyrogallol and quinones can be used in the thermosetting resin composition of the present invention. Further, cobalt salts of naphthenic acid or octenoic acid as a curing accelerator, manganese, iron, may be used metal salts such as lead, the amount used in the total weight of the above (a) ~ (c) and (II). On the other hand, the range of 0.1 to 5.0% by weight is preferable.
Examples of coils for electric equipment to which the thermosetting resin composition of the present invention can be applied and treated include stator coils for motors, armature coils for motors, electromagnetic coils, and small transformers for adapters. The treatment method can be performed by hardening after impregnation such as immersion impregnation and drop impregnation.

[0010]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an example means a weight part. Example 1 1.5 mol of hydrogenated bisphenol A, 5 mol of propylene glycol, 4.5 mol of neopentyl glycol,
10.5 mol of maleic anhydride and 0.01% by weight of hydroquinone with respect to the above materials were charged into a synthesis kettle and synthesized at 210 ° C. for 12 hours. When the acid value became 30 or less, the reaction was terminated. To obtain unsaturated polyester.
100 parts of the obtained unsaturated polyester and 300 parts of 2-hydroxyethyl methacrylate were mixed and dissolved at 80 ° C. for 1 hour, cooled to 30 ° C. or lower, 4.0 parts of benzoyl peroxide was added and mixed, and thermosetting A resin composition was obtained. 10 g of this composition was placed in a metal dish having a diameter of 60 mm and cured at 130 ° C. for 1 hour using a hot-air box-type drying oven, and the odorous component amount and styrene volatilization amount of the obtained cured product upon heating were as follows. The results are shown in Table 1.

(1) Amount of odor component during heating of cured product A 1 kg square can was heat-treated at 160 ° C. for 2 hours to remove the odor component from the container. Next, put the cured product in the square can and seal it.
Heat treatment at 0 ° C for 2 hours, and then in a container at a temperature of 85 to 90 ° C, using a self-contained pump of an odor detection sensor (heat wire type semiconductor gas sensor XP-329, manufactured by New Cosmos Electric Co., Ltd.) Was sucked and the amount of odorous components was measured. The larger the value of the odor sensor sensitivity, the larger the amount of odor components. (2) Styrene volatilization amount when the cured product is heated The above odor detection sensor is a styrene concentration meter (XP-316).
Type, manufactured by Shin Cosmos Electric Co., Ltd.) and the styrene volatilization amount was measured. Other conditions were the same as (1).

Example 2 The same as Example 1 except that the unsaturated polyester obtained by reacting 2 mol of hydrogenated bisphenol A, 9 mol of propylene glycol and 10 mol of maleic anhydride was used. To produce a thermosetting resin composition, and to produce a cured product using the composition, and to evaluate the amount of odorous components and styrene volatilization amount during heating of the obtained cured product in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1 In Example 1, 2.7 mol of propylene glycol,
A resin composition and a cured product were prepared in the same manner as in Example 1 except that the unsaturated polyester obtained by reacting 1.5 mol of isophthalic acid and 1 mol of maleic anhydride was used, and the cured product was heated. The amount of odorous components and the amount of styrene volatilized at that time were evaluated in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 5 mol of dimethyl terephthalate, 10 parts of ethyl glycol
Mol and tetrabutyl titanate were added as 0.07% by weight to the above materials and hydroquinone as 0.10% by weight to the above materials in a synthetic kettle and reacted at 200 ° C. for 5 hours, then at 90 ° C. Cool, charge 5 mol of maleic anhydride, synthesize at 210 ° C. for 18 hours, acid value 30
The reaction was terminated when the following was reached, and an unsaturated polyester was obtained. After 100 parts of the obtained unsaturated polyester and 250 parts of styrene were mixed and dissolved at 80 ° C. for 1 hour,
Cooled to 30 ° C or below, benzoyl peroxide 3.5
Parts were added and mixed to obtain a resin composition. Next, using this resin composition, a cured product was prepared in the same manner as in Example 1, and the odorous component amount and styrene volatilization amount during heating of the cured product were evaluated in the same manner as in Example 1, and the results are shown. The results are shown in Table 1.

Comparative Example 3 A resin composition and a cured product were prepared in the same manner as in Example 1 except that styrene was used in place of 2-hydroxyethyl methacrylate, and the amount of odorous components in the cured product. The volatile content of styrene was evaluated, and the results are shown in Table 1.

Comparative Example 4 A resin composition and a cured product were prepared in the same manner as in Comparative Example 2 except that 2-hydroxyethyl methacrylate was used in place of styrene in Comparative Example 2, and the cured product was heated. Evaluate the amount of odor components and the amount of styrene volatilization,
The results are shown in Table 1.

[0017]

[Table 1] From Table 1, it is shown that the cured product obtained from the thermosetting resin composition of the present invention does not generate odor and has a small amount of styrene volatilization.

[0018]

EFFECTS OF THE INVENTION According to the thermosetting resin composition of claim 1 or 2, since the amount of odor generated in the cured product is small and the amount of styrene volatilized is small, there is no discomfort during operation.
Further, it is possible to reduce the occurrence of cracks in the housing and the like. Therefore, this thermosetting resin composition is particularly useful for insulating a closed coil for electric equipment.

Claims (2)

[Claims] 1. (I) (a) hydrogenated bisphenol A and
100 parts by weight of unsaturated polyester obtained by subjecting an alcohol component containing (b) an alkylene dialcohol or an alkenylene dialcohol having 6 or less carbon atoms and (c) an acid component containing maleic acid, maleic anhydride or fumaric acid to a condensation reaction , (II) 2-hydroxyethyl methacrylate 50
~ 500 parts by weight and (III) an organic peroxide in the above (a),
A thermosetting resin composition containing 0.5 to 2.0% by weight based on the total weight of (b) and (c). 2. The unsaturated polyester comprises (a) 1 to 3 mol of hydrogenated bisphenol A and (b) 7 to 11 alkylene dialcohol or alkenylene dialcohol having 6 or less carbon atoms.
2. The thermosetting resin composition according to claim 1, which is obtained by subjecting 8 to 11 mol of (c) maleic acid, maleic anhydride or fumaric acid to a condensation reaction.