JPS59210919A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:A thermosetting resin composition capable of providing electrical insulation molding excellent in heat resistance, dielectric property, adhesion, dimensional stability, etc., prepared by mixing a diene polymer with an unsaturated bisimide compound and a radical generator. CONSTITUTION:100pts.wt. diene polymer or diene vinyl copolymer (preferably, one having at least 30% 1,2-butadiene units in the polymer chain) is mixed with about 10-1,000pts.wt. unsaturated bisimide compound of the formula (wherein R is a 2C or higher bivalent organic groups), e.g., a reaction product between 4,4'-diaminophenylmethane and Himic anhydride) and about 0.1-10pts.wt., per 100pts.wt. bisimide compound, radical generator (e.g., benzoyl peroxide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermosetting resin composition, and more specifically, it is preferably used for electrical insulation, and the resulting cured product has good moisture resistance and heat resistance, and has excellent resistance to moisture and heat resistance. The present invention relates to a thermosetting resin composition with excellent adhesive properties and high-frequency electrical properties.

Conventionally, diene polymers or diene-vinyl copolymers have been used in the field of various electrical insulation materials, but they have problems such as poor adhesion with inorganic materials and metals, dimensional stability, and especially high thermal expansion. It had the following drawbacks. In an attempt to improve these conventional drawbacks, two types of modified diene polymers have been proposed, such as epoxy-modified polybutadiene, carboxy-terminated polyphtadiene, and maleated polybutadiene, but these have poor adhesive properties, etc. Although it was found to be effective, it did not solve the problems of heat resistance and dimensional stability.

The present inventors have conducted extensive studies with the aim of obtaining a thermosetting resin composition with good heat resistance, dielectric properties, adhesion to different materials, and two-dimensional stability of the cured product. This has led to the present invention.

Zunawaji1 The present invention uses (a) a diene polymer or a diene-vinyl copolymer.

A thermosetting product obtained by mixing an unsaturated bisimide compound represented by general formula (1) (in which R represents a divalent organic group having 2 or more carbon atoms) and (C) a radical generator. It is a resin composition.

The diene polymer or diene-vinyl copolymer that is a component of the resin composition of the present invention includes:

Examples include polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, isobutylene-isoprene copolymer, polychloroprene, styrene-butadiene copolymer, etc., including liquid types with a number average molecular weight of about 500 to 5000, and high molecular weight ones. Solid ones are preferably used, but mixtures thereof can also be used. Among these, diene polymers or diene-vinyl copolymers with 1,2-butadiene units having double bonds in side chains are preferred from the viewpoint of strength and thermal stability, and are particularly preferred. A diene copolymer or a diene-vinyl copolymer containing 30% or more of 1,2-butadiene units in the polymer chain is preferably used. A particularly preferred example is a 1,2-butadiene unit containing about 90% of the 1,2-butadiene units.
Polybutadiene or a copolymer with a weight ratio of butadiene and styrene of 80:20.

Examples include polymers having the following repeating units.

Diene polymers or diene-vinyl copolymers include those in which part of the polymer armor or side chain double bonds are epoxidized, maleic anhydride, or carboxyl groups in the side chains or terminals of the molecule. Various modified diene polymers, such as those having hydroxyl groups, amino groups, etc., or diene-vinyl copolymers can also be used.

Unsaturated bisimyl which is a constituent component of the resin composition of the present invention
- The compound is represented by the above general formula (1). In the general formula (1), R represents carbon or a divalent organic group having a prime number of 2 or more, such as a linear or branched alkylene group, a cyclohexylene group, a phenylene group, a naphthalene group, etc. arylene group, or -CI+2
, - C(CH3)-CO-+ -o -1-
502, -3-, -Ni+-.

-N=N-, -COO-, -CONH-, -C, -N-
.

I A polyaromatic group bonded by a group such as X).

A polyalicyclic group is exemplified. Note that these aromatic nuclei and alicyclic nuclei may have a substituent such as a halogen or an alkyl group as appropriate.

Preferred examples of the unsaturated bisimide compound represented by the general formula (I) include the following nine compounds (a) to (nl), where f- represents.

(α) 揖(lh辷f (b)-5%'y (c)5-@衿td,)'t<Ihe)子<C> -f @)-c rii-ef(child) Ji+5
O2-＠-f 傅光-cHsusuC)12-f Zoilperoquinto.

dicumyl peroxide, t-phthyl perhensoate,
Examples include sheet t-butyl peroxyphthalate.

These radical generators can be used in combination of two or more.

The mixing ratio of each of the above components in the resin composition of the present invention is as follows:
The type of diene polymer or diene-vinyl copolymer, the type of unsaturated hisimide compound represented by general formula (T), or the obtained 46 (depending on the purpose of use of the fat composition, etc.)・10 parts by weight of unsaturated bisimide compound per 100 parts by weight of vinyl copolymer
~1000 car parts.

In particular, it is preferably 50 to 200 parts by weight.

The radical generator is preferably used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the unsaturated jadeite compound.

For example, the resin composition of the present invention can be prepared by adding a predetermined amount of the diene polymer or diene-vinyl copolymer, an unsaturated bisimide compound represented by the general formula (1), and a radical generator, either simultaneously or sequentially.

It can be produced by stirring and mixing in a solvent-free system, and the resulting resin composition can be applied to a general casting mold or molded by hot pressing. Furthermore, the resin composition of the present invention can be produced by simultaneously or sequentially dissolving each of the above components in an organic solvent such as dimethylformamide, N-methylpyrrolidone, or dimethylacetamide, and the resulting resin composition can be prepared as a solution. After coating or impregnating a substrate, the solvent can be removed, and a molded article can be obtained by heating and curing under normal pressure or pressure. The curing temperature of the resin composition of the present invention varies depending on the types and proportions of the components used, but is generally 100°C.
to 280°C, preferably from 50°C to 240°C. The curing time is also selected within the range of 30 minutes to 24 hours when energized.

As described below, the resin composition of the present invention can be used, for example, as a powder for general molding, or as a solution as a coating resin, an impregnating resin for various lamination applications, or an adhesive resin.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1. Comparative Example 1 ■ 60 g of 1,2-polybutadiene (number average molecular weight 1500) containing approximately 90% of 2-butadiene units, 4.4'
- 40 g of the bisimide compound represented by formula (e) obtained by the reaction of diaminophenylmethane and Himic anhydride and 3 g of dicumyl peroxide were mixed at 85°C.
The mixture was heated and stirred at C for 10 minutes to obtain a uniform molten composition of 1#.

45 g of the prepared composition was placed in a Teflon-coated, preheated to 95°C, length 12 cm, width 10 cm,
After pouring into a steel container with a height of + i cm and degassing under vacuum.

The temperature was raised to 150 °C at a temperature increase rate of 5 °C per minute, then cooled, removed from the container9, then sandwiched between release films, and then heated using a preheated thread (IOJ/
It was heated under cJG pressure at 180°C-ir for 2 hours and then at 200°C for 1 hour. After cooling, it was removed from the press to obtain a thermoset resin plate.

The obtained cured resin plate was analyzed for dielectric constant, electric tangent, water absorption, and thermal gravity. Table 1 shows the results and measurement conditions.
Shown below.

As shown in the physical property measurement results in Table 1, the cured product obtained from the resin composition of 2-piece J had excellent dielectric properties and heat resistance.

Table 1 For comparison, 80 g of the same 1,2-polybutene used in Example 1, 20 g of vinyltoluene, 5 g of h-methylolpropane trimethacrylate, and 1 g of dicumyl peroxide were mixed and heated at 150°C for 4 hours. Heat,
The mixture was further heated at 180° C. for 2 hours to obtain a cured product. This cured product had poor thermal stability compared to Example 1 at a temperature at which weight loss started at 285°C.

Example 2 1,2-polybutadiene containing approximately 90% of 1,2-butadiene units (number average molecular weight 1500) 50 g, 4.4
- 40 g of the bisimide compound represented by the formula (f) obtained by the reaction of diaminophenyl sulfone and Himic anhydride and 3 g of dicumyl peroxide are mixed;
Heat and mix at 0°C to obtain a composition fj.

The resulting composition was heat-cured under the same thermosetting conditions as in Example 1 to obtain a cured resin plate with a thickness of 3 mm. When the obtained cured resin plate was measured in the same manner as in Example 1, the dielectric constant was 2.71. The temperature at which weight loss started was 328° C. with a dielectric loss tangent of 0.006, and the dielectric properties and heat resistance were excellent.

Example 3 A modified 1,2-polybutadiene consisting of about 90% 1,2 bonds, epoxidized 1.2 represented by the following formula:
~50 g of polybutadiene (manufactured by Adeka Argus Chemical, average molecular weight 1000, trade name BF 1000 ), 30 g of the bisimide compound represented by the formula +21 used in Example 1, and 3 g of dicumyl peroxide were heated at 80 °C for 10 g.
The mixture was stirred and mixed for a minute to obtain a uniform molten composition.

The obtained composition was transferred to the same container as used in Example 1, and after defoaming under vacuum, the temperature was raised to 130°C at a rate of 5°C per minute, then cooled, and removed from the container. 5 Next, after sandwiching it between mold release films, heat it to 200°C.
It was heated between two intercostals under a pressure of 15 kg/c+δG using a press machine. The obtained cured resin plate has a dielectric constant of 2.
74. Dielectric loss tangent 0.005, thermal decomposition start temperature 330°
C7 water absorption: 0.09%, low water absorption rate of 8 and dielectric properties.

It had excellent heat resistance.

Example 4 A styrene-butadiene copolymer (manufactured by Esso, trade name: C-0il
20 g of the hisimide compound represented by the Fe1 formula used in Example 1 and 1 g of dicumyl peroxyt were mixed and heated on a heating table at 90°C for 10 minutes to obtain a molten composition. Ta.

Example 1 in which this composition was preheated to 100°C
Pour into the same Teflon-coated steel container used in 1. After vacuum defoaming, heat to 50°C at a rate of 5°C per minute.
After that, the mixture was cooled, taken out from the container, and heated under the same conditions as Example J using a heat press. The obtained cured resin plate has water absorption *o, o7%, dielectric loss tangent 0.0
06, had a weight loss start temperature of 320°C, 2 good heat resistance, and excellent dielectric properties.

Patent applicant: Unitika Co., Ltd.

Claims (1)

[Claims] (ll (al diene polymer or diene-vinyl copolymer). (bl general formula ([) (in the formula, R represents a divalent organic group having 2 or more carbon atoms). A thermosetting resin composition formed by mixing the shown unsaturated bisimide compound and a Cl radical generator.