JPS5884812A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:The titled composition, prepared by incorporating a composition consisting of a polyfunctional epoxy compound and a specific amount of an unsaturated monocarboxylic acid compound with a composition consisting of a polyfunctional maleimide compound and a nadicimide prepolymer, and having improved heat resistance. CONSTITUTION:A composition prepared by incorporating (A) 20-95pts.wt. composition consisting of a polyfunctional epoxy compound, e.g. bisphenol A type, and an unsaturated monocarboxylic acid compound, e.g. acrylic acid, at (0.8- 1.5):1 equivalent ratio between the carboxyl groups and the epoxy groups with (B) 80-5pts.wt. composition obtained by polymerizing 5-95wt% polyfunctional maleimide compound, having two or more maleimide groups in one molecule, with 95-5wt% nadic inside prepolymer expressed by the formula[R1 is fatty aliphatic (or aromatic) diamino residue; R2 is aliphatic (or aromatic) tetracarboxylic acid; (n) is 0 or a natural number 1-5], and if necessary adding an additive thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to thermosetting resin compositions. More specifically, the present invention relates to a thermosetting resin composition that provides a cured product with excellent heat resistance and excellent mechanical and electrical properties by heat curing.

The cured product of the resin composition of the present invention is particularly useful as an electrical insulating material, and has a wide range of other uses such as impregnating resins, casting resins, and laminating resins.

Conventionally, epoxy resin has been widely used as an electrical insulating material, and although it exhibits excellent properties under normal conditions, it cannot withstand high temperatures or long-term use, and is classified as ydan (1) in the heat-resistant category.
(Can be used continuously at 55°O) is the limit. but,
With the recent improvements in performance and reliability of electrical equipment, the need for even better heat-resistant resins is increasing.

In the field of such heat-resistant resins, cured products of resin compositions containing maleimide compounds have been attracting attention, and many technologies have been disclosed in patents, literature, etc., starting with French Patent No. L455,514. However, all of them have drawbacks such as too high crosslinking density and brittle materials, which limits their range of use.

The present invention was made in view of such conventional problems,
It is an object of the present invention to provide a thermosetting resin composition that can provide a cured product with excellent heat resistance and good mechanical and electrical properties, and is easy to perform operations such as rough impregnation casting. 1 That is, the present invention provides: (a) a polyfunctional epoxy compound and its epoxy group;
, on the other hand, 20 to 95 parts (n11
) and (B) polyfunctional! Reimide compound 5-95% (this tht%
, hereinafter the same) and general formula (I): 0 0 0
0 amino acid residue, R2 represents an aliphatic tetracarboxylic acid residue or an aromatic tetracarboxylic acid residue, and n
represents a natural number of 0 or 1 to 5) and 95 to 5% of a nadic imide prepolymer. relating to things.

During curing of the composition of the present invention, the carboxyl group of the unsaturated carboxylic acid compound and the epoxy group of the polyfunctional epoxy compound react, and at the same time, the vinyl group of the former reacts with the maleimide group of the polyfunctional maleimide compound and the epoxy group of the nadic imide prepolymer. Since it is copolymerized with nazic imide groups, it forms a crosslinkable network structure and provides a cured product with excellent properties.

In the present invention, the composition has a composition in which the blending ratio of the unsaturated monocarboxylic acid compound to the polyfunctional epoxy compound is such that the former has an epoxy group of 0.8 to 1.5 carboxyl groups. It is blended as follows. If the amount of carboxyl groups is less than 0.8 equivalents or more than 1.5 equivalents, the electrical properties will deteriorate, possibly due to an increase in the amount of epoxy groups or carboxyl groups remaining after curing, respectively, which is undesirable.

Specific examples of polyfunctional epoxy compounds that can be used in the present invention include bisphenol A type Ebicor) 82
8, Epicote 864, Nipif, -) 1001 (all manufactured by Shell Chemical ■), alicyclic type 0Y-179, ay
-18 Lisuis (manufactured by Chipa), Novotic type D11i
4i51, DItN458 (manufactured by Dow Chemical Company, USA)
, moN1275 (manufactured by Ciba, Switzerland).

Specific examples of unsaturated monocarboxylic acid compounds that can be used in the present invention include acrylic acid, methacrylic acid, and silica acid.

Furthermore, in the present invention, it is also possible to use a compound prepared by reacting the composition of the body) in advance, and specific examples thereof include Aroex M-6100 and 70Nix U-6500 (both manufactured by Toagosei Chemical Industry Co., Ltd.). III)
Commercially available products such as

The composition (B) used in the composition of the present invention is formed by copolymerizing the constituent components, that is, the polyfunctional maleimide compound and the nadic imide prepolymer during curing, resulting in dense crosslinking II.
It has a strong structure and provides excellent heat resistance. Furthermore, by using a higher grade nadic imide prepolymer, the number of crosslinked molecules in the cured product increases, improving heat resistance and at the same time imparting flexibility.

The nadic imide prepolymer represented by the general formula (1) can be easily obtained by reacting a diamine compound, a tetracarboxylic acid compound, and nadic acid anhydride according to a conventional method.

Such diamine compounds may be either aliphatic diamine compounds or aromatic diamine compounds, and specifically include hexamethylene diamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, and 4,4-diaminodiamine. Diphenylsulfone, 4.4'-
Examples include diaminodicyclohexylmethane and isophoronediamine. Specific examples of tetracarboxylic acid compounds include benzophenonetetracarboxylic acid, pyromellitic acid, butane-1,2,3,4-tetracarboxylic acid, E)-(2゜5-dioxotetrahydrofuryl)-6 -Methyl-6-cyclohexene-1,2-dicarboxylic acid anhydride and the like.

Further, as the nadic imide prepolymer represented by the general formula (1), those in which n is a natural number of 0 or 1 to 5 are used. If n is larger than 5, the molecular weight of the compound will increase too much, resulting in lower solubility during blending, resulting in problems such as lower working efficiency.

The polyfunctional maleimide compound used in the present invention has two
More than one! Any substance having a leimide group may be used, and specifically, examples include N, N-(methylenedi-p-phenylene) simaleimide, N, N-(t+syzyp-phenylene) simaleimide, M, M-trr-phenylene rangemaleimide, M, N'-p-phenylene dimaleimide, m,
m-2,4-) lylene cymaleimide s'#lI'
-2*6-) Relencymaleimide, M, H'
-m-xylylene dimaleimide, /-hexamethylene dimaleimide, and the like.

Furthermore, a maleimide compound obtained by reacting a mixture of aromatic amines obtained by the reaction of aniline and formaldehyde with maleic anhydride can also be used in the present invention.

The blending ratio of the nadic imide prepolymer and the polyfunctional maleimide compound on the ridges is in the range of 5 to 95% of the latter, compared to 95 to 5% of the former. If the latter is less than 5%, the reactivity of the nagic imide group in the nagic imide prepolymer is low, resulting in an insufficient nail base, and if it is more than 95%, the effect obtained by blending the nagic imide prepolymer, That is, imparting heat resistance to the cured product becomes insufficient.

The combination of the composition of body) and the composition of CB) is the total composition 1.
00 copies include 20 to 95 copies of the former and 80 to 5 copies of the latter. If the latter is less than 5 parts, the heat resistance of the cured product becomes opaque, and if more than 80 parts is used, the heat resistance improves, but the crosslinking density becomes too high, resulting in a decrease in mechanical properties. Therefore, both are unfavorable.

The resin composition of the present invention optionally contains (i) a vinyl monomer such as styrene, vinyltoluene, divinylbenzene, etc.; Amine gradients, quaternary ammonium salts, Lewis acids, (flat) benzoyl peroxide, dicumyl peroxide
Addition of polymerization initiators for curing such as hydroxide, cumene hydroperoxide, etc.; (b) Fillers such as silica, calcium carbonate, alumina, zirconium silicate, lithium silicate, iron powder, alryonium, mica, etc. You can also do it.

When the thermosetting resin composition of the present invention having a ridge-like structure is heated and cured according to a conventional method, a cured product with excellent heat resistance (H8i or higher) and good electrical and mechanical properties can be obtained. It has a wide range of uses, including impregnating resins for electrical equipment, gripping resins, and laminating resins.

Next, the thermosetting resin composition of the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The nadic imide prepolymer used in the following examples is either of the following two types.

In other words, -1 (hereinafter referred to as N-engine P-A1) and (hereinafter referred to as N-engine P-A1)
-A2).

Example 1 D■-352 (U.S. Dow Co., Ltd.) was used as a polyfunctional epoxy compound.
Chemical Co., Ltd., 1709 with an epoxy equivalent of 170), 72 g of acrylic acid as an unsaturated monocarboxylic acid compound, and MDA-1, which is an aromatic amine mixture produced by the reaction of aniline and formaldehyde as a polyfunctional maleimide compound.
50 (Mitsui Toatsu Chemical ■l1l) anhydrous! A maleimide compound (hereinafter referred to as
A thermosetting resin composition was obtained by blending 121 g of a maleimide compound (referred to as a maleimide compound) and 409 of 1iIP-M1 as a nadic imide prepolymer.

The obtained composition was heat treated at 150 qo for 15 hours and at 220°0 for 8 hours to obtain a cured product.

The properties of this cured product were investigated with respect to the following items.

0) Bending strength (Kg/mm2) Measured at ambient temperatures of 25°0 and 200°0 according to the method of J.

(b) Tan δ value (support)) According to the method of J Engineering S 6911, the ambient temperature is 25°C.
and measured at 200°0.

(c) Volume resistivity (0 am) Measurements were made at ambient temperatures of 25°0 and 200°0.

) Heat distortion temperature (00) It was measured according to the method of J Engineering SK 7207.

(e) Weight loss on heating (2)) The cured product of the sample was left at an ambient temperature of 240° 0 for 500 hours, and then the weight loss rate was measured.

The results obtained are shown in Table 1.

Examples 2 to 5 Resin compositions having the amounts shown in Table 1 were prepared, and cured by heating under the same conditions as in Example 1 to obtain cured products.

The properties of each cured product were investigated in the same manner as in Example 1. The results obtained are shown in Table 1.

Comparative Example 1 An acid anhydride-cured epoxy resin consisting of Epikote 828, 1009 and methyltetrahydrophthalic anhydride@809 was cured at 15080 for 15 hours.

The obtained cured product was characterized in the same manner as in Example 1. The results are shown in Table 1.

Claims (1)

[Claims] (1) (A) 20 to 95 parts and (B) Polyfunctional maleimide compound 5 to 95% by weight and the general formula () is represented by a niamino residue, R2 is an aliphatic tetracarboxylic acid residue or an aromatic tetracarboxylic acid a! 80 to 5 parts by weight of a composition formed by blending 95 to 5 weight percent of a nadic imide prepolymer represented by n, where n represents a residue and n represents 0 or a natural number from 1 to 5. A thermosetting resin composition characterized by: