JPH04120160A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermosetting resin composition, excellent in heat resistance, quick curability and moldability and suitable as resins for multilayered lamination, sliding materials, etc., by blending polystyrylpyridine resin with a specific polyfunctional maleimide resin in a specified amount. CONSTITUTION:A thermosetting resin composition is obtained by blending (A) 100 pts.wt. polystyrylpyridine resin with (B) 5-50 pts.wt., preferably 10-30 pts.wt. polyfunctional maleimide resin, expressed by formula I (M1 is formula II; R is H or methyl; n is 0-2) and having >=4 maleimide groups in the molecule.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides resins for multilayer lamination, sliding materials, sealing materials, molding materials, composite materials, and heat-resistant, fast-curing, This invention relates to a resin composition with excellent moldability.

[Prior art and problems]

Various resin compositions have been developed for the electrical, electronic, and aerospace fields, but in recent years, there has been a strong demand for improved heat resistance. Traditionally, epoxy resins, bismaleimide resins, and polyimide resins have been used in these fields, but epoxy resins and bismaleimide resins do not have sufficient heat resistance, and polyimide resins are insoluble and infusible, resulting in poor moldability. be.

Polystyrylpyridine resin (hereinafter referred to as PSP resin) is known as a resin that satisfies the requirements regarding moldability and heat resistance.

However, PSP resin is
It is necessary to cure for 8 hours, which poses a major problem in terms of poor productivity. For this reason, modification by blending various thermosetting resins has been proposed for the purpose of imparting fast curing properties to PSP resins. For example, ■ Japanese Patent Publication No. 6 [
1-149851 and JP-A-82-48759, regarding the phenol resin formulation, ■ JP-A-62-1
8460, JP-A No. 82-48759, and JP-A-62-58386, regarding epoxy resin formulation, JP-A-62-201960, JP-A-62-
No. 215617 and Jikai [No. 15286 proposes a poly(N-phenylmethylene) maleimide resin formulation, and JP-A-62-270650 proposes a vinyl ester resin formulation.

However, the above-mentioned thermosetting resin (modifier) has very little effect on improving moldability unless it is blended in an amount of 50 to 100 parts by weight or more to 100 parts by weight of the PSP resin. If the content of the modifier is increased, the heat resistance will be significantly reduced.

In addition, poly(N-phenylmethylene) maleimide resin, which has relatively high heat resistance, has poor impact resistance and poor moldability, as pointed out in JP-A No. 1-95151, so it is not suitable for practical use. It is not suitable as a modifier for PSP resin.

[Object and structure of the invention]

The present inventors have conducted extensive research to solve the above-mentioned problems with PSP resins, and as a result, have arrived at the present invention. An object of the present invention is to provide a thermosetting resin composition that can be cured at low temperatures and in a short time without impairing the heat resistance of PSP resin by adding a specific polyfunctional maleimide resin to PSP resin. be.

The configuration of the present invention is as follows.

(1) A thermosetting resin composition containing the following [A] acid component and [B] acid component.

[A] Component: Polystyrylpyridine resin [B] Component: Polyfunctional maleimide resin having at least 4 maleimide groups in the molecule (2) [B] component is 5 parts by weight per 100 parts by weight of [A] component.
50 parts by weight of the thermosetting resin composition according to claim 1.

(3) The thermosetting resin composition according to claim (1), wherein the polyfunctional maleimide resin of component (l) is represented by the following general formula.

l is an integer of old and old 0 and 2. ) [Component A), the PSP resin, is, for example, French Patent No. 22
61296 and 2378052, and US Pat. No. 3,994,862, it can be produced by the reaction of methylated pyridine with an aromatic dialdehyde.

For example, the PSP resin as the component [A] has the following general formula (
Examples include those shown in I).

Here, R represents a hydrogen atom, a methyl group, an ethyl group,
Among them, methyl group is preferred.

A particularly preferable prepolymer structure is represented by the following structural formula (I):
It has the repeating structure shown in FIG. This prepolymer is also called PSP6022 resin and is published in "Plastics J Vol. 36. No.

77 (1985).

[B] Acid component Examples of the polyfunctional maleimide resin include those represented by the following general formula (III). The polyfunctional maleimide resin represented by general formula (III) is MP2000
Also known as r 32nd International
l SAMPE SymposiumJ Vol, 32
．． April 16-9.33 (1987).

It is an integer between old and old 0 and 2. ) CB] component polyfunctional maleimide is [Al component PSP
It is usually 5 to 50 parts by weight, particularly preferably 10 to 30 parts by weight, based on 100 parts by weight of the resin.

If the content of component [B) is less than 5 parts by weight, the quick curing properties will be poor, and if it exceeds 50 parts by weight, the heat resistance will be poor. Furthermore, when a reinforcing material is impregnated with the resin composition to form a prepreg, if the content of component [B] exceeds 50 parts by weight, the handleability of the prepreg, such as tackiness, decreases.

The following components can be added to the thermosetting resin composition of the present invention as necessary.

■ Powdered reinforcing materials and fillers, such as silica, acid clay,
Bentonite, glass peas, carbon black, zeolite, diatomaceous earth, mica, kaolin, talc, etc.

The amount of these reinforcing materials and fillers used is [PSP of Al component]
5 for 100 parts by weight of resin! It is desirable that the amount is less than Ii parts.

■Fibrous reinforcing materials and fillers, such as glass fiber, carbon fiber, alumina fiber, ceramic fiber, silicon carbide fiber,
Aromatic polyamide fibers (aramid fibers), etc. The fibrous filler can be used in any form such as long fibers, short fibers, chopped, sheet, woven, knitted, mat, or paper. Use of these fibrous reinforcing materials and fillers
Although it varies depending on the use, up to 400 parts by weight of the resin composition can be used as a laminated material or a molding material based on 100 parts by weight of the resin composition.

■Colorants, pigments, flame retardants and flame retardant aids, such as titanium dioxide, yellow lead, carbon black, antimony trioxide, etc. The amount of these colorants, pigments, flame retardants and flame retardant aids used is desirably less than 5 parts by weight per 100 parts by weight of the [A] acid component PSP resin.

(2) Furthermore, other resins can be used for the purpose of improving the physical properties of resin molded products. Other resins that can be used in the present invention include, for example, phenolic resins,
Melamine resin, urea resin, furan resin, xylene resin,
Thermosetting resins such as polyimide resins and polyisoimide resins with acetylene ends, polyimide resins with nadic acid ends, and amide bonds, imide bonds, ester bonds, ether bonds, carbonate bonds, urethane bonds, urea bonds, thioether bonds, etc. , sulfone bond, imidazole bond, carbonyl bond, etc., such as polyamide, polyamideimide, polyimide, polyetherimide, polyether ether ketone, polyester, polycarbonate, polysulfone, polyether sulfone, polyphenylene. These include sulfide, polyphenylene oxide, polyoxybenzoyl, and polyketone imide. The amount of these resins used is within a range that does not impair the inherent properties of the resin composition of the present invention, and preferably the ps of component [A]
r' resin 1 resin 1 amount 0 [Effect of the invention] The thermosetting resin composition of the present invention has good fast curing properties without impairing heat resistance by blending a specific polyfunctional maleimide resin with PSP resin. , easy moldability can be obtained.

[Examples and comparative examples]

The present invention will be explained in more detail by giving examples.

Unless otherwise specified, "%" and "part" are based on weight.

Example 1 and Comparative Example 1 psp resin PSP8022PL (manufactured by SNPIE) 10
Add 10 parts of polyfunctional maleimide resin MP-2000xC manufactured by Mitsubishi Yuka Co., Ltd. to 0 parts and heat at 80°C for 30 minutes.
A resin mixture was obtained. Since this resin mixture had a very low viscosity, it was also possible to impregnate reinforcing fibers such as carbon fibers without using a solvent.

The gelation time of the resin mixture was measured using a culastometer. For comparison, a prepreg was made in the same manner without the addition of the polyfunctional maleimide resin, and measurements were also taken. The results are shown in Table 1. From the results in Table 1, it can be seen that the curing time could be significantly shortened.

Table 1 Note*: Measurement temperature Examples 2 to 4 and Comparative Example 2 Resin mixtures of various compositions consisting of PSP resin and polyfunctional maleimide were prepared in the same manner as in Example 1. The gelation time n1 was determined for this product.

Here, as a comparative example, bismaleimide resin Compimi
The gelation time of the system containing de (manufactured by Technochemy Co., Ltd.) was measured. The results are also shown in Table 2.

From the results in Table 2, it can be seen that the system in which polyfunctional maleimide is blended with PsP resin has a significantly shorter curing time than the system in which bismaleimide is blended, and is effective even with a small amount of blending. .

Kawamata (Note) H: 1TIII Constant Temperature Ne2: Curing Catalyst Diazabicyclooctane Example 5 and Comparative Example 3 After curing the PsP resin of Example 4 Resin Mixture and Comparative Example] under the following conditions, Post-curing was performed under various conditions shown in Table 4.

Table 3: Glass transition temperature of the obtained cured resin according to ASTM D34
Measured by DSC according to 1g-82. The results are shown in Table 4.

From the results in Table 4, it can be seen that the cured resin made by blending polyfunctional maleimide resin with PSP resin can be molded at low temperatures in 1 hour as described above, and has a sufficiently high glass transition temperature with a short post-cure time. It can be seen that the curing and post-curing times are significantly shortened and heat resistance is maintained.

Table 4 (Note) *: Post-cure time at 260°C Patent applicant: Toho Rayo' / Patent attorney representing Hayashi Roku Company: Doi Mibe

Claims (3)

[Claims] (1) A thermosetting resin composition containing the following [A] component and [B] component. [A] Component: Polystyrylpyridine resin [B] Component: Polyfunctional maleimide resin having at least 4 maleimide groups in the molecule (2) 5 parts of [B] component per 100 parts by weight of [A] component
50 parts by weight of the thermosetting resin composition according to claim 1. (3) The thermosetting resin composition according to claim (1), wherein the polyfunctional maleimide resin of component [B] is represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, MI indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼, R indicates a hydrogen atom or a methyl group, and n is an integer from 0 to 2.)