JPH0311294B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of Application of the Invention] The present invention relates to a heat-resistant molding composition, and more particularly to a heat-resistant molding composition that provides molded articles with excellent mechanical properties at high temperatures and does not deteriorate even when used at high temperatures for long periods of time. [Prior art] Epoxy resins are cured by reaction with acid anhydrides, amines, phenols, isocyanates, polyamino bismaleimide compounds, etc., have excellent mechanical and electrical properties, and are relatively chemically and thermally stable. Because it gives a good cured product, it is used in a wide range of fields such as casting, impregnation, lamination, molding, and painting. The properties of the cured resin are largely influenced by the type of curing agent, so the curing agent is selected depending on the application. By the way, epoxy resins cured with phenolic compounds are chemically inert and have good electrical and mechanical properties, so they are used as structural materials for electrical equipment and electronic components, sealing materials, and insulating materials. In particular, molded products using alkenylphenol polymers have excellent deterioration characteristics at high temperatures. On the other hand, in recent years, heat resistance requirements for various plastic parts have become increasingly strict, and materials with heat resistance of 200° C. or higher are strongly desired. For such uses, cured products using alkenylphenol polymers have problems in mechanical properties at high temperatures. Conventionally, aromatic polyimides, aromatic polyamideimides, maleimide compounds, and the like have been known as heat-resistant resins for such uses. However, although molding materials using these imide compounds have excellent high-temperature mechanical properties, when molding workability and molded products are used continuously for long periods of time at temperatures above 200°C, mechanical properties and electrical insulation properties deteriorate significantly. There were some shortcomings such as:
Therefore, we attempted to improve the high-temperature mechanical properties by blending an imide compound into a composition using an alkenylphenol polymer. However, there was a problem in that the long-term deterioration characteristics at high temperatures, which is a characteristic of cured products using alkenylphenol polymers, were significantly reduced. Conventionally, silane-based coupling agents have been widely used in such molding materials. [Object of the Invention] In view of the above, an object of the present invention is to provide a heat-resistant molding composition that provides molded articles with excellent high-temperature physical properties and long-term heat deterioration characteristics. [Summary of the Invention] The present invention is characterized by (a) an epoxy resin, (b) an alkenylphenol polymer, (c) a maleimide compound, (d) a coupling agent that is an organic titanium compound or an organic aluminum compound, (e) a fiber and/or Or a heat-resistant molding composition characterized by comprising a granular filler. The epoxy resin (a) used in the present invention refers to all known epoxy resins having at least two or more epoxy groups in one molecule. Specifically, bisphenol type epoxy resin obtained from bisphenol A and epichlorohydrin, novolak type epoxy resin obtained by reacting novolac resin with epichlorohydrin, and xylene obtained by reacting xylene and formalin or toluene and paraformaldehyde. Polyphenol-based epoxy resin obtained by reacting epichlorohydrin with a resin or a condensate of toluene resin and phenols; polyhydroxybenzene-based epoxy resin obtained by reacting epichlorohydrin with a polyhydric phenolic resin such as resol or hydroquinone. , epoxy resins obtained by reacting aromatic or aliphatic carboxylic acids with epichlorohydrin, epoxy resins obtained from vinyl polymers, epoxy resins obtained from polyhydric alcohols such as glycerin, cyclohexene, cyclopentadiene, dicyclopentadiene, etc. Epoxy resins obtained from natural products such as starch or unsaturated higher fatty acids, nitrogen-containing epoxy resins obtained from aniline or aliphatic amines, nitrogen-containing heterocycles obtained from isocyanuric acid, etc. silicon-containing epoxy resin obtained by reacting an epoxy resin with silanol, a silicon-containing epoxy resin obtained by oxidizing a silicon compound having a carbon-carbon double bond, and a silicon-containing epoxy resin having an olefinic unsaturated group. Epoxy resins include epoxidized phosphoric acid esters epoxidized with peracetic acid, silicon, and epoxy resins containing heavy metals other than phosphorus in the form of chelates, and these can be used alone or in combination of two or more. In addition, (b) alkenylphenol-based polymers are polymers obtained by thermal polymerization, ionic polymerization, or radical polymerization of vinylphenol, n-propenylphenol, isopropenylphenol, n-butenylphenol, or derivatives thereof. . The degree of polymerization varies over a wide range from a few polymers to tens of thousands of polymers, but it depends on the handling of the resin composition, the workability in preparing the molding composition, the moldability of the molding composition, and the various properties of the molded product. In relation to this, the degree of polymerization is 20 to 80 (average molecular weight about 3000 to 8000, melting temperature 160 to 220).
℃) is desirable. (c) As a maleimide compound, the general formula is (In the formula, R is a divalent organic group, such as a linear or branched alkyl group, a cyclic alkylene group consisting of 5 to 6 carbon atoms, a heterocyclic group containing at least one of oxygen, nitrogen, and sulfur atoms) , phenylene group or polycyclic aromatic group, -COO-, -SO ₂ -, -O-, -N
=N- (multiple arylene groups connected by at least one digit), or the general formula (In the formula, n is 1 to 5) Examples of maleimide compounds include N,N'-ethylene bismaleimide, N,N'-
Hexamethylene bismaleimide, N,N'-m-
Phenylene bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide, N,N'-methylenebis(3-chloro-P-phenylene)bismaleimide, N,N'-4,4'-diphenylmethane bismaleimide Enylsulfone bismaleimide, N,N'-dicyclohexylmethane bismaleimide, N,N'-m-xylene bismaleimide, N,N'-4,4'-diphenylcyclohexane bismaleimide and poly(phenylmethylene)polymaleimide etc. can be given. (d) Organotitanium compounds and organoaluminum compounds used as coupling agents have the general formula (R ₁ O) _n -Ti[-X ₁ (-OR ₂ ) _l ] _o or (R ₁ O) _o -Ti[-P (-OR ₂ ) _l OH〕 _o (However, in the formula, R ₁ is an alkyl group having 1 to 4 carbon atoms,
R ₂ is an alkyl group having 8 to 30 carbon atoms, and X ₁ is

【formula】

【formula】

【formula】

【formula】 [Embodiments of the invention]

Next, the present invention will be explained in more detail with reference to Examples. [Reference Examples] 1 to 4 Novolac type epoxy resin DEN438 (manufactured by Dow Chemical Company, epoxy equivalent: 190) 100 parts by weight, poly-
P-vinylphenol (trade name Resin M, manufactured by Maruzen Oil Co., Ltd., hydroxyl equivalent 120, weight average molecular weight 6000)
Four types of resin compositions were mixed with 68 parts by weight of N,N'-4,4'-diphenylmethane bismaleimide in the proportions shown in Table 1, and 400~400~ of fused silica glass powder with an average particle size of 4 μm was added as a filler. 950 parts by weight, 100 to 240 parts by weight of glass fiber with a length of 6 mm as a reinforcing agent, 3 parts by weight of epoxy silane as a coupling agent, and 3 parts by weight of montanic acid ester wax as a mold release agent.
A molding material was prepared by kneading for 15 minutes using a kneader heated to 75°C. Using this molding material, various test pieces were molded using a transfer molding machine. The molding conditions were a mold temperature of 180° C. and a pressure of 150 kg/cm ² . The weight loss rate of each molded article at 250°C was measured.
As a result, as shown in Table 1, when the maleimide compound is contained in the resin composition in a range of 30 to 120 parts by weight, molded products with excellent high-temperature mechanical properties and long-term deterioration properties can be obtained.

〔Effect of the invention〕

Various test pieces were molded using each of the above molding materials, and various properties of the materials were examined. The results are shown in Table 2 and Figure 1. As is clear from Table 2 and Figures 1 and 2, the material of the present invention uses an organic titanium compound or an organic aluminum compound as a coupling agent, so that the high-temperature mechanical properties of the molded product are good and the material lasts for a long time. Excellent thermal deterioration properties.

【table】 [Brief explanation of the drawing]

FIGS. 1 and 2 are diagrams showing the results of various properties of the material.

Claims (1)

[Claims] 1 (a) an epoxy resin, (b) an alkenylphenol polymer, (c) a maleimide compound, and (d) a coupling agent having the general formula (R ₁ O) _n −Ti[—X ₁ OR ₂ ) _l ] _o or (R ₁ O) _n -Ti[-P(-OR ₂ ) _l OH] _o (wherein R ₁ is an alkyl group having 1 to 4 carbon atoms,
R ₂ represents an alkyl group having 8 to 20 carbon atoms, and X ₁ represents an integer of 1 to 4. ) or (However, in the formula, R ₃ is an alkyl group having 1 to 8 carbon atoms,
R ₄ and R ₅ represent an alkyl group or an alkoxy group having 1 to 30 carbon atoms, and m' represents an integer of 1 to 3. 1. A heat-resistant molding composition comprising an organic titanium compound or an organic aluminum compound represented by (e) fibers and/or granular fillers.