JPH0688382B2 - Heat resistant resin composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a composite material having excellent heat resistance and mechanical strength, which is used as a structural material in various fields such as electric / electronic fields, automobile fields and the like. Is.

[Prior Art] In recent years, miniaturization has rapidly progressed in the electric and electronic fields, and accordingly, there is a strong demand for improvement in reliability. Therefore,
Materials used therefor are required to have better electrical characteristics and heat resistance.

Further, in the field of automobiles or other structural materials, the use of plastics as a substitute for metal is rapidly increasing for weight reduction. For such applications, plastics having excellent mechanical strength, heat resistance and environment resistance are desired. Under such circumstances, various plastics have been developed and used properly depending on the purpose and application. When the required performance is not sufficiently satisfied with the plastics alone, various reinforcing materials and fillers are compounded and compounded to improve the performance. It is considered that such composite materials will become more important materials in the future because they have characteristics that other materials do not have. However, there are few composite materials that can cope with the rapid miniaturization and weight reduction of recent products, and each has its advantages and disadvantages, so that a higher performance composite material is required.

[Problems to be Solved by the Invention] An object of the present invention is to provide a novel heat-resistant resin composite material that can be used as a structural material in other fields such as electric / electronic fields, automobile fields, space, and aircraft fields. It is what

[Means for Solving the Problems] The present invention provides a heat-resistant resin composite material comprising an aromatic polythioethersulfone polymer or a cured product thereof and various fibrous materials, and is obtained by the present invention. Because of its excellent heat resistance, mechanical strength, electrical properties, and chemical resistance, composite materials are widely used as insulating materials in the electric and electronic fields, automobile parts, mechanical parts, space / aircraft parts, and other structural materials. Can be used.

The aromatic polythioether sulfone-based polymer in the present invention is a copolymer represented by the following general formula. This aromatic polythioether sulfone-based polymer is composed of the following n thioether sulfone residues and m ether sulfone residues (m and n are integers of 1 or more), and each residue is linked in block or random form. It is a copolymer. This copolymer is described in Japanese Patent Application No. 59-193968 (Japanese Patent Publication No. 141169) disclosed by the present inventors, and its manufacturing method is described in the same application and Japanese Patent Application No. 59-196723 (Japanese Patent Publication No. -47690), Japanese Patent Application No. 60-8386 (Japanese Patent Publication No. 4-58807).
It is described in. This copolymer is a thermoplastic resin having excellent mechanical properties at high temperatures, and can be a cured product as described later.

(However, Ar in the formula is R ^{1 to} R ⁷ represent a hydrocarbon group having 1 to 8 carbon atoms and may be the same or different from each other;
4, f and g are integers of 0 to 3 and may be the same or different; Y is a single bond -O-,-S-,-SO-,-SO _2- , R is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; m and n are each an integer of 1 or more which represents the degree of polymerization) and are aromatic polythioether sulfone polymers.

In the above formula, m: n represented by the degree of polymerization, m: n
= 1: 20 to 20: 1 is preferable. And in view of the characteristics as a copolymer, moldability, etc., preferably m: n is 1: 1.
It is 0 to 15: 1, and more preferably m: n is 1: 4 to 10: 1.
The degree of polymerization of aromatic polythioether sulfone polymer was measured at 30 ℃ in a solution of phenol / 1,1,2,2-tetrachloroethane (3/2 polymerization ratio) at a concentration of 0.5g / dl. When expressed by the logarithmic viscosity number ηinh, it is usually preferably 0.1 to 1.5. And more preferably, the logarithmic viscosity number ηinh is 0.1 to 1.3, and particularly preferably 0.1 to 1.
It is 0. Such copolymers include, for example, dihalodiphenyl sulfones having a halogen atom such as a chlorine atom in the para position or ortho position in each aromatic nucleus, HO-Ar-
It is obtained by reacting a diphenol represented by OH and an alkali metal sulfide. In this reaction, an alkali metal hydroxide or carbonate is used as a dehalogenating agent, but diphenols may be used in advance instead of the corresponding alkali metal phenoxide. This reaction may be carried out in a single stage, or a multi-stage method using a precursor may be adopted as a suitable method.

The cured product of the aromatic polythioether sulfone-based polymer in the present invention is a three-dimensionally cross-linked cured product obtained by crosslinking the above aromatic polythioether sulfone-based polymer. As the cross-linking agent, an epoxy compound having at least two epoxy groups in one molecule (that is, a so-called epoxy resin), an isocyanate compound having at least two isocyanate groups in one molecule or an aminoplast resin, metal acetylacetoacetate Nates, Group VIII or Group IB metal halides of the Periodic Table are preferred.

A cured product is obtained by mixing these cross-linking agents with an aromatic polythioether sulfone-based polymer and subjecting to heat treatment.

As the epoxy compound, a liquid or solid one can be used, and a partial polymer (prepolymer) can also be used. Such epoxy compounds include glycidyl ether-based, glycidyl ester-based, glycidyl amine-based glycidyl epoxy resins, non-glycidyl epoxy resins,
A so-called general epoxy resin such as a novolac type epoxy resin can be used, and a trifunctional or higher functional polyfunctional epoxy resin is preferably used. As the isocyanate compound, a liquid or solid one can be used, and a partial polymer (prepolymer) can also be used. As the isocyanate compound, any of aliphatic and aromatic isocyanates such as hexamethylene diisocyanate and tolylene diisocyanate can be used, and it is preferable to use these as a trimethylolpropane modified product or an isocyanurate modified product.

Aminoplast resins are aldehyde condensates of melamine, urea, guanamine and their analogs and aliphatic or aromatic polyamino compounds.

Among these, the compound obtained by reacting melamine, urea, or benzoguanamine with formaldehyde is the most well known, and is most preferably used.

The above amine / aldehyde condensation product may have an alkylol group such as methylol, and in many cases,
At least a part thereof is etherified by a reaction with alcohol to obtain an organic solvent-soluble resin.
For this purpose it is preferred to use amine-aldehyde resins etherified with methanol or butanol.

In the cross-linking agent, the metal acetylacetonate and the metal halides of Group VIII and Group IB of the Periodic Table have a different mechanism of action from the cross-linking agent having a cross-linkable group as described above, and are radicalized by heating. It is considered that the radical is decomposed into active radicals, and these radicals oxidatively crosslink aromatic nuclei. Metal acetylacetonate
It is a metal chelate compound of acetylacetone, and examples of such a compound include (1) Group IA and (2) of the periodic table.
Group IIA, (3) Group IIIB, (4) Group IVB, (5) Group VB
Clan, (6) VIB group, (7) VIIB group, (8) VIII
Group, (9) Group IB, (10) Group IIB, (11) Group IIIA,
(12) Each acetylacetonate of the lanthanide family is preferred.

Among such acetylacetonates, Cu (II), Mn (II), Mn (III), Fe (III), Co (II), N are particularly preferable.
Acetylacetonates such as i (II), Al (III), and Zn (II).

FeCl ₃ and CuCl ₂ are particularly preferably used as the metal halides of Group VIII and Group IB of the periodic table.
In the method for obtaining a cured product in the presence of a crosslinking agent as described above, the amount of the crosslinking agent is 0.05 to 50% by weight, preferably 0.1 to 20% by weight based on the aromatic polythioether sulfone polymer.
% By weight. The metal chelate of acetylacetone is effective even in a very small amount.

Two or more kinds of such cross-linking agents may be used in combination within a suitable addition amount range. When these crosslinking agents are used, the curing temperature in the heat treatment is usually 150 to 400 ° C, preferably Tg or higher to 350 ° C or lower of the aromatic polythioether sulfone polymer. If it is lower than this, the curing rate is slow, and if it is higher than this, a decomposition reaction occurs, which is not preferable. The curing time varies variously depending on the temperature, but usually 5 minutes to 10 hours can cure.

As the fibrous material that can be used in the present invention, glass, polyparaphenylene terephthalamide, aromatic polyamide such as polymetaphenylene isophthalamide, carbon, metal such as steel, alumina, ceramics such as silica, and the like, As the form, various forms such as short fiber, long fiber, cloth, non-woven fabric, paper and surface mat can be used.

The composite of the fiber material and the aromatic polythioether sulfone-based polymer or a cured product thereof can be carried out by using a usual general method. For example, extrusion molding, injection molding, compression molding, melt impregnation method, solution impregnation method and the like can be integrated to form a composite. The composite material of the present invention thus obtained can take various forms such as a film shape, a sheet shape, a block shape, and the like. Electric / electronic parts, automobile parts, machine parts, space / aircraft parts, other structural materials, etc. Can be used for.

Examples Example 1 4,4'-dichlorodiphenyl sulfone, bisphenol
To a precursor obtained by reacting A and sodium hydroxide, 4,4'-dichlorodiphenyl sulfone and sodium sulfide were added and reacted to obtain an aromatic polythioether sulfone polymer represented by the following formula. (For details, see Japanese Patent Application No. 60-8386).

m: n = 10: 1 ηinh = 0.45; measured in PhOH / 1,1,2,2-tetrachloroethane 3/2 (weight ratio) at 30 ° C. and 0.5 g / dl.

50 g of this polymer and 2 g of hexamethoxymethylmelamine
A varnish was prepared by dissolving it in 300 g of 1,2,2-tetrachloroethane. Use this varnish with a 30 μm thick glass fiber cloth (“KS
1020 "Kanebo Co., Ltd.), dried at 100 ° C. for 1 hour, and then heat-treated at 280 ° C. for 1 hour to obtain a composite film having a thickness of 65 μm and a resin content of 70%. The physical properties of this composite film are shown in Table 1.

Example 2 N, N, N ', N' instead of hexamethoxymethylmelamine
-Tetraglycidyl-m-xylylenediamine was used to prepare a varnish prepared in the same manner as in Example 1, except that the thickness was 300 μm.
Glass fiber paper (manufactured by Nippon Vilene) of No. 2 and impregnated with it and dried in the same manner as in Example 1, and then 280 under a pressure of 50 kg / cm ² .
Heat treatment was carried out for 1 hour at ℃ to obtain a composite film having a thickness of 250 μm and a resin content of 70%. The physical properties of this composite film are shown in Table 1.

Example 3 A 100 μm thick polyparaphenylene terephthalamide fiber cloth (“Keplar S-120” manufactured by DuPont) was impregnated with the varnish prepared in the same manner as in Example 1, dried in the same manner as in Example 1, and then crosslinked. Thickness 150μm, resin content 60
% Composite film was obtained. The physical properties of this composite film are shown in Table 1.

Example 4 A varnish prepared in the same manner as in Example 1 was impregnated into a polymetaphenylene isophthalamide fiber paper (“Nomex 410” manufactured by DuPont) having a thickness of 50 μm, followed by drying and crosslinking as in Example 1. A composite film having a thickness of 100 μm and a resin content of 70% was obtained. The physical properties of this composite film are shown in Table 1.

Example 5 A varnish prepared in the same manner as in Example 1 was impregnated into a polymetaphenylene isophthalamide fiber non-woven fabric (“Nomex Spunlace E-88” manufactured by DuPont) having a thickness of 64 μm,
After drying in the same manner as in Example 1, crosslinking was performed to obtain a composite film having a thickness of 130 μm and a resin content of 85%. The physical properties of this composite film are shown in Table 1.

Example 6 The following copolymer was produced in the same manner as in Example 1 except that bisphenol A was replaced by 4,4-dihydroxydiphenyl.

(M: n = 1: 1, ηinh = 0.62) 50 g of this polymer, 2.5 g of hexamethoxymethylmelamine
A varnish was prepared by dissolving it in 320 g of 1,2,2-tetrachloroethane. Use this varnish with a glass fiber cloth ("H
1080 "Asahi Fiberglass) impregnated at 100 ℃ 1
After drying for 1 hour, heat treatment was performed at 280 ° C. for 1 hour to obtain a composite film having a thickness of 140 μm and a resin content of 75%. The physical properties of this composite film are shown in Table 1.

Example 7 A varnish prepared in the same manner as in Example 6 was impregnated into a polymetaphenylene isophthalamide fiber paper (“Nomex 410” manufactured by DuPont) having a thickness of 50 μm, and dried and crosslinked in the same manner as in Example 6 to give a thickness. A composite film having a length of 80 μm and a resin content of 60% was obtained. The physical properties of this composite film are shown in Table 1.

Example 8 50 g of the copolymer prepared in Example 6 and 0.5 g of Cu (acac) ₂ were N--
It was dissolved in 250 g of methyl-2-pyrrolidone to prepare a varnish. This varnish was impregnated into the glass fiber cloth of 50 μm used in Example 6 and the same drying and heat treatment as in Example 6 were carried out to obtain a composite film having a thickness of 120 μm and a resin content of 70%. The physical properties of this composite film are shown in Table 1.

Comparative Example 1 A varnish prepared in the same manner as in Example 1 was cast on a glass substrate with a doctor blade, and dried and heat treated in the same manner as in Example 1 to obtain a film having a thickness of 50 μm.
The physical properties of this film are shown in Table 1.

Example 9 Fifteen composite films obtained in Example 6 were stacked and thermocompression bonded under the conditions of 300 ° C., 50 kg / cm ² and 5 minutes using a press molding machine to obtain a laminated plate having a thickness of 2 mm. The physical properties of this plate are shown in Table 2.

Example 10 The varnish prepared in Example 6 was treated with 100 μm thick polyparaphenylenephthalamide fiber cloth (“Kevlar S-120”).
Dupont) and dried at 100 ° C for 1 hour, then 280
It was heat-treated at ℃ for 1 hour to obtain a composite film having a thickness of 150 μm and a resin content of 60%. Fifteen composite films were stacked and thermocompression bonded under a condition of 300 ° C., 50 kg / cm ² , and 5 minutes using a press molding machine to obtain a laminated plate having a thickness of 2.2 mm. The physical properties of this plate are shown in Table 2.

Example 11 The varnish prepared in Example 6 was impregnated with a carbon fiber cloth (“# 6151 B” manufactured by Toray Industries, Inc.) having a thickness of 140 μm, and the varnish was dried at 100 ° C. for 1 hour.
After drying for 1 hour, heat treatment was performed at 280 ° C. for 1 hour to obtain a composite film having a thickness of 170 μm and a resin content of 50%. This composite film 12
Stack the sheets and press them at 300 ℃, 50kg / cm ² , 5
It thermocompression-bonded on the conditions of minutes, and obtained the laminated board of thickness 1.9mm. The physical properties of this plate are shown in Table 2.

Example 12 10 In a stainless steel autoclave 4,4'-diphenol 559.2g (3.0mol), anhydrous potassium carbonate 539g (3.9mo
l), 4,4'-dichlorodiphenyl sulfone 947.7g (3.3m
ol), N-methyl-2-pyrrolidone 2 and 500 ml of toluene were charged and heated under a nitrogen stream to continuously remove water produced by azeotropic distillation, and toluene was dehydrated while returning it to the reactor. When the water was no longer distilled off, the temperature was gradually raised, and finally the temperature was raised to 190 ° C to distill off the toluene. Thereafter, the mixture was reacted at 200 ° C. for 3 hours and then cooled. Subsequently, sodium sulfide (60% purity) 385.6 g (3.0 mol), 4,4'-dichlorodiphenyl sulfone 775.4 g (2.7 mol), N-methyl-2-pyrrolidone 2 were added to the reaction mixture.
Was charged, and the mixture was pressurized and sealed with nitrogen gas at 5 kg / cm ² (gauge pressure), and reacted at 200 ° C. for 3 hours. After the reaction, the temperature was cooled to 150 ° C., the reactor was opened, and methane chloride was passed for 1 hour to stop the reaction.

The reaction mixture was filtered to remove by-produced salts and then poured into a large amount of water to precipitate a polymer. This polymer was pulverized, washed with hot water three times and twice with methanol, and dried under reduced pressure at 150 ° C. to obtain 1950 g of a white polymer. This polymer Ηinh = 0.63 with a production of (m: n = 1: 1). This polymer has a glass fiber (“Glasslon chop strand
03MA497 ": manufactured by Asahi Fiber Glass Co., Ltd.), mixed by 30%, extruded under the following conditions to form pellets, and then injection molded to a thickness
A 2 mm plate was obtained.

Extrusion conditions Cylinder temperature 330 ℃ / 330 ℃ / 330 ℃ Abapter temperature 330 ℃ Die temperature 330 ℃ L / D 24 Injection condition Cylinder temperature Hopper 310 ℃ 〃 Middle 340 ℃ 〃 Nozzle 350 ℃ Mold temperature 130 ℃ Injection pressure 1500kg / cm ² Holding pressure 400 kg / cm ² Injection speed High speed Cycle time 40 seconds Table 2 shows the physical properties of the obtained plate.

Comparative Example 2 The polymer obtained in Example 12 was extruded and pelletized by injection molding to obtain a plate having a thickness of 2 mm.
Same as). Table 2 shows the physical properties of the obtained plate.

[Effects of the Invention] The composite material comprising the aromatic polythioether sulfone-based polymer of the present invention or a cured product thereof and a fibrous material is excellent in heat resistance, mechanical strength and chemical resistance, and is greatly improved as compared with a resin alone. ing. When the fibrous material is an electric insulating material, the composite material is also excellent as an electric insulating material.

Claims (3)

[Claims] 1. A heat-resistant resin composite material comprising an aromatic polythioether sulfone-based polymer represented by the following general formula and a fibrous material. (However, Ar in the formula is R ^{1 to} R ⁷ represent a hydrocarbon group having 1 to 8 carbon atoms and may be the same or different from each other;
4, f and g are integers of 0 to 3 and may be the same or different; Y is a single bond —O—, —S—, —SO—, —SO ₂ —, R is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; m and n are integers of 1 or more each representing the degree of polymerization. ) 2. A heat-resistant resin composite material comprising a cured product of an aromatic polythioether sulfone polymer represented by the following general formula and a fibrous material. (However, Ar in the formula is R ^{1 to} R ⁷ represent a hydrocarbon group having 1 to 8 carbon atoms and may be the same or different from each other;
4, f and g are integers of 0 to 3 and may be the same or different; Y is a single bond —O—, —S—, —SO—, —SO ₂ —, R is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms; m and n are integers of 1 or more each representing the degree of polymerization. ) 3. A cured product of an aromatic polythioether sulfone-based polymer, an aromatic polythioether sulfone-based polymer and an epoxy compound having at least two epoxy groups in one molecule or at least two in one molecule. A cured product obtained by mixing the above-mentioned isocyanate compound having an isocyanate group, or an aminoplast resin, a metal acetylacetonate, and at least one metal halide of Group VIII or Group IB of the periodic table, and heat-treating the mixture. The composite material according to claim 2.