JPS5927942A - Thermoplastic polymer composition having good heat resistance - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to oil and heat and mechanical strength, consisting of an arom. polyether resin, a specified copolymer, a polyamide, an impact modifier and a phosphorus compd. CONSTITUTION:1-30pts.wt. phosphorus compd. of formula I or II (wherein X is H, OH; Z is O, S; n, p are each 0-4) is blended with 100pts.wt. resin compsn. consisting of 5-95wt% arom. polyether resin (A) such as poly (2,6-dimethylphenylene-1,4-ether), 0.5-90wt% copolymer (B) composed of 60-99wt% styrene compd. and 40-1wt% alpha,beta-unsaturated dicarboxylic acid anhydride such as maleic anhydride, 1-90wt% polyamide (C) having an MW of 5,000-50,000 obtd. from xylylenediamine and an aliph. dicarboxylic acid such as adipic acid, and 0-80wt% impact modifier (D) such as styrene/butadiene block copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly heat-resistant thermoplastic resin composition with excellent oil resistance. More specifically, the present invention provides an aromatic polyether resin, a copolymer containing a styrene compound and an α,β-unsaturated dicarboxylic acid anhydride as components, and a copolymer obtained from a xylylene diamine and an aliphatic dicarboxylic acid. The present invention relates to compositions made of 1-lyamide resins and resin compositions made by adding an impact strength reinforcing agent to these compositions.

Aromatic polyether resin has mechanical properties, electrical properties,
It is attracting attention as a resin suitable for a wide range of applications due to its properties such as excellent heat resistance and excellent dimensional stability, but it is also attracting attention as a resin suitable for a wide range of applications. A major drawback is that it has poor oil resistance.

Japanese Patent Publication No. 45-997 proposes adding polyamide to improve the moldability of aromatic polyether resins, but aromatic polyether resins and polyamides are highly compatible. The resulting resin composition has poor mechanical properties (especially when the polyamide content is around 20% by weight), and the molded product obtained by injection molding exhibits a delamination phenomenon. Molded products cannot be obtained.

In addition, in order to improve moldability and impact strength, Japanese Patent Publication No. 43-17812 and Japanese Unexamined Patent Publication No. 49-98858
Aromatic polyether resin while busy with publications? It has also been proposed in JP-A-52-128947 to blend listyrene or rubber-reinforced polystyrene with a copolymer of a rubber-reinforced styrenic compound and an α,β-unsaturated dicarboxylic acid anhydride and an aromatic polystyrene. Although it has been proposed to blend ether resins, the major drawback of these tung fat combination acids is that they also have poor oil resistance.

Resin compositions such as rubber-reinforced polystyrene/aromatic polyether resins have excellent impact resistance and moldability, and are widely produced industrially. The scope of use is limited.

When it comes to engineering plastics, it is important to have excellent heat resistance, impact resistance, and oil resistance. W, its range of applications can be greatly expanded.

There is almost no prior art regarding aromatic polyether resins that have excellent oil resistance, high heat resistance, and high impact strength, and no resins have been put to practical use.

The present inventors have conducted intensive studies to obtain a resin composition that has excellent oil resistance, high heat resistance, and high impact strength, and can be used in a wide range of applications. Furthermore, by further blending a copolymer containing a styrene compound and an α,β-unsaturated decal anhydride as components, and an impact strength reinforcing agent, a resin composition having h performance compared to the conventional one can be obtained. The very interesting fact that this can be obtained was reported in Japanese Patent Application No. 55-110360. The present inventors further discovered that the use of a copolymer obtained from xylylene diamine and a resin group dicarboxylic acid as the polyamide improves the dimensional accuracy, hygroscopicity, and mechanical strength of the resulting resin composition. The present invention has been completed based on the discovery that favorable results can be obtained in terms of less deterioration.

The resin composition of the present invention contains less phosphorus, aliphatic hydrocarbons, and more than a resin composition consisting of an aromatic polyether resin and rubber-reinforced polystyrene, or a rubber-reinforced styrene-maleic anhydride copolymer. It is a molding material that has significantly improved resistance to chemicals such as compounds, and has excellent heat resistance and mechanical properties.

Aromatic polyether resin, polyamide obtained from xylylene diamine and aliphatic dicarginic acid, styrene compound and α,β-unsaturated dicaru? By further blending an impact strength reinforcing agent into a copolymer containing phosphoric acid anhydride as a component, a resin composition having extremely excellent impact strength can be obtained. On the other hand, a resin composition with excellent impact resistance cannot be obtained by combining an aromatic polyether resin, a preamide obtained from xylylene diamine and a resinous dicarboxylic acid, and an impact strength reinforcing agent, and injection molding The molded product obtained by this method exhibits a layered peeling phenomenon, which is not desirable. The synergistic effect of the four-component mixture according to the present invention is remarkable, especially the effect due to the presence of a copolymer containing a styrene compound and an α,β-unsaturated dicargonic acid anhydride as components.

Regarding the effects of the copolymer containing the styrene compound of the present invention and α, β-, β-dicarboxylic acid anhydride as components, Japanese Patent Application No. 54-127298, No. 54-12
As seen in Publication No. 9467, styrene compounds and α
, β-, β-dicarboxylic acid anhydride as a component and polyamide, a copolymer in which both are bonded can be obtained. It is thought that chemical bonds are similarly formed between the polyamide and the copolymer containing the styrene compound and the α,β-unsaturated decal anhydride as components in the product. Through such chemical bonding, a dispersion state of a copolymer containing an aromatic polyether resin, a preamide, a styrene compound and an α,β-unsaturated decal anhydride as components, and an impact strength reinforcing agent are obtained. It is believed that this resin composition exhibits a microstructure that has not been previously available at all, and that a resin composition with excellent performance and high impact strength can therefore be obtained. This indicates that the resin composition of the present invention is a resin composed of an aromatic polyether resin, a polyamide obtained from xylylene diamine and an aliphatic dicarboxylic acid, and an impact strength reinforcing agent in electron micrograph observation of the resin composition. It is also envied because it shows a more microscopic dispersion state compared to the composition.

The aromatic polyether resin of the present invention has the general formula [1] [11] as a repeating unit, and the structural units are [1] or [1] and [1]
A homopolymer or a copolymer consisting of the above-mentioned polymer, and a graft copolymer obtained by graft-polymerizing styrene or the like to the above-mentioned polymer are used.

Representative examples of homopolymers of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyk-6-ethyl-1,4-phenylene 1 ether, 2<2゜6-danityl-1,4-
phenylene) ether, poly(2-ethyl-6-n propyl-1,4-phenylene) ether, po! J(2,6
-di-n-propyl-1,4-phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-itzolobyl-1,4-phenylene) ether , poly(2-methyl-6
-10 ru 1.4-phenylene) Needa/L', Po! j
Examples include homopolymers such as (2-methyl-6-hydroxyethyl-1,4-phenylene) ether and poly(2-methyl-6-1t-loethyl-1,4-phenylene) ether.

The polyphenylene ether copolymer is an orthocresol or a monovalent compound having the general formula (herein, R3, R4, R8%, R11 is an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, a hydrogen atom, hydrogen, etc.) polyphenylene mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as 2,3,6-dolimethylphenol, which is a residue of (R@, Rs are not hydrogen at the same time) Includes ether copolymers.

Furthermore, the polyphenylene ether may be graft-copolymerized with styrene alone or with a monomer copolymerizable with styrene.

As the monomer copolymerized with styrene, for example, α-methylstyrene, methylstyrene, dimethylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, and esters of methacrylic acid are used.

The means for grafting these monomers onto polyphenylene ether is not particularly limited, but for example,
The method proposed in Japanese Patent Publication No. 30991, Japanese Patent Publication No. 52-38596, Japanese Patent Application Laid-Open No. 52-142799, etc., that is, the addition of styrene to polyphenylene ether alone in the presence of peroxide. , t or the heating graph of the above-mentioned single valve bodies) can be used.

Styrenic compounds used in the present invention and α, β-
Copolymers containing unsaturated dicardic anhydride as a component include non-rubber-reinforced copolymers and impact-resistant rubber-reinforced copolymers. In general, the copolymers used in the present invention can be prepared by conventional bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization techniques that utilize radical polymerization to form the copolymers used in the present invention. As the styrene compound, styrene, orthomethylstyrene, tsukuramethylstyrene, dimethylstyrene, metaethylstyrene, chlorstyrene, inpropylstyrene, tert-butylstyrene, alphamethylstyrene, ethylvinyltoluennate, or a mixture thereof is used. . The α,β-unsaturated dicarboxylic acid anhydride may be a monomer that can be copolymerized with a styrene compound, such as maleic anhydride, chlorotetramaleic anhydride, citraconic anhydride, butenylconomonolilic anhydride, Such as cutrahydrotetraphthalic anhydride. Furthermore, as a third component, a monomer copolymerizable with a styrene compound and an α,β-unsaturated dicarboxylic acid anhydride may be introduced, examples of which include methacrylic ester, acrylic ester, Acid, methacrylic acid, vinyl cyanide compound, etc. may also be used.

The rubber-reinforced copolymers used in the present invention include polybutadiene rubber, styrene/-butadiene rubber, polybutene rubber, hydrogenated styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene rubber, polyacrylate rubber, polyisoprene rubber. , can be obtained by polymerizing a comb-like material 1 such as natural rubber with the above-mentioned monomers in the presence of a coagulant.

Examples of suitable copolymers for use in the present invention include styrene-maleic anhydride copolymer, styrene-maleic anhydride-methacrylate ester copolymer, styrene-maleic anhydride-acrylic acid ester copolymer, etc. and so i
This is a rubber reinforced heavy duty structure made by T et al.

Furthermore, the copolymer used in the present invention is a copolymer containing 60 to 99% by weight of a styrene compound as a component and having an amount of α,β-unsaturated decarboxylic acid anhydride in the range of 1 to 40% by weight-J1%. , or a copolymer containing a styrene compound and α, β-, β-dicarboxylic acid anhydride as components,
60-96% by weight of styrenic compound and 2-30ii%
A copolymer of α, β-, β-dicarboxylic acid anhydride and 2 to 20 weight portions of methacrylic acid ester or nitrous acrylate is preferred. In the case of a rubber-reinforced copolymer, the composition of the resin phase excluding the rubber component is preferably within the above range. If the content of styrene compounds is too small, α.

β-unsaturated radical? If the amount of acid anhydride is too small or too large, the mechanical properties such as impact strength of the resin composition will deteriorate, which is undesirable.

The polyamide used in the present invention is a polyamide obtained by the reaction of xylylene diamine and an aliphatic dicarboxylic acid. The xylylene diamines used to obtain the polyamide include metaxylylene diamine, mixtures of metaxylylene diamine and laxylylene diamine, and mixtures of these with a trace amount of ortho-xylylene diamine, and also aliphatic dicarboxylic acids. has the general formula % and includes, for example, adipic acid, speric acid, nananosinic acid, undecaniic acid, dodecanoic acid, and the like.

Molecular node of polyamide v: J, 5,000-50, 0
00, preferably in the range of 10,000 to 40,000.

As a specific example of a suitable polyamide, poly(methaxylylene adipamide) or the like can be incorporated.

4) Impact strength reinforcement agents that are highly effective in improving impact strength used in the present invention include graft copolymers obtained by graft polymerizing monomers containing styrene-based compounds as a main component to rubber-like polymers, and various types of Thermoplastic nilastomers are preferred. A graft copolymer obtained by graft polymerizing a monomer mainly composed of a styrene compound to a rubber-like polymer is a graft copolymer obtained by emulsion graft polymerization of a styrene compound to a latex-like rubber-like polymer. Polymers obtained by dissolving the obtained polymer, comb-shaped polymer in a solvent containing a styrene compound as a main component, and polymerizing the solution by a method such as bulk polymerization, solution polymerization, suspension polymerization, etc. say. Examples of the rubbery polymer used here include polygetadiene, styrene-butadiene copolymer, ethylene-propylene copolymer, polyacrylic acid ester, and polyisozolene. Styrene compounds include styrene, orthomethylstyrene, paramethylstyrene, dimethylstyrene,
Isop-tetrabylstyrene, tertiary-butylstyrene,
Examples include alpha methylstyrene and ethylvinyltoluene. Monomers used with styrenic compounds include nisglu acrylate, methacrylate ester, acrylonitrile, methacrylonitrile, methacrylic acid, and acrylic acid. Styrenic compounds - α, β-unsaturated difluoric acid anhydride copolymer, in addition to the compatibility of polyamides obtained from xylylene diamine and 1f ribonic acid. Used as long as it does not cause any harm.

The content h1 in the graft copolymer is preferably 20% by weight or less.

] "The commercially available high-impact polystyrene also has a high resistance to lf.
Although it can be used as an IA strength reinforcing agent, a more preferable graft copolymer has a high content of rubbery polymer, and preferably the content of rubbery polymer in the graft copolymer is 12 polymers. 'Regret or above, most preferably 30-7
0 times - regrettable. The particle size of the dispersed rubber in the graft copolymer can range from small particles obtained by emulsion polymerization to large particles obtained by bulk polymerization, solution polymerization, and suspension polymerization. .

The thermoplastic distomers included in the present invention include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-propylene elastomers, styrene-grafted ethylene-propylene elastomers, thermoplastic polyester elastomers, and ethylene-based It is an ionomer resin. Styrene-butadiene block copolymers include AB type, ABA type, AHA tenozo type, radial teleblock type, and the like. In addition,
Graft copolymers and thermoplastic elastomers may be used alone or in combination as impact reinforcing agents.

The above-mentioned aromatic polyether resin, a copolymer containing a styrene compound and an α,β-unsaturated decal anhydride as a component, a polyamide obtained from xylylene diamine and an aliphatic dicarboxylic acid, and The impact strength reinforcing agents can be combined with each other in any ratio, but from the viewpoint of balance of mechanical properties etc., aromatic poly-1--f yarn 11 resin may be added to the resin composition from 5 to 50%. 95 weight t1 molecule 1 styrenic copolymer containing α,β-unsaturated logical acid anhydride as a component is 0.5 to 90 weight 1.1
? Liamide is 1 to 90 weight ratio, impact strength reinforcing agent is θ to
It is preferable that each component selected from a range of 80% by weight is contained. More preferably, a polyamide made of xylylene diamine and an aliphatic dicarzenic acid;
Styrenic compounds and α.

The proportion of the copolymer containing β-unsaturated dicarboxylic acid anhydride as a component is 1.4 to 100
The amount of the copolymer containing the styrene compound and α,β-unsaturated 11th dicardic acid anhydride as components is 5 parts by weight or more, most preferably 30 parts by weight or more.

'i1, rubber-reinforced styrene compound and α.

A rubbery polymer consisting of a rubbery polymer in a copolymer containing β-unsaturated')fu dicarboxylic acid anhydride as a component, a rubbery polymer in a graft copolymer, and a thermoplastic elastomer. It is most preferable that the resin composition of the present invention contains 0 to 30 times more. If the rubbery polymer contains too much, the heat resistance and rigidity of the resin composition will decrease, which is undesirable.In addition, the resin composition of the present invention described above may be further blended with other polymers. Among these, polymers containing 80% by weight of styrene compounds are particularly preferred from the viewpoint of improving moldability, examples of which include polystyrene, styrene-1-butylstyrene copolymer, and styrene. - Methyl methacrylate copolymer, styrene-methyl acrylate copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, and the like. If the content of the styrene compound in such a copolymer is too low, the impact resistance strength of the resin composition will drop significantly, which is undesirable.

Additives such as flame retardants and plasticizers can also be added to the resin composition of the present invention described above. Among them, phosphorus-based compounds are preferred from the viewpoint of improving moldability and flame retardancy.
(Bl [Here, X is water, hydroxyl group, amine group, carbon number 1-1
0 alkyl group, alkoxy group having 1 to 10 carbon atoms, or allyloxy group having 1 to 10 carbon atoms, Yl and Y2 are each an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, z is Oxygen or gold sulfate, 11% p is 0-4
indicates an integer. ] Compounds represented by these are preferred. Although there are no restrictions on its use, the resin composition 100. It is preferable to add 0.1 to 30 parts of the above-mentioned compound to the i opening.

As a method for obtaining the resin composition of the present invention, a method of melt-mixing using an extruder, roll mixer, Banbury mixer, Nigoo mixer, etc. can be used.

Regarding the order of melt mixing, all the components may be melt-mixed at the same time, two or three components may be melt-mixed in advance, or the styrene compound may be mixed simultaneously when graft polymerizing the aromatic polyether resin with the styrene compound. A method such as melting and mixing some of the other components can also be used. In order to strengthen the reaction or interaction between the polyamide and the copolymer containing the styrene compound and α,β-unfiiii*++ dicarboxylic acid anhydride as components, the styrene compound and α,β - A method for obtaining the resin composition of the present invention by melt-mixing a copolymer containing an unsaturated dicarboxylic anhydride as a component and polyamide, and then adding other components and melt-mixing the polyamide. In some cases, it may be preferable in terms of physical characteristics, etc.

Furthermore, the resin composition of the present invention may contain glass fibers, carbon fibers, aromatic polyamide fibers, fibrous reinforcing agents such as asbestos, calcium carbonate, talc, zinc oxide, wollastonite,
It can be used as a composite side slope by adding an inorganic filler such as silica or graphite.

In particular, when combined with glass fiber, a remarkable improvement in heat resistance is observed, and a molded side slope with good mechanical properties can be obtained. Another desirable characteristic is that the paintability is far better than that of glass fiber-reinforced polyamide and glass fiber-reinforced polystyrene. In addition, the composite material of the present invention does not have the problem of forming molded products, which is a major drawback of glass fiber reinforced polyamide, and can be used in the fields of large molded products such as automobile parts and home appliance parts, as well as precision molded products. No suitable side slope.

In addition, by combining with carbon fiber, heat resistance is significantly improved, mechanical properties are also good, and a good molded side slope with excellent electromagnetic shielding effect and excellent conductivity can be obtained.

The content of glass fiber or carbon fiber in the glass fiber or carbon fiber reinforced resin composition of the present invention is 5 to 60. m'J
! 4 is preferred, and 60. If it exceeds Fil, the moldability deteriorates, and if it is less than 5'j1, a sufficient reinforcing effect cannot be obtained.

When carrying out the present invention, the resin components are bath-melted in advance to obtain a pellet-shaped resin composition, and glass fibers or carbon fibers are blended with the resin composition, and the glass fibers or carbon fibers are melt-mixed in an extruder. It is also possible to obtain a reinforced Gl fat silk acid. In addition, pelletized resin components and glass fibers,
Alternatively, the mixture with carbon fiber may be placed in the hopper of a surface injection molding machine to obtain a molded product at the same time as melting and mixing, or the above three-way mixture may be melt-kneaded in an extruder to form a glass fiber or carbon fiber reinforced resin composition. You can also get things.

In addition, some of the glass fibers or carbon fibers in the resin composition of the present invention may be substituted with fibrous reinforcing agents such as asbestos, aromatic polyamide fibers, potassium titanate fibers, calcium carbonate, talc, titanium oxide, zinc oxide, water, etc. It can also be replaced with an inorganic filler such as magnesium oxide graphite.

In addition, other additives such as plasticizers, colorants, stabilizers, etc. may be contained in the resin composition of the present invention, and other polymers such as polyethylene, polypropylene, polyester, etc. may be added to improve mechanical properties, etc. They can also be mixed in amounts that do not impair their properties.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited thereto.

Parts are measured by weight.

Examples 1 to 3 50 parts of styrene-maleic anhydride copolymer (maleic anhydride-containing 110-maleic anhydride copolymer) and poly(methaxylylene azide/
, a sheet) and 5 ( ) parts in a twin-screw extrusion machine.
41r-0 obtained polymer A and η'! '/c=0.64
(measured in chloroform solution at 30°C) of poly(2°6-
dimethylphenylene-1,4-ether) were mixed in a blender in the proportions shown in Table 1, and melt-kneaded using a twin-screw extruder at a temperature of 290'C to obtain a resin composition. .

A test piece was made by injection molding from the obtained resin composition, and JI
The tensile strength, elongation, isot punch strength, and heating deformation temperature were measured using the method described in II6''5 in S test method 6871. After performing a peel test, the condition was observed with the naked eye. The results are shown in Table 1.

Example 4 50 parts of poly(2,6-dimethylphenylene-1,4-ether) with η”p/c=0.64, 10 parts of styrene,
Styrene grafted poly(2,6 -dimethylphenylene-1,4-ether) 50M, 20 parts of yj?su (methaxylylene azinoya mido), 20 parts of styrene-maleic anhydride copolymer (Dylark@232...manufactured by Arco Polymer Co., Ltd.) Part, polystyrene (Styron ■685...
(manufactured by Asahi Dow) were mixed and melt-kneaded using a twin-screw extruder at a temperature of 290°C to obtain a resin composition. A test similar to Example 1 was conducted. The results are shown in Table 1.

Comparative Example 1.2 Polystyrene (Styron [F] 685) was used instead of the styrene-maleic anhydride copolymer of Example 4 [Comparative Example 1]
or styrene-methyl methacrylate copolymer (containing methyl methacrylate 1°10 weight ratio) in place of styrene-maleic anhydride copolymer and polystyrene.
A resin composition was similarly obtained using [Comparative Example 2] and tested. The results are shown in Table 1. The molded product obtained here exhibited a remarkable delamination phenomenon and had poor mechanical strength.

Examples 5 to 7 Poly(2,6-dimethylphenylene-1,4-ether) used in Example 1,! : yj? IJmer A was further mixed with a graft copolymer obtained by emulsion graft polymerization of 40 parts of styrene in the presence of 60 parts of polyptazoene latex in the proportions shown in Table 2, and further 100 parts of the resin mixture. To the mixture, 05 parts of a phosphorus compound represented by the following formula was added and mixed in a blender, followed by bath melt kneading using a twin-screw extruder at a temperature of 129 (1'0) to obtain a resin composition. Example 1 for the obtained resin composition
The test was conducted in the same manner. Furthermore, gasoline resistance r1-test j%
The injection-molded test piece was immersed in gasoline at 23° C. for 15 hours, and the appearance of cracks was observed. The results are shown in Table 2.

Actual car l+1+su8~IO Styrene-grafted poly(2゜6-dimethylphenylene-1,4-ether), poly(methaxylylenoazino-4mide), styrene-maleic anhydride copolymer used in Example 4 The emulsion graft copolymers used in the coalescence and Example 5 were mixed in the proportions shown in Table 2 to obtain a resin composition in the same manner as in Example 5 and tested. The results are shown in Table 2.

Comparative Example 3.4 In place of the styrene-maleic anhydride in Example 8, polystyrene/(Styron ■685...manufactured by Asahi Dow) [Comparative Example 3
] or a styrene-methyl methacrylate copolymer (methyl methacrylate content: 10% by weight) [Comparative Example 4], a resin composition was obtained in the same manner as in Example 8, and a test was conducted. The results are shown in Table 2.

The impact strength was low and the molded product showed peeling, so a desirable molding material could not be obtained.

Comparative Example 5 The styrene graft poly(2゜6-dimethylphenylene-1,4-needle), styrene-maleic anhydride copolymer, and emulsion graft copolymer used in Example 8 are shown in Table 2. A resin composition was obtained in the same manner as in Example i+lJ 8 by mixing at the same ratio, and a test was conducted. The results are shown in Table 2.

When an injection-molded test piece was immersed in gasoline, significant cracking was observed, and no molded side slopes with excellent gun rinsing resistance were obtained.

Example 1 1 to 1 3 50 parts of rubber-strengthened styrene-maleic anhydride copolymer (Dylark@250...manufactured by Arco Polymer Co., Ltd.) and 50 parts of poly(methaxylylene adipacide). The mixture was melt-kneaded using a two-way extruder to obtain a pelletized resin (referred to as Polymer B). The obtained polymer B1 used in Example 4 was the styrene graft poly(2,6-dimethylphenylene-1.
4-Ether), abrasive shock sequence? Listyrene (polybutadiene-containing i4: 2 (containing -1f1 in solution R1) and hydrogenated styrene-butadiene block copolymer (Craton Gl 650, manufactured by Shell) were added. A resin composition was obtained in the same manner as in Example 1, and tested.
Examples 14 to 16 are shown in the table. Poly(2,6-dimethylphenylene-1,4-ether) used in Example 1, poly(methaxylylene azinoxide), impact resistance used in Example 11. Polystyrene, styrene-maleic anhydride-methyl methacrylate copolymer (maleic anhydride content: 9 by weight, methyl methacrylate content: #5 by weight), styrene-maleic anhydride copolymer (maleic anhydride content: 1 by weight) containing end 5-fold leaf), and Example 4
The polystyrene used in Table 3 was mixed in the combinations and ratios shown in Table 3, and 6 parts of triphenyl phosphate was added to 100 parts of the resin mixture, mixed in a blender, and heated in a two-way extruder at a temperature of 280°C. A resin composition was obtained by melt-kneading. The obtained resin composition was tested in the same manner as in Example 1. The results are shown in Table 3.

Example 80 parts of the reaction product obtained in Example 10 and 2 glass fibers
This mixture was put into a vent-type extruder and mixed at 290°C to obtain a glass fiber reinforced resin composition in the form of pellets. A physical property test and a paintability test were conducted. Regarding paintability, after painting the molded product with acrylic thread coating, its appearance was judged with the naked eye, and the adhesion test of the paint film was conducted by iJ
The test was carried out on molded products after conducting a wet test. The results obtained are shown in Table 4.

The glass fiber reinforced resin composition of the present invention has a heat resistance of IFf.
j<, it can be seen that the coating properties are good and the mechanical properties are also excellent.

Table 4 Agent: San Tadashi, husband and 1 other person

Claims (1)

[Scope of Claims] (n) A copolymer containing 5 to 95 polymers of an aromatic polyether resin, a styrene compound, and an α,β-unsaturated dicardic acid anhydride as components. 90 weight, v
A thermoplastic resin composition having good heat resistance, comprising 1 to 90% by weight of a polyamide obtained from xylylene cyanide and an aliphatic dicarboxylic acid, and 0 to 80% by weight of an impact strength reinforcing agent. (2) Aromatic polyether resin is PO! J(2', 6-
The resin composition according to claim 1, wherein the resin composition is 1,4-ether (dimethylphenylene-1,4-ether). (3) Aromatic polyether resin or styrene compound kraft poly(2,6-dimethylphenylene-1.4
- ether) in the patent claim (1). (4) A copolymer containing a styrene compound and an α,β-unsaturated dicarbonyl anhydride as a component is a copolymer containing an Okibe ren compound of 60 to 99 Jukei and 1 to 40 The resin composition according to claim (1), which is a copolymer with α,β-unsaturated dicargonic acid anhydride in weight ratio.(5) A styrenic compound and α,β-unsaturated unsaturated. The copolymer containing decal anhydride as a component is 60 to 96
Styrenic compound of weight range and α, β of 2 to 30 weight range
The resin composition according to claim 1, which is a copolymer of -, β-dicarboxylic acid anhydride and 2 to 20 weight percent methacrylic ester or acrylic ester. (6) A copolymer containing a styrene compound and an α, β-, β-dicarboxylic anhydride as a component is a copolymer containing a rubber-reinforced styrene compound and an α, β-, β-dicarboxylic anhydride. The resin composition according to claim (1), (4), or (5), which is a copolymer containing as a component. (7) The resin composition according to claim (1), wherein the polyamide is poly(methaxylylene azinogamide). (8) The impact strength reinforcing agent is a graft copolymer obtained by graft-polymerizing a monostate whose main component is a styrene compound to a rubber-like polymer. (!Jl The graft copolymer is a comb-like polymer with 12
Specified FIFm-required range (
8) The resin composition described in item 8). (10) The RFA resistance strength reinforcing agent is a styrene-butadiene block copolymer, a hydrogenated styrene-butadiene block copolymer, an ethylene-fO pyrene elastomer,
Styrene grafted ethylene tetrapyrene elastomer
, 1? Claim No. 1 (1) is one or more types of polyester elastomer and ethylene ionomer resin.
The resin composition according to item 1. (11) A thermoplastic resin composition comprising the resin composition according to claim 17, further containing a polymer containing 80% or more of a styrene compound. Knowledge: Claim No. (11) in which the polymer containing one or more is polystyrene.
The resin composition listed in Section d. (I3) A thermoplastic resin composition comprising the resin composition according to claim (1) or (2) and further containing a phosphorus compound. (14) The resin composition according to claim 13, wherein the phosphorus compound is a phosphoric acid ester or a sulfite varnish. (15) The phosphorus compound has the general formula (Al and (B) [Here, XX z (A) (s) is hydrogen, hydroxyl group, amino group, alkyl group having 1 to 1 carbon atoms, or
10 alkoxy group or an allyloxy group having 1 to 1 o carbon atoms, Y! and Y! each represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, 2 represents oxygen or sulfur, and n. p represents an integer from θ to 4. ] The resin composition according to claim (13), which is a compound represented by: (16) Resin composition 4 according to claim No. 11
A glass fiber-reinforced resin composition comprising 0 to 95 parts by weight and 5 to 60 parts by weight of glass fibers. (17) Resin composition 4 according to claim (1)
A carbon fiber reinforced resin composition comprising 0 to 95 weight i1 and 5 to 60 weight 41% carbon fibers.