JPS5927943A - Highly heat-resistant polymer composition having good oil resistance - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent resistance to oil and heat and mechanical properties. consisting of an arom. polyether resin, a specified copolymer, a polyamide, an impact modifier and a phosphorus compd. CONSTITUTION:0.1-30pts.wt. phosphorus compd. such as phosphate ester or phosphite ester is blended with 100pts.wt. resin compsn. consisting of 5-95wt% polyether resin (A) such as poly (2,6-dimethyl-phenylene-1,4-ether), 0.5-90wt% copolymer (B) of at least 70mol% of a styrene compd. with 1-30mol% of an imide compd. of an alpha,beta-unsaturated dicarboxylic acid, such as styrene/maleimide copolymer, 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 relates to a copolymer containing an aromatic polyether resin, a styrene compound and an imide compound of an α,β-unsaturated zocarboxylic acid, and a copolymer containing xylylene diamine and an aliphatic zocarboxylic acid. The present invention relates to a resin composition made of the obtained polyamide resin and a resin composition made by adding an impact strength reinforcing agent to the resin composition.

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 good dimensional stability. A major drawback is that surface 1 oil resistance to chemicals such as lubricating oils and varnishes is poor.

In order to improve the moldability of aromatic polyether resins, it was proposed in Japanese Patent Publication No. 45-997.
However, the aromatic polyether resin and polyamide have very poor compatibility, and the resulting resin composition has poor mechanical properties (particularly when the polyamide content is 20%).
If it exceeds Juhoutei, it is markedly inferior), and the molded product obtained by injection molding exhibits a delamination phenomenon, making it impossible to obtain a desirable molded product.

However, in order to improve moldability and impact strength, polystyrene or rubber-reinforced polystyrene is blended with aromatic polyether resin in Japanese Patent Publications No. 17812/1982 and Japanese Patent Application Laid-Open No. 98858/1989. Has it been proposed that rubber-reinforced polystyrene/aromatics still be used? Although resin compositions made of riether resins have excellent impact strength and moldability and are produced in large quantities industrially, their range of use is limited due to their poor oil resistance. For example, it is widely used in electrical equipment due to its excellent electrical properties, heat resistance, and flame retardancy. However, cracks often occur in molded products due to contact with machine oil and varnish, and improvements in oil resistance are eagerly anticipated. has been done.

In engineering plastics, it is important to have excellent heat resistance, impact resistance, and oil resistance, and the emergence of resins that have excellent oil resistance, heat resistance, and impact resistance. For example, its range of applications can be greatly expanded.

There is almost no prior art regarding aromatic polyether resins that have excellent oil resistance, heat resistance, and pot impact strength, and no resins have been put to practical use. For example, in JP-A-52-28947, it was proposed to blend a copolymer of a rubber-reinforced styrene compound and an α,β-unsaturated dicarboxylic acid anhydride with an aromatic, l? However, a major drawback of these resin compositions is that they have poor oil resistance.

The present inventors have worked diligently to obtain a vine resin composition that has excellent oil resistance, high heat resistance, and high impact strength, and can be used in a wide range of applications. By further blending a copolymer containing a styrene compound and an imide □ compound of α,β-unsaturated zocarzenic acid as ingredients, and adding an impact strength reinforcing agent, we have created a resin with unprecedented performance. He discovered the very interesting fact that a composition could be obtained, and filed a patent application in 1984-1.
No. 39947.

The present inventors further discovered that by using a copolymer obtained from xylylene diamine and an aliphatic dicarboxylic acid as the polyamide, the dimensional accuracy, hygroscopicity, and mechanical strength upon moisture absorption of the resulting resin composition are reduced. The present inventors have discovered that preferable results can be obtained in terms of a small number of particles.

The resin composition of the present invention is different from resin compositions consisting of aromatic polyether resin and rubber-reinforced polystyrene, which are currently being produced and used industrially.
It is a molding material with extremely high industrial value as it has significantly improved resistance to chemicals such as machine oil, lubricating oil, and varnish, and has excellent heat resistance and mechanical properties.

An aromatic I-reather resin, a polyamide obtained from xylylene diamine and an aliphatic dicarboxylic acid, and a copolymer containing as components a styrene compound and an imide compound of α,β-unsaturated dicarzene acid have additional impact resistance strength. By incorporating a reinforcing agent, a resin composition with extremely high impact resistance can be obtained. On the other hand, a resin composition with excellent impact resistance cannot be obtained by adding an impact strength reinforcing agent to aromatic polyether resin, polyamide obtained from xylylene diamine and aliphatic dicarboxylic acid, or polystyrene. First, the molded product obtained by injection molding still exhibits a layered peeling phenomenon, which is undesirable. In the resin composition of the present invention, polyamide, a styrene compound and α, β
- The coexistence of the ibad compound of unsaturated dicarboxylic acid with the copolymer containing the ibad compound as a component is an important point in obtaining a quality that has not been obtained in the past. Regarding the effect of coexisting polyamide with a copolymer containing as components a styrene compound and an imide compound of an α,β-unsaturated dicarboxylic acid, consider the idea of polyamide, a styrene compound, and an α,β-unsaturated dicarboxylic acid. It will be done. Such chemical bonds are present in aromatic polyneedle resins, polyamides, styrenic compounds, and d, β-unsaturated logical 11? A copolymer containing an imide compound of phosphoric acid as a component and a surface 1 impact strength reinforcing agent have a dispersion state of the surrounding structure that has not been previously possible, and as a result, it has oil resistance, Aspect 1: It is believed that a resin composition with good performance, which has excellent thermal properties and moldability, and high impact strength, can be obtained.

This indicates that the resin composition of the present invention is a polyamide obtained from aromatic s51) ether thread resin, xylylene diamine, and aliphatic dicarboxylic acid, and 7I? It is also envisaged because it exhibits a finer dispersion state than resin compositions made from listyrene, an impact strength reinforcing agent.

The aromatic thiliether resin of the present invention refers to a homopolymer or copolymer having the general formula % as a repeating unit and the constitutional units consisting of [I] or CI] and [lI], and This includes graft copolymers made by graft polymerizing styrene, etc.

Representative examples of homopolymers of polyphenylene ether include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, and poly(2,6-dimethyl-1,4-phenylene) ether. -danityl-1,4-phenylene)conythyl2. NIJ (2-ethyl-6-n
7'Glue 1,4-phenylene)ether, poly(2
, 6-GH7'opi/l/-1,4-phenylene)
Ether, BoIJ (2-methyl-6-n-butyl-1,4
-phenylene) ether, ylE' +7 (2-ethy-6-imbrobyl-1,4-phenylene) ether, poly(2-methyl-6-chloro-1,4-phenylene) ether1. I? (2-methyl-6-hytroquinethyl-1,4-phenylene) ether, yJ91J
Examples include homochimers such as (2-methyl-6-chloroethyl-1,4-phenylene)ether.

The polyphenylene ether copolymer is an orthocresol or a general formula (where Rs + R4* R51R6 is an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, a Ryl group,
It is a monovalent residue such as a halogane or hydrogen, and R1+R6
is not hydrogen at the same time. ) 2, 3.6-1
It includes a tylphenylene ether copolymer mainly having a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as 7-methylphenol.

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

Examples of monomers that can be copolymerized with styrene include α-methylnutyrene, methylstyrene, dimethylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, and esters of methacrylic acid.

The means for grafting these monomers onto polyphenylene ether is not particularly limited, but for example,
0991, Japanese Patent Publication No. 52-38596, Japanese Patent Publication No. 52-142799, etc. ftj2 on fctri
A method of carrying out a heating graft reaction of monocorticoids can be used.

The styrenic compound used in the present invention and (χ, β
−For the symelectron with the imide compound of unsaturated dicargenic acid, □
, non-rubber reinforced copolymers and impact resistant rubber reinforced copolymers. In general, the copolymer used in the present invention can be prepared by conventional bulk polymerization using radical polymerization, solution polymerization, or emulsion polymerization technology, as disclosed in Japanese Patent Application Laid-Open No. 54-93091 and German Patent No. 2,644,492. It can be manufactured by the method described in et al. Also, US RP6 Patent No. 3,998,907, German Patent No. 2,343,408
As stated in the issue, styrenic compounds and α,
The copolymer of the present invention can also be obtained by treating a copolymer with a β-unsaturated cyclic anhydride with a basic aqueous nitrogen-containing compound.

Examples of the styrene compounds forming the copolymer used in the present invention include styrene, orthomethylstyrene, paramethylstyrene, dimethylstyrene, metaethyl 7-styrene, chlorstyrene, inglobyl styrene, terjariftyl styrene, and alpha-methylstyrene. , ethylvinyltoluenate and mixtures thereof are used.

The imide compound of α,β-unsaturated dicarboxylic acid which still forms the copolymer used in the present invention has the following formula (wherein R1, R2
+Rs represents hydrogen, an alkyl group, an alkenyl group, an cycloalkyl group, a phenyl group, a phenylene group, an alkylene group, etc. ).

Examples include maleimide, N-methylmaleimide, N--r thylmaleimide, N-7 chlorohexylmaleimide, N-phenylmaleimide P, N
-(p-methylphenyl)maleimide, N-(3,
Examples include 5-dimethylphenyl)maleimide, N-(p-methoxyphenyl)maleimide, N-benzylmaleimide, and N-(1-naphthyl)-maleimide.

Still a styrene compound and α as a third component.

A monomer copolymerized with an imide compound of β-unsaturated dicarboxylic acid may be introduced. Examples thereof include methacrylic ester, acrylic ester, acrylic acid, methacrylic acid, vinyl cyanide compound, etc. It's okay.

The comb-reinforced styrenic compound used in the present invention and α
, a β-unsaturated dicarboxylic acid imide compound, polybutadiene rubber, styrene-butadiene rubber, polybutene rubber, hydrogenated nuthylene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-butadiene rubber, etc.
It can be obtained by polymerizing the monomers described above in the presence of a rubbery polymer such as propylene rubber, polyacrylic ester rubber, polyisozolene rubber, or natural rubber.

Examples of suitable copolymers for use in the present invention include styrene-N-phenylmaleimide copolymer, styrene-maleinoimide copolymer, cutyleph-N-phenylmaleimide-methacrylate ester copolymer, and styrene-N-phenylmaleimide copolymer. These include N-phenylmaleimide-acrylic acid ester copolymers and rubber-reinforced polymers thereof.

Furthermore, the copolymer used in the present invention contains 70 mole or more of a styrene compound as a component, and contains α, β unsaturated salts (
``A copolymer containing as a component a dicarboxylic acid imide compound with a content of 1 to 98 mol styrene compound, and α of 1 to 30 mol.

It is preferably a copolymer of an imide compound of β-unsaturated dicarboxylic acid and 1 to 20 moles of methacrylic ester or acrylic ester.

In the case of a rubber-reinforced copolymer, the composition of the resin phase excluding the rubber component is preferably within the above range. Even if the content of the styrene compound is too small, the imide compound of α,β-unsaturated dicardic acid is too small, or too large, the INt of the resin composition
Mechanical properties such as impact strength deteriorate, which is undesirable.

The polyamide used in the present invention is a polyamide obtained by a reaction between xylylene diamine and an aliphatic dicarboxylic acid. The xylylene diamines used to obtain the polyamide include metaxylylene diamine, a mixture of metaxylylene diamine and para-xylylene diamine, and a mixture of these and ortho-xylylene diamine, and aliphatic dicarboxylic acids include , general formula l100C(CH
2) Represented by nC00H (n-4 to 10), examples of which include adipic acid, speric acid, sepacic acid, undecanoic acid, and dodecanoic acid. The molecular liquid of polyamide is 5. (100-50,000, preferably tJ:
The range is 10,000 to 40,000.

A specific example of a preferred polyamide is poly(methaxylylene adipamide).

The impact strength reinforcing agents used in the present invention that have a large effect of improving impact strength include graft copolymers obtained by graft-polymerizing monomers mainly containing styrene compounds to rubber-like polymers, and various thermoplastics. Elastomers are preferred. A graft copolymer obtained by graft polymerizing a monomer mainly composed of a styrene compound onto a rubber-like polymer is a graft copolymer obtained by graft polymerizing a styrene-based compound onto a latex-like rubber polymer. The resulting polymer or rubber-like polymer is dissolved in a solvent containing a styrene compound as a main component, and the resulting solution is polymerized by bulk polymerization, solution polymerization, or suspension polymerization. It will be done.

Examples of the rubbery polymer used here include polybutadiene, styrene-butadiene copolymer, ethylene-globylene copolymer, polyacrylic acid ester, and polyimprene. Styrene compounds include styrene,
Examples include orthomethylstyrene, halamethylstyrene, dimethylstyrene, insolobylstyrene, tertiary-butylstyrene, alpha-methylstyrene, and ethylvinyltoluene. Monomers used with styrene compounds include acrylic esters, methacrylic esters, acrylonitrile, methacrylonitrile, methacrylic acid, and acrylic acid. Compounds - α, β
- An imide compound copolymer of unsaturated dicardic acid, used in addition to a polyamide obtained from xylylene diamine and aliphatic dicarboxylic acid, to the extent that compatibility is not impaired. The content thereof is preferably 20% by weight or more F in the graft copolymer.

Although commercially available high-impact polystyrene can also be used as an impact strength reinforcing agent, more preferred graft copolymers are those with a high content of rubbery polymers, preferably rubbery polymers in the graft copolymer. Polymer content is 12
% by weight or more, most preferably 30-70% by weight.

The particle size of the dispersed rubber in the graft copolymer ranges from small particles obtained by emulsion polymerization to large particles obtained by bulk polymerization, solution polymerization, and suspension polymerization.

The thermoplastic nydistomers referred to in the present invention include styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, ethylene-zolopyrene elastomers, styrene-grafted ethylene-globylene elastomers, thermoplastic polyester elastomers, and ethylene ionomer resins, etc. Styrene-butadiene block copolymers include AB type, ABA type, ABA tapered type, radial teleblock type, and the like. Incidentally, as the impact reinforcing agent, a graft copolymer and a thermoplastic nidistomer can be used alone or in combination.

Polyamide obtained from the above-mentioned aromatic polyether resin, a copolymer containing a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid as a component, xylylene diamine and aliphatic dicarboxylic acid, and impact strength The reinforcing agents can be combined with each other in any proportion, but
In view of the balance of its mechanical properties, the resin composition contains 5 to 95% by weight of aromatic polyether thread resin, a styrene compound, and an imide compound of α,β-unsaturated dicardic acid as components. The copolymer is selected from a range of 0.5 to 90% by weight, the polyamide obtained from xylylene diamine and aliphatic dicarboxylic acid is selected from a range of 1 to 90% by weight, and the impact strength reinforcing agent is selected from a range of 0 to 80% by weight. It is preferable that each component is contained. More preferably, in the proportion of the polyamide obtained from xylylene diamine and aliphatic dicarboxylic acid and the copolymer containing as components a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid, xylylene diamine Polyamide 100 obtained from and aliphatic dicarboxylic acid The copolymer containing a styrene compound and an imide compound of an α,β unsaturated dicarboxylic acid as components is 5 parts by weight or more based on the heavy salmon part, most preferably tL< Viao parts by weight or more.

Still, α with rubber reinforced styrenic compound.

A gono-like polymer in a copolymer containing an imide compound of β-unsaturated dicarboxylic acid as a component, a rubbery polymer in a graft copolymer used as an impact strength reinforcing agent, and a thermo-OJ plastic elastomer. Most preferably, the resin composition of the present invention contains 0 to 30% by weight of the synthetic rubber-like polymer. If the content of the rubbery polymer is too large, the heat resistance and rigidity of the resin composition will decrease, which is not preferable.

Furthermore, other polymers may be used as a blend in the resin composition of the present invention described above. Among these, polymers containing 80% by weight or more of styrene compounds are particularly preferred from the viewpoint of improving moldability, examples of which include polystyrene, styrene-t-butylstyrene copolymer, and styrene-methacrylic. Examples include acid methyl copolymer, styrene-methyl acrylate copolymer, styrene-acrylic acid copolymer, and styrene-methacrylic acid copolymer.

Additives such as flame retardants and plasticizers can also be added to the resin composition of the present invention described above. Among them, phosphorus compounds are preferred in terms of improving moldability and flame retardant effects, and phosphoric esters, phosphite esters, and general formulas (A) and (B) are particularly preferred. , X is hydrogen, hydroxyl group, amine group, alkyl group having 1 to 10 carbon atoms, and 1 carbon number.
~10 alkoxy group or a C1-100 alkoxy group, Y and Y each represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and 2 represents oxygen or sulfur. , nsp represents an integer from 0 to 4. ] Compounds represented by these are preferred. There is no limit to the amount added, but 0.1 to 0.1 to 100 parts by weight of the above compound may be added to 100 parts by weight of the resin composition.
It is preferable to add 30 parts by weight.

The resin composition of the present invention can be obtained by melt-mixing using an extruder, roll mixer, Banbury mixer, kneader mixer, or the like.

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 melt-mixing some of the other components can also be used. Styrenic compounds and α,β-unsaturated radicals? In order to strengthen the reaction or interaction between the polyamide and the copolymer containing an imide compound of phosphoric acid as a component, a styrene compound and an imide compound of α,β-unsaturated dicarboxylic acid are added as components in advance. In some cases, it may be preferable in terms of mechanical properties etc. to obtain the resin composition of the present invention by melt-mixing the copolymer and polyamide contained in .

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 material by adding inorganic fillers such as silica and graphite.

In particular, when combined with glass fiber, a molding material with markedly improved heat resistance and good mechanical properties can be obtained. Another desirable feature is that it has much better paintability than glass fiber-reinforced polyamide and glass fiber-reinforced polystyrene. Moreover, the composite material of the present invention is glass fiber reinforced, J?
There is no warping of molded products, which is a major drawback of Liamide, making it an unprecedentedly suitable molding material for use in the fields of large molded products such as automobile parts and home appliance parts, and precision molded products.

Moreover, by combining with carbon fiber, a molding material with remarkable improvement in heat resistance, good mechanical properties, excellent conductivity, and electromagnetic shielding effect can be obtained.

In the glass fiber or carbon fiber reinforced resin composition of the present invention, the glass fiber or carbon fiber chain tr is preferably 15 to 60% by weight; if it exceeds 60% by weight, the moldability decreases, and if it is less than 1% by weight, the No reinforcing effect can be obtained.

In carrying out the present invention, step 1, resin components are melt-mixed in advance to obtain a resin composition in the form of pellets, and then glass fibers or carbon fibers are blended and melt-mixed in an extruder to form a glass resin composition. It is also possible to obtain fiber or carbon fiber reinforced resin compositions. In addition, the mixture of pelletized resin component and glass fiber or carbon fiber can be directly injected into the injection molding machine.
It is also possible to obtain a molded product at the same time as melting and mixing.
A glass fiber- or carbon fiber-reinforced resin composition can also be obtained by melt-blending the above-mentioned three-way mixture in an extruder.

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

The resin composition of the present invention may also contain other additives such as plasticizers, colorants, stabilizers, etc., 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 the properties.

The present invention is not limited thereby. The department will hail the Okabe department.

Examples 1 to 3 Styrene-N-phenylmaleimide copolymer (N-
50 parts of phenylmaleimide (WJi 14 mol %) and 50 parts of poly(methaxylylene adipamide) were melt-mixed in a twin-screw extruder to obtain a pellet-shaped resin (referred to as Polymer A). The obtained polymer A and ηgp/C=0.64 (
Poly(2,6-dimethylphenylene-1,4-L-f) (chloroform solution, measured at 30°C) was mixed in a blender in the proportions shown in Table 1 and extruded at a temperature of 290°C. A resin composition was obtained by melt-kneading using a machine.

A test piece was made by injection molding from the obtained resin composition, and its tensile strength, compression strength, Izot impact strength, and heating deformation temperature were measured by the method described in JIS Test Method K 6871.
Shita. The peeling state of the molded product was visually observed after a peeling test was performed by attaching an adhesive tape to the fractured surface of the test piece and then removing it. The results are shown in Table 1.

Example 4 50 parts of poly(2,6-dimethylphenylene-1,4-ether) with ηsp/C=0.64, 10 parts of styrene
Styrene grafted poly(2,6- dimethylphenylene-1
．． 4-ether) 50 parts, poly(methaxylylene adipamide) 20 parts, styrene-N-phenylmaleimide copolymer (N-phenylmaleimide content 14 mol%) 209, 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. The resin composition thus obtained was subjected to the same tests as in Example 1. The results are shown in Table 1.

Example 5 Styrene graft poly(slow) y used in Example 4
'tylphenylene-1,4-ether) 70 parts, poly(
metaxylylene adipamide) 10 parts, styrene-maleimide copolymer (maleimide-containing it 9 mol%)
) and 12 parts of polystyrene (Styron ■685), a resin composition was prepared in the same manner as in Example 4, and tested. The results are shown in Table 1.

Example 6 Styrene-grafted poly(2,6-dimethylphenylene-1,4-ether) used in Example 41. ] e13 (metaxylylene adipamide) and styrene-N-phenylmaleimide copolymer were mixed in the proportions shown in Table 1,
A resin composition was obtained and tested in the same manner as in Example 4. The results are shown in Table 1.

Comparative Examples 1 and 2 Actual Ml Example 4 o Polystyrene (Styron ■685
) [Comparative Example 1] or with the styrene-N-phenylmaleimide copolymer, J? A resin composition was similarly obtained using styrene-methyl methacrylate copolymer (containing methyl methacrylate in a density of 15 mol %) [Comparative Example 2] instead of listyrene, and a test was conducted. The results are shown in Table 1. The molded product obtained here exhibited a remarkable delamination phenomenon and had poor mechanical strength.

Examples 7 to 9 In addition to the poly(2,6-dimethylphenylene-1,4-ether) used in Example 1 and Polymer A, 40 parts of styrene was added in the presence of 60 parts of I Lipkuziev 22F. The graft copolymer obtained by emulsion graft polymerization of 100 parts of the resin mixture was mixed in the proportions shown in Table 2, and 5ANKO-HCA (9°10-dihydro-9-oxa-10-phosphatide) was added to 100 parts of the resin mixture. 0.5 part of faphenanthrene-10-oxide) was added thereto, mixed in a blender, and melt-kneaded using a twin-screw extruder at a temperature of 290°C to obtain a resin composition. The obtained resin composition was tested in the same manner as in Example 1. Further, as a gasoline resistance test, the injection molded test piece was immersed in gasoline at 23° C. for 1.5 hours, and the state of crack generation was observed. The results are shown in Table 2.

Examples 10 to 12 Styrene grafted poly(slow dimethylphenylene-1,4-ether), poly(methaxylylene adipamide), styrene-N-phenylmaleimide copolymer used in Example 4 and Examples The emulsion graft copolymer used in Example 7 was mixed in the proportions shown in Table 2 to obtain a resin composition in the same manner as in Example 7, and the test was conducted. The results are shown in Table 2.

Comparative Examples 3 and 4 7z Restyrene (Styron q°685
) [Comparative Example 1] or Nutylene-methyl methacrylate copolymer (methyl methacrylate content: 15 molt) [Comparative Example 4], a resin composition was obtained in the same manner as in Example 10, and the test was carried out. went.

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 5.6 Styrene graft poly(2°6-) used in Example 10
)'-f-lephenylene-1,4-ether), styrene-N-phenylmaleimide copolymer, polystyrene (Styron ■685), and emulsion graft copolymer were mixed in the proportions shown in Table 2, and Example A resin composition was obtained and tested in the same manner as in Example 10. The results are shown in Table 2.

When the injection molded test piece was immersed in gasoline, significant cracking was observed, and a molding material with good gasoline resistance could not be obtained.

Examples 13-15 50 parts of rubber-reinforced lettuce styrene-N-phenylmaleimide copolymer (N-phenylmaleimide content 10 mol, rubbery polymer content 9% by weight) and poly(methaxylylene adipamide) 50 parts of the polymer were melt-kneaded in a twin-screw extruder to obtain a pellet-shaped resin (referred to as Polymer B). Obtained Irif-B1 Styrene grafted poly(2゜6-dimethylphenylene-1,4-ether) used in Example 4, impact-resistant polystyrene (polybutadiene content 20
(obtained by solution polymerization), and hydrogenated styrene-butadiene block copolymer (Kraton G 165)
A resin composition was prepared in the same manner as in Example 1, and tested. The results are shown in Table 3.

Examples 16 to 18 Poly(slodimethylphenylene-1 used in Example 1)
,4-ether)1. +9S (methaxylylene adipate), impact-resistant polystyrene used in Example 14, styrene-N-phenylmaleimide-methyl methacrylate copolymer (N-phenylmaleimide content 14
molti, methyl methacrylate content 5 mol%), styrene-N-phenylmaleimide copolymer (N-phenylmaleimide-containing liquid 5 mol%), and Example 4
Mix the polystyrene used in Table 3 in the combinations and ratios shown in Table 3, add 6 parts of triphenyl phosphate to 10 parts of the resin mixture, mix in a blender,
A resin composition was obtained by melt-kneading at a temperature of 90° C. using a twin-screw extruder, and the same test as in Example 1 was conducted. The results are shown in Table 3.

Finally, the resin composition of the present invention and rubber-reinforced polystyrene/'
Aromatic, j? In order to compare the chemical resistance with the riether resin composition, the chemical resistance of the composition of the present invention in Example 10 and the composition consisting of rubber-reinforced polystyrene/aromatic polyether resin in Comparative Example 6 was compared. compared. 4th result
Shown in the table. Chemical resistance is 100X for parabolic bending mold
Attach a 12.7 x 3 mm test piece and bring it into contact with cyclohexane while applying uniform and continuous strain to the test piece. Observe the cracks that occur on the test piece and determine the curvature of the point at which the crack begins. The strain of the test piece at this point was calculated and evaluated as critical strain.

Table 4 Chemical Resistance Comparison Example 19 80 parts of the reaction product obtained in Example 6 and 20 parts of glass fiber were mixed, and this mixture was put into a vented extruder.
Kneading was performed at 0°C to obtain a glass fiber reinforced resin composition in the form of pellets. Physical property test and painting After painting with acrylic paint, the appearance was judged with the naked eye, and the adhesion test of the paint film was conducted on the molded product after conducting a moisture resistance test for 72 hours at 50 ° C and 98% RH or higher. Shida. The results obtained are shown in Table 5.

The glass fiber reinforced resin composition of the present invention has high heat resistance,
It can be seen that the paintability is good and the mechanical properties are also excellent.

5th Representative Attorney Masao Miyake and 1 other procedural amendment (method) % formula % 1 Indication of the case 1982 Patent Application No. 137427 2 Name of the invention Highly heat-resistant polymer composition with good oil resistance Thing 3, the case of the person making the amendment. Related ・Patent applicant address (046) Asahi Dow Co., Ltd. Name 4. Agent 〒100 7. Subject of amendment) Special friI? ! A thermoplastic resin composition comprising the resin composition according to item (1) or item (2) and further containing a phosphorus compound.

(14117) The resin composition according to claim (L3), wherein the compound is a phosphoric acid ester or a phosphite.

(]5 The phosphorus compound has the general formulas (A) and (B) [where X is hydrogen, hydroxyl group, amine group, alkyl group having 1 to 1 carbon atoms, alkoxy group having 1 to 10 carbon atoms, or carbon number 1 to 10 allyloxy groups, Y, and Y.

are each an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, 2 is oxygen or sulfur, and n and p are O-4
indicates an integer. ] A homopolymer or copolymer with the general formula % formula %: [:] as a repeating unit and the constituent units consisting of [I] or [I] and [■], and the polymer containing styrene, etc. A graft copolymer obtained by graft polymerization of

Typical examples of homopolymers of polyphenylene ether include pri(2,6-dimethyl-1,4-phenylene) ether, poly(2-methy/l/-6-x thi/I/-1)
．． 4-phenylene ether, poly(2,6-danityl-1,4-phenylene) ether, 1J(2-ethyl-5-n7'-biyl-1,4-phenylene) ether, poly(2,6 -di-n-propyl-1,4-phenylene) ether, ylelJ (2-)methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4- phenylene) ether,
Poly(2-methyl-6-chloro-1,4-phenylene)
Examples include homopolymers such as ether, ylelJ (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly(2-methyl-6-chloroethyl-1,4-phenylene) ether.

The polyphenylene ether copolymer is orthocresol or has the general formula (where Rs + R4 + R1! R6 is t, e r
Aluol group having 1 to 4 carbon atoms, aryl group, )-log [wherein, X is hydrogen, hydroxyl group, amine group, alkyl group having 1 to 10 carbon atoms, alkoxy having 1 to 10 carbon atoms, excluding t-butyl group] group, or an allyloxy group having 1 to 10 carbon atoms,
Y, and Y! each represents an argyl group having 1 to 80 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, 2 represents oxygen or sulfur,
nsp represents an integer of 0 to 4. ] Compounds represented by these are preferred. There is no limit to the amount added, but the resin composition 10
The above compound may be added in an amount of 0.1 to 30 parts by weight per 0 part by weight.

Methods for obtaining the resin composition of the present invention include an extruder, a roll mixer, and a Panbury mixer. +, = - A method of melting and mixing using a der mixer or the like can be used.

The order of melt mixing is to melt and mix all the components at the same time.
, 45 A drug dark comparison゛? 1) ji 1 row 19 80 parts of reaction product and glass m<ta2
This mixture was put into a vent-type extruder and kneaded at 290"C to obtain a pellet-shaped glass mechanical composition. °Captive and Painting No. 5 Representative Masao Miyake 1-1 person

Claims (1)

[Scope of Claims] (1) A copolymer containing as components an aromatic polyethylene resin 5 to 95% polyester, a styrene compound, and an imide compound of α,β-unsaturated dicardic acid. A thermoplastic resin composition with good oil resistance, comprising 1 to 90% by weight of a polyamide obtained from 5 to 90% by weight, Hakaze silylene diamine and an aliphatic dicarboxylic acid, and 0 to 80% by weight of an impact strength reinforcing agent. . (2) The resin composition according to claim (1), wherein the aromatic polyether resin is poly(slodimethylphenylene-1,4-ether). (3) Aromatic polyether, the resin is grafted with a styrene compound 7J (λ6-dimethylphenylene-1°4
-ether) according to claim (1). (4) A copolymer containing a styrene compound and an imide compound of α, β-, β-dicarboxylic acid as a component has a styrene compound in a proportion of 70 to 99 moles and an α, β-dicarboxylic acid in a proportion of 1 to 30 moles. The resin composition according to claim (1), which is a copolymer of β-dicarboxylic acid and an imide compound. (5) A copolymer containing a styrene compound and an imide compound of α, β-, β-dicarboxylic acid as components is 7
0 to 98 molar styrene compound, 1 to 30 molar α, β-, β-dicarboxylic acid imide compound, 1 to 30 molar
Claim 1, which is a copolymer with 20 molar methacrylic ester or Nisdel acrylate
The resin composition of No. 14. (6) A copolymer containing a styrene compound and an α,β-unsaturated decarbic acid compound as components is a styrene compound reinforced with rubber, and α. The resin composition according to claim 1, which is a copolymer containing as a component an imide compound of β-unsaturated dicardic acid. (7) Polyamide is poly(meta-xylylene diamide)
The resin composition according to claim (1). (81ii) The resin composition according to claim (1), wherein the impact strength reinforcing agent is a graft copolymer obtained by graft-polymerizing a monomer mainly composed of a styrene compound to a rubber-like polymer. ( 9) The graft copolymer contains 12% by weight of the rubbery polymer.
The resin composition according to claim (8), which contains the above. The impact strength reinforcing agent is styrene-butadiene block copolymer, hydrogenated nutylene-butadiene block copolymer, ethylene-propylene elanutomer, nutylene-grafted ethylene-propylene elastomer, polyester elastomer, ethylene-based The resin composition according to claim (1), which is one or more ionomer resins. 01 A thermoportable resin composition comprising the resin composition according to claim (1) and further containing a polymer containing 80% by weight or more of a styrene compound. @ The resin composition according to claim α0, wherein the polymer containing 80% by weight or more of a styrene compound is polystyrene. α Feng Thermal oJ made by further containing a phosphorus compound in the resin composition according to claim (1) or (2)
Plastic resin composition. 041 17. The resin composition according to claims 0 to 17, wherein the thread compound is a phosphoric acid ester or a phosphorous acid ester. αQ The phosphorus compound has the general formula (At and (B) [where 1 ((A) (B) -r alkoxy group or 1 carbon number
~10 allyloxy groups, Y, and Y2 each represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, 2 represents an acid group or sulfur, n. p represents an integer of 0 to 4. ] The resin composition according to claim θ1, which is a compound represented by: (2) Resin composition 40 according to claim (1)
-95% by weight of glass fibers and 5-60% by weight of glass fibers. 07! The resin composition according to Claims No. (1) Ring 0d has a content of 40 to 95% and 11%. I,~6o Ya hook 1.
ga. Carbon fiber reinforced resin composition.