JPH03181556A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a polyphenylene ether, a propylene polymer and a modified ethylene/alpha-olefin copolymer- nonconjugated diene copolymer rubber at specific ratios, having excellent heat- resistance, impact resistance and dart impact strength and giving an injection molded article free from peeling defect. CONSTITUTION:The objective composition is composed of (A) 1-99wt.% of a polyphenylene ether and/or a composition containing the same, (B) 1-99wt.% of a propylene polymer and/or propylene polymer graft-copolymerized with styrene and/or a styrenic monomer or a mixture of a styrenic monomer and a monomer copolymerizable with the styrenic monomer and (C) 1-60wt.% (based on 100 pts.wt. of A+B) of a modified ethylene/alpha-olefin copolymer-nonconjugated diene copolymer rubber graft-copolymerized with a styrenic monomer and/or a monomer copolymerizable with the styrenic monomer and an unsaturated dicarboxylic acid anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel thermoplastic resin composition that can be used for molded products by injection molding or extrusion molding.

[Prior art] Generally, polyphenylene ether has heat resistance, hot water resistance,
Although this resin has excellent properties such as dimensional stability and mechanical and electrical properties, it has drawbacks such as poor moldability due to its high melt viscosity, poor chemical resistance, and low impact resistance. have.

A mixture of polyphenylene ether and polystyrene resin is known as a method for improving molding processability by lowering the melt viscosity while maintaining the excellent properties of polyphenylene ether, but this method still does not improve chemical resistance.

On the other hand, propylene polymer has excellent properties such as moldability, toughness, water resistance, and chemical resistance, and is also low in specific gravity and inexpensive, so it can be used in various molded products, films, and sheets. It has been widely used for a long time.

However, propylene polymers have drawbacks or points that require improvement in heat resistance, rigidity, impact resistance, paintability, adhesion, etc., and these are obstacles to the development of new practical applications. In particular, improvements in heat resistance, impact resistance, falling weight strength, paintability, etc. are strongly desired by the market.

[Problems to be Solved by the Invention] From this point of view, a resin composition that combines polyphenylene ether and propylene polymer, has the features of both, and has improved paintability, falling weight strength, moldability, and impact resistance. If a product is obtained, it is expected that it will have a wide range of new uses.

However, in reality, even if propylene polymer is blended with polyphenylene ether, the compatibility is poor, and molded products obtained by injection molding, etc., have phase separation between polyphenylene ether and polypropylene, resulting in extremely poor appearance. , and its mechanical properties are also poor, making it unsuitable for practical use. However, in the market, there is a demand for a resin composition that has high impact resistance and excellent weather resistance while maintaining the excellent heat resistance of polyphenylene ether.

A method for improving the compatibility between polyphenylene ether and propylene polymer is described in JP-A-1999-1. As described in Japanese Patent No. 207349, there is a method of blending a propylene polymer obtained by graft copolymerizing a styrene monomer with polyphenylene ether.

In addition, by blending polyphenylene ether with styrene and/or a propylene polymer, rubber, etc., which is obtained by graft copolymerizing styrene and/or a mixture of styrene and a monomer copolymerizable with styrene, a composition with excellent heat resistance and mechanical properties can be obtained. is obtained as described in JP-A No. 1-207349 and JP-A No. 1-207349.
It is described in No. 234462, etc.

However, even if polyphenylene ether is blended with the propylene polymer, rubber-like substances, etc., physical properties such as processability, heat resistance, impact resistance, paintability, and falling weight strength do not necessarily fully meet market demands. There were times when it wasn't there.

If these physical properties can be achieved, it is expected that the composition will have further expanded applications.

[Means for Solving the Problems] The present inventors have conducted extensive studies over many years in order to develop a composition that can improve the various physical properties in question, and as a result, they have arrived at the present invention.

That is, the present invention provides the following features: 1) (a) polyphenylene ether or a Mihomono containing polyphenylene ether; (1),) styrene and/or a styrenic monomer and a monomer copolymerizable with the styrene monomer; and (c) a styrenic monomer and/or a monomer copolymerizable with the styrenic monomer and an unsaturated dicarboxylic acid anhydride. A modified ethylene-α-olefin copolymer rubber and/or a modified ethylene-α-olefin copolymer-nonconjugated diene copolymer rubber obtained by graft copolymerization of , component (a) is 99-11% by weight, component (b) is 1-1% by weight.
99% by weight, and the sum of the weights of component (a) and component (b) is 1
This relates to a composition excellent in heat resistance, impact resistance, processability, paintability, and falling weight strength made from a thermoplastic resin composition containing 1 to 60 parts by weight of component (c) per 00 parts by weight. be.

The polyphelene ether of component (a) used in the present invention has the general formula [I] 3 (wherein R1, R2, R3, R4 and R5 may be the same or different, each hydrogen atom, halogen atom,
Represents a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group. However, R1-
One of R5 is always hydrogen. ) It can be obtained by oxidative polymerization using oxygen or an oxygen-containing gas using one or two weighed phenolic compounds represented by the following and an oxidative coupling catalyst.

- Also Rt1R2, R3, R4 in the general formula shown in
Specific examples of 5 include hydrogen atom, chlorine atom, bromine atom, fluorine atom, iodine atom, methyl, ethyl, n- or 1
so-propyl, pri-5ec= or t-butyl, chloroethyl, hydroxyethyl, phenylethyl,
Examples include benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl groups.

Specific examples of phenolic compounds represented by the above general formula include phenol, 0-1m-1 or p-cresol, 2.6-2.5-2.4- or 3.5-dimethylphenol, 2-methyl -6-phenylphenol, 2
, 6-diphenylphenol, 2,6-ethylphenol, 2-methyl-6-ethylphenol 1.2,3°5-2.3.6- or 2.4.6-drimethylphenol, 3-methyl -6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like.

Furthermore, phenolic compounds other than the "biped general formula, such as bisphenol-A1 tetrabromobisphenol-A
1 Copolymerization of a polyvalent hydroxy aromatic compound such as resorcinol, hydroquinone, or novolak resin and a phenol compound of the above general formula may be used.

Among these compounds, preferred are 2.6-dimethylphenol (2,6-xylenol) or 2.6-dimethylphenol (2,6-xylenol).
A homopolymer of 6-diphenylphenol and a large amount of 2,6-xylenol and a small amount of 3-methyl-6-t-
Copolymers of butylphenol or 2,3,6-drimethylphenol may be mentioned.

The oxidative coupling catalyst used for oxidative polymerization of a phenol compound is not particularly limited, and any catalyst having polymerization ability can be used in the present invention.

Typical examples include catalysts consisting of cuprous salts and tertiary amines such as cuprous chloride-triethylamine and cuprous chloride-pyridine; cupric chloride-pyridine-
Catalyst consisting of cupric salt such as potassium hydroxide-amine-alkali metal hydroxide; Catalyst consisting of manganese salts such as manganese chloride-ethanolamine, manganese acetate-ethylenediamine, and primary amines; Manganese chloride-sodium methane Catalysts made of manganese salts such as manganese chloride-sodium phenol-1 and alcoholade or phenolate; and catalysts made of a combination of cobalt salts and tertiary amines.

Depending on the oxidative polymerization reaction temperature used to obtain polyphenylene ether, there are two types: high-temperature polymerization, in which the reaction is carried out at a temperature higher than 40°C, and low-temperature polymerization, in which the reaction is carried out at 40°C or lower. Although it is known that there are differences in physical properties etc. in materials obtained by polymerization, both high-temperature polymerization and low-temperature polymerization can be employed in the present invention.

Furthermore, the polyphenylene ether used in the present invention also includes modified products obtained by grafting other polymers onto the above polymers or copolymers.

For example, products obtained by oxidative polymerization of phenols represented by the general formula (each symbol in the formula has the same meaning as above) in the presence of an ethylene-propylene-polyene terpolymer; has the same meaning as above), styrene and/or other polymerizable monomers are graft copolymerized with organic peroxide in the presence of polyphenylene ether polymer or copolymer. (Special Publication No. 47-47862, Special Publication No. 48-[21
No. 97, Special Publication No. 49-5623, Special Publication No. 52-385
No. 96, Japanese Patent Publication No. 52-30991, etc.), the above-mentioned polyphenylene ether polymer or copolymer and polystyrene polymer are kneaded and reacted together with a radical generator (peroxide, etc.) in an extruder (Special Publication No. 52-30991, etc.). 1.42, 1977
No. 799), etc.

In the present invention, the intrinsic viscosity of polyphenylene ether (measured at 30'C in chloroform) is not particularly limited, but is preferably 0.2 to 0.6 dl/g, more preferably 0.25 to 0.55 dl/g. Therefore, the optimum intrinsic viscosity can be selected depending on the situation.

Furthermore, the polyphenylene ether of component (a) in the present invention includes modified polyphenylene ethers described in detail below, and the modified polyphenylene ethers can be used as appropriate according to market demands.

Here, the polyphenylene ether modified product typically refers to polyphenylene ether in the presence or absence of a radical initiator, with carbonic acid groups, acid anhydride groups, etc.
Refers to the compound obtained by modifying with a polyfunctional compound (E) having one or more types of acid amide group, imide group, carboxylic acid ester group, epoxy group, amino group or hydroxyl group, and other epoxy compounds (J) or It also includes those modified with organosilane compounds (K) and the like.

In the present invention, the polyfunctional compound (E) used as a modifier for polyphenylene ether includes a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an epoxy group, an amino It is a polyfunctional compound having one or more types of groups or hydroxyl groups. Preferably, the molecule contains ([) a carbon-carbon double bond or a carbon-carbon triple bond and (11) a carboxylic acid group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group, epoxy group, or amino group. Or a compound having one or more types of hydroxyl groups at the same time (F
).

Specific examples of compound (F) include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, and a reaction product of maleic anhydride and diamine, such as 0 0 0 Qo
0 0
Those having a structure such as Q (where RL3 represents an aliphatic or aromatic group), methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, linseed oil , natural oils and fats such as hempseed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive ura, coconut oil, sardine oil, epoxidized natural oil fat such as epoxidized soya ura, acrylic acid, butenoic acid, crotonic acid , vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α
-Ethyl acrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl -3-butenoic acid, 2-heptenoic acid,
2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 1
o-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid,
4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadenoic acid, 2-octadecenoic acid, 9-octadecenoic acid,
Icosenoic acid, tocosenoic acid, erucic acid, tetraenoic acid,
Mycolibenic acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylic acid, geranic acid, 2,4-decadienoic acid, 2°4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9.12- Octadecadienoic acid, hexadecatrienoic acid, linoleic acid, lylunic acid, octadecatrienoic acid, icosadienoic acid, icosaj-lienoic acid, icosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, icosapene Unsaturated carboxylic acids such as citric acid, erucic acid, docosadienoic acid, docosa), citric acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacosenoic acid, oftacosenoic acid, and traacontenoic acid, or these unsaturated Esters of carboxylic acids, acid amides, anhydrides, or allyl alcohol, crotyl alcohol, methylvinylcarbinol, allylcarbinol, methylpropenylcarbinol, 4-penten-1-ol, lO-undecen-1-ol, propargyl alcohol, 1,4
-Pentadien-3ol, 1,4-hexadiene-3
-ol, 3,5-hexadien-2-ol, 2,4
-hexadien-1-ol, general formula CnH2, -50
H.

CH0H1CnH2n-90H (however, n is positive n 2
n-7 integer), 3-butene-1゜2-
Diol, 2,5-dimethyl-3-hexene-2,5-
Diol, 1,5-hexadiene-3゜4-diol,
2. Unsaturated alcohols such as 6-octanonine-4,5-diol, unsaturated amines in which the 10H group of such unsaturated alcohols is replaced with -NH2 group, or low Polymers (e.g.
Those with an average molecular weight of about 500 to 1oooo) or polymers (for example, those with an average molecular weight of 10,000 or more) to which maleic anhydride or phenols are added, or amino groups, carboxylic acid groups, hydroxyl groups, epoxy groups, etc. Examples include those that have introduced .

Other preferred polyfunctional compounds (E) have the general formula [
V] (RO) R(cOOR16)n(cONR, □R1
8) Aliphatic carboxylic acids, acid esters and acid amides represented by Sl, 5 m 14 [V] (wherein R14 is a linear or branched aliphatic saturated chain having 2 to 20 carbon atoms) is a hydrocarbon group, R15 is a hydrogen atom and a group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group, an acyl group, and a carbonyldioxy group, and each of R16 is a hydrogen atom and a group consisting of a carbonyldioxy group; A group independently selected from the group consisting of alkyl groups and aryl groups having 1 to 20 atoms, and each of R and RI8 is a hydrogen atom and a group consisting of alkyl groups and aryl groups having 1 to 10 carbon atoms. m, n and S are integers greater than or equal to 0, and m + n
+s≧2. ) and derivatives thereof.

Specific examples of compound (G) include oxyacetic acid, lactic acid, α
-oxy-n-butyric acid, α-oxyisobutyric acid, α-oxy-n-valeric acid, α-oxyisovaleric acid, 2-oxy-2
-Methylbutanoic acid, α-oxy-n-caproic acid, α-
Oxyisocaproic acid, 2-ethyl-2-oxybutanoic acid, 2-oxy-3,3-dimethylbutanoic acid, 2-oxy-2-methylpentanoic acid, 2-oxy-5-methylhexanoic acid, 2-oxy- 2,4-dimethylpentanoic acid,
3-oxypropionic acid, β-oxybutyric acid, β-oxyisobutyric acid, β-oxy-n-valeric acid, β-oxyisovaleric acid, 2-oxymethylbutanoic acid, oxymethyl acid, 3
-oxy-2-methylpentanoic acid, 1,1-oxytetradecanoic acid, yarabinolic acid, 1,4-oxyhexadecanoic acid, sabinic acid, uniperinic acid, oxymalonic acid,
Methyl tartronic acid, ethyl tartronic acid, n-propyl tartronic acid, isopropyl tartronic acid, oxymethyl malonic acid, oxyisopropyl malonic acid, ethyl-
Oxymethyl-malonic acid, linchoic acid, α-methylmalic acid, α-oxy-α′-methylsuccinic acid, α-oxy-α, α′-dimethylsuccinic acid, α-oxy-α, α
-diethylsuccinic acid, α-oxy-α′-ethylsuccinic acid, α-oxy-α-methyl-α-ethylsuccinic acid, trimethylmalic acid, α-oxyglutaric acid, β-oxyglutaric acid, β-oxy-β- methylglutaric acid,
α-oxyadipic acid, citric acid, isocitric acid, norcaberalic acid, agaritic acid, glyceric acid, α, β-
Dioxybutyric acid, α, β-dioxyisobutyric acid, β, β′
-dioxyisobutyric acid, β, γ-dioxybutyric acid, α, γ-
Dioxy-β.

β-dimethylbutyric acid, α,β-dioxy-α-isopropylbutyric acid, ibrolic acid, ustyric acid-A.

9.10-dioxyoctadecanoic acid, tartaric acid (optically active or racemic), mesotartaric acid, methyltartaric acid, α,
β-Dioxyglutaric acid, α, γ-dioquine glutaric acid, α, γ-dioxy-β-methylglutaric acid, α, γ
-dioxy-β-methyl-β-ethylglutaric acid, α,
γ-dioxy-α.

γ-dimethylglutaric acid, α, δ-dioxyadipic acid, β, γ-dioxyadipic acid, 6,7-cyoxydodecanoic acid, 7,8-dioxyoctadecanoic acid, furionic acid, trioxybutyric acid, trioxyiso Butyric acid, trioxyglutaric acid, succinic acid, glutaric acid, adipic acid, α
-Methylglutaric acid, dobucanic acid, etc.

Further, "double derivative of general formula [V]" means lactone,
These include acid anhydrides, alkali metal salts, alkaline earth metal salts, salts with amines, etc. Specific examples include β-propiolactone, glycolide, lactide, β-methylpropiolactone, β, β dimethyl Propiolactone, β-
n-propylpropiolactone, β-isopropylpropiolactone, β-methyl-β-ethylpropiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, 1,5 -Oxypentadecanoic acid lactone, γ-butyrolactone-α-carboxylic acid, paraconic acid, α-methylparaconic acid, β-methylparaconic acid, α-ethylparaconic acid, α-isopropylparaconic acid, γ-methylparaconic acid, γethylparaconic acid, α , γ-dimethylparaconic acid, β, γ-dimethylvalaconic acid, α, α, β-trimethylparaconic acid, γ2 γ-dimethylparaconic acid, nephrostellanic acid, γ-valerolactone-γ-carboxylic acid,
γ-isopropyl-γ-butyrolactone-γ-carboxylic acid, α,α-dimethyl-γ-butyrolactone-γ-carboxylic acid, β-methyl-γ-valerolactone-γ-carboxylic acid, α,β-dimethyl-γ-valerolactone-γ -Carboxylic acid, α,β-dimethyl-γ-butyrolactone-γ
-carboxylic acid, homoisocarpic acid, α-(γ-oxycarbonylpropyl)-γ-butyrolactone, β-oxyadipic acid-γ-lactone, α,δ-dimethyl-β-
Oxyadipic acid-γ-lactone, β-oxy-β-methyladipate-γ-lactone, α-(δ′-carboxy n-butyl)-γ-butyrolactone, α-methylisocitric acid lactone, cinchonic acid, α- Oxy-γ-butyrolactone, β-oxy-γ-butyrolactone, δ
-Oquin-γ-valerolactone, vantolactone, mevalonic acid, malic anhydride, tartaric anhydride, oxyglutaric anhydride, α, β, γ-trioxyvaleric acid lactone,
α-oxy-α-oxymethyl-γ-butyrolactone,
Examples include succinic anhydride and glutaric anhydride. One or more of these may be used.

Particularly preferred among these are tartaric acid, malic acid, citric acid, and derivatives thereof. Also included are various commercially available forms of such acids (eg, anhydrous and hydrated acids).

Examples of useful derivatives include acetyl citrate, monostearyl and/or distearyl citrate, N,
N'-diethylcitrate amide, N,N'-dipropylcitrate amide, N-phenylcitrate amide, N-
Mention may be made of dodecyl citric acid amide, N,N'-didodecyl citric acid amide and N-dodecyl citric acid amide, calcium malate, calcium citrate, potassium malate and potassium citrate.

Other preferred polyfunctional compounds (E) include (i) an acid halide group, most preferably an acid chloride group;
) A compound (H) having at least one carboxylic acid group, carboxylic acid anhydride group, acid ester group or acid amide group, preferably a carboxylic acid group or carboxylic acid anhydride group in the molecule.

Specific examples of compound (H) include anhydrotrimelide acid chloride, chloroformylsuccinic anhydride, chloroformylsuccinic acid, chloroformylglutaric anhydride, chloroformylglutaric acid, chloroacetylsuccinic anhydride, chloro Included are acetylsuccinic acid, trimelide acid chloride and chloroacetylglutaric acid. Among these, anhydrotrimelide acid chloride is preferred.

These compounds (F), (G), and (H) are described in detail in US Pat. Nos. 4,315,086 and 4,642,358.

In the present invention, in addition to the above compounds, the following epoxy compounds (J) and organosilane compounds (K) can also be used as modifiers for polyphenylene ether.

In the present invention, the epoxy compound 0) used as a modifier for polyphenylene ether refers to a compound having an oxirane group in the molecule and/or an epoxy compound consisting of a condensation polymer of dihydric phenol and shrimp chlorohydrin. .

Specific examples of the epoxy compound 0) include epoxidized products of olefins or cycloalkenes such as ethylene oxide, propylene oxide, and cyclohexene oxide.

Furthermore, products obtained by condensing dihydric phenols and shrimp chlorohydrin in various ratios can also be used.

A typical example is a condensate of bisphenol A and shrimp chlorohydrin (products such as ELA
-115, ELA-127, ELA-128, ELA-
134, ESA-011, ESA-014, ESA-0
19 [trade name, manufactured by Sumira Chemical Co., Ltd.], and Union Carbide phenoxy resin, etc.), condensates of resorcinol and shrimp chlorohydrin, condensates of hydroquinone and shrimp chlorohydrin, tetrabromobisphenol A and shrimp chlorohydrin, glycidyl etherification of phenol novolak or talesol novolac (e.g. Sumiepoxy ESCN-220
[Product name, manufactured by Sumira Chemical Industries, Ltd.] series, etc.).

Condensates of polyhydric alcohols and shrimp chlorohydrin can also be used. Representative examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and the like.

Glycidyl etherified products of -hydric phenols or monohydric alcohols, such as phenyl glycidyl ether, butyl glycidyl ether, cresyl glycidyl ether, etc., can also be used.

Also usable are glycidylated amine compounds (for example, Sumiepoxy ELN-125 [trade name], which is a diglycidylated aniline commercially available from Sumira Chemical Co., Ltd.)).

Additionally, polymers of epoxy-containing unsaturated compounds (e.g., glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether) or epoxy-containing unsaturated compounds and other monomers (e.g., ethylene, propylene, butene, styrene, α -methylstyrene, 4-
Methyl-pentene, chlorostyrene, bromostyrene,
Acrylic acid, acrylic ester, acrylonitrile,
A copolymer containing one or more of vinyl chloride, methacrylic acid, methacrylic ester, maleic anhydride, vinyl acetate, etc. can also be used.

Among these polymers, styrene glycidyl (meth)acrylate copolymers and ethylene-glycidyl (meth)acrylate copolymers are particularly preferred.

In the present invention, the organosilane compound (K) used as a modifier for polyphenylene ether is defined as having in its molecule (i) at least one silicon atom bonded to a carbon atom via an oxygen atom, and (jl) a carbon- A carbon double bond or a carbon-carbon triple bond, and (I Ii) a functional group selected from an amino group, a mercapto group, a carboxylic acid group, an acid anhydride group, an acid amide group, a carboxylic acid ester group, an imide group, and a hydroxyl group It is an organosilane compound having one or more types of groups at the same time.

In such compound (K), the C-0-8i component usually exists as an alkoxy group or an acetoxy group directly bonded to the silicon atom. Such alkoxy or acetoxy groups generally have less than 15 carbon atoms and may also contain foreign atoms (eg, oxygen).

Furthermore, more than one silicon atom may be present in such compounds. When multiple silicon atoms are present, they may be bonded via oxygen bonds (e.g. in the case of cyclohexane), silicon-silicon bonds, or difunctional organic groups (e.g. methylene or phenylene groups). .

Examples of suitable organosilane compounds (K) include γ
-aminopropyltriethoxysilane, 2-(3-cyclohexenyl)ethyltrimethoxysilane, 1,3-divinyltetraethoxysilane, vinyltris(2-methoxyethoxy)silane, 5-bicyclohebutenyltriethoxysilane and γ -mercaptopropyltrimethoxysilane.

In the present invention, compounds (E), (F), (G), (H
), (J) and (K) are selected depending on the purpose, but generally 200 parts by weight or less, preferably 80 parts by weight or less, more preferably 2Offi amount per 100 parts by weight of polyphenylene ether. parts by weight, most preferably from 0.01 to 10 parts by weight.

The various compounds (E), (F), (G), (
When modifying polyphenylene ether with H), (J), or (K), a radical generator may be used depending on the case. Examples of the radical generator used include known organic peroxides and diazo compounds.

For example, azo compounds such as 2.2'-azobisisobutyronitrile, 2.2'-azobis(2,4,4)-1-limethylvaleronitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3. 3.5-trimethylcyclohexanone peroxide, 2.2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 25-dimethylhexane-2,5- Cibidrobar oxide, di-t-butyl peroxide, 1.3-bis(t-butylperoxyisopropyl)benzene, 2.5-dimethyl-2,5-di(t-butylperoxy)hexane, 2.5- Dimethyl-2,5-di(t-butylperoxy)hexyne-3, lauroyl peroxide, 3.3.5-1-limethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl peroxide Oxyisobutylene-1., t-butyloxypivalate, t-butyl-oxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy Laurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxy Various organic peroxides such as propyl carbonate and polystyrene peroxide.

Preferred specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, terL-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, and the like. .

The amount of radical generator used is polyphenylene ether 1
The amount ranges from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight.

The polyphenylene ether modified product in the present invention may be obtained by chemically reacting two pairs of compounds and polyphenylene ether, or by physical interaction (for example, physical adsorption to polyphenylene ether). You can.

Furthermore, as a preferable polyphenylene modified product in the present invention, the above-mentioned polyfunctional compound (F) having an unsaturated group
or the above-mentioned polyfunctional compound (F) having an unsaturated group, and an unsaturated monomer other than that,
Examples of the radical initiator include those obtained by graft polymerization with polyphenylene ether.

Preferably, such unsaturated monomers include vinyl and/or vinylidene compounds (L). Specific examples of the compound (L) are shown below.

That is, aromatic vinyl or vinylidene compounds such as α-methylstyrene, o, m and p-methylstyrene, chlorostyrene, bromostyrene, divinylbenzene, hydroxystyrene, aminostyrene; olefins such as ethylene; ) Methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, octyl (meth)acrylate, etc.
meth)acrylic acid ester compound: acrylonitrile,
These include cyanovinyl compounds such as methacrylonitrile; vinyl ester compounds such as vinyl acetate; vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; and unsaturated halogen compounds such as vinyl chloride and vinylidene chloride. More than one species may be used.

Preferred unsaturated monomers for graft polymerization are styrene, styrene-glycidyl methacrylate, styrene-glycidyl acrylate, styrene-maleic anhydride, styrene-acrylic acid, and styrene-methacrylic acid.

In the present invention, the amount of the compound (L) used is 200 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 part by weight, based on 100 parts by weight of polyphenylene ether.
~50 parts by weight.

There is no limitation to the method for producing the modified polyphenylene product in the present invention, and known methods can be used.

For example, (1) a method in which polyphenylene ether and the above compound are uniformly mixed in the form of pellets, powder, or pieces using a high-speed stirrer, etc., and then melt-kneaded and blended; (2) polyphenylene ether is dissolved; Alternatively, the above compound is added to a swollen solution, dissolved or swollen, and heated while stirring, or (3) the above compound is added to polyphenylene ether, dispersed in water, and heated while stirring.

In these methods, it is preferable to use a dispersion stabilizer such as polyvinyl alcohol, sodium dodecylbenzenesulfonate, or calcium phosphate.

Further, a solvent that dissolves or swells polyphenylene ether may be added depending on the case.

In the method (1), there are no particular restrictions on the temperature and time of melt-kneading. Although the temperature varies slightly depending on the type and amount of the compound, it is generally in the range of 150 to 350°C.

As the melt-kneading device, any method may be used as long as it can handle a molten viscous material, and either a batch method or a continuous method can be used.

Specific examples thereof include, for example, a single-screw or multi-screw extruder, a Banbury mixer roll, a kneader, and the like.

There are no particular limitations on the solvent used in methods (2> and (3)), as long as it can dissolve or swell polyphenylene ether.

Specific examples include chloroform, methylene chloride, benzene, xylene, chlorobenzene, cyclohexane,
Examples include styrene, toluene, and 0-chlorophenol. Further, a mixed solvent may be used as long as it can be dissolved or swelled.

There are no particular restrictions on the temperature and time for blending, and the temperature is generally 20 to 250°C and the time is 1 minute to
Ranges of up to 10 hours are taken.

In the present invention, when using a polyphenylene ether modified product, it is preferable to prepare the polyphenylene ether modified product in advance and then mix it with other components to produce the resin composition of the present invention. It is also possible to prepare a resin composition by mixing polyphenylene ether and other components of the present invention all at once.

In the present invention, the above-mentioned component (a) polyphenylene ether and polyphenylene ether modified product can be used alone or in combination of two or more.

The resin composition containing polyphenylene ether as component (a) in the present invention means a resin composition comprising the aforementioned polyphenylene ether and/or modified polyphenylene ether and one or more other polymer compounds.

Other polymer compounds include, for example, polyolefins such as polymethylpentene; polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyvinylpyridine,
Homopolymers and copolymers of various vinyl compounds such as polyvinylcarbazole, polyacrylamide, polyacrylonitrile, ethylene-vinyl acetate copolymer, alkenyl aromatic resin; polycarbonate, polysulfone, polyethylene terephthalate, polybutylene terephthalate, polyarylene, Examples include stellate (for example, Unitika's U polymer), polyphenylene sulfide; polyamides such as 6-nylon, 6,6-nylon, and 12-nylon; and condensation polymer compounds such as polyacetal. Further examples include various thermosetting resins such as silicone resins, fluororesins, polyimides, polyamideimides, phenolic resins, alkyd resins, unsaturated polyester resins, epoxy resins, and Dapon resins.

In the thermoplastic resin composition used in the present invention, in addition to component (a) as described above, component (b) is (1) a styrenic monomer, or a combination of a styrenic monomer and a styrenic monomer. A modified propylene polymer obtained by graft copolymerizing a mixture with a polymerizable monomer, or (11) a composition containing the modified propylene polymer and a propylene polymer is used.

The modified propylene polymer herein refers to 100 parts by weight of the propylene polymer, and 0.2 to 100 parts by weight of a styrene monomer or a monomer that can be copolymerized with the styrene monomer and the styrene monomer. It is obtained by graft copolymerizing 150 parts by weight, preferably 2 to 90 parts by weight.

If the amount of monomer to be graft copolymerized is less than 0.42 parts by weight, no resin modification effect will be observed, and if it exceeds 150 parts by weight, chemical resistance will decrease.

Here, the propylene polymer means a propylene homopolymer or a propylene copolymer, and the propylene copolymer refers to propylene and other α
- means a random or block copolymer with an olefin.

Specific examples of propylene copolymers include ethylene-propylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, and propylene-1-hexene copolymer. Examples include 1-octene copolymer.

Moreover, an ethylene-α-olefin copolymer and/or a styrene-modified product of the copolymer can be blended with the propylene polymer, if necessary. The density of the ethylene-α-olefin copolymer to be blended is 0.
．． 82 to 0.92 g/cm" is preferably used.

As the propylene polymer, a highly crystalline propylene polymer can be used if necessary.

The highly crystalline propylene polymer herein refers to the isotactic pentad fraction of the butane-insoluble portion of the propylene homopolymer, which is the first segment polymerized in the first step of the propylene homopolymer or block copolymer. is 0970 or more, or the isotactic pentad fraction of the butane-insoluble part of the homopolymer part of the propylene polymer is 0.970 or more,
The content of the boiling hebutane soluble portion is 5.0% by weight or less, and the content of the 20° C. xylene soluble portion is 2.0% by weight or less.

Such highly crystalline propylene polymers are disclosed in, for example, JP-A-60-28405, JP-A-60-228504, and JP-A-61.
-21.8606 and 61-287917.

Furthermore, in fields where high rigidity is required, it is preferable to blend a nucleating agent into the propylene polymer. For example, aluminum or sodium salts of aromatic carboxylic acids (Japanese Patent Publication No. 58-80829), aromatic carboxylic acids, metal salts of aromatic phosphates, sorbitol derivatives (Japanese Patent Publication No. 55-80829),
12460, JP-A No. 58-129036), etc., it is known that these become nucleating agents for crystal nuclei (hereinafter referred to as "nucleating agents") and high crystallinity can be obtained.

In addition to these nucleating agents, vinylcycloalkane polymers having 6 or more carbon atoms are also known to act effectively as nucleating agents (Japanese Patent Laid-Open No. 1738/1986).

That is, it is a composition obtained by blending a propylene polymer with a vinylcycloalkane polymer having 6 or more carbon atoms, and the composition has a vinylcycloalkane unit of 0.0%.
A propylene polymer composition containing 5 wtppm to 10000 wtppm has higher crystallinity.

Moreover, a highly rigid propylene polymer can be obtained by blending the vinylcycloalkane polymer with the above-mentioned highly crystalline propylene polymer.

Propylene polymers (propylene homopolymers and propylene copolymers thereof) may be used alone or in combination of two or more.

In the composition of the present invention, the styrenic monomer used for modifying the propylene polymer in component (b) has the general formula [I
I] (wherein R6, R7, R8, R9 and Rlo are hydrogen, halogen, hydrocarbon or substituted hydrocarbon group, hydrocarbonoxy group or substituted hydrocarbonoxy group, R11 is a hydrogen atom, It is a lower alkyl group having 1 to 4 carbon atoms.)

R6, R7, R8R9 and R in the above general formula [■]
Specific examples of lo include hydrogen atoms; halogen atoms such as chlorine, bromine, and iodine; hydrocarbon groups such as methyl, ethyl, propyl, vinyl, allyl, benzyl, and methylbenzyl; and substituted hydrocarbon groups such as chloromethyl and bromomethyl. ; Includes hydrocarbon oxy groups or substituted hydrocarbon oxy groups such as methoxy, ethoxy, phenoxy, and monochloromethoxy.

Further, specific examples of R1□ include a hydrogen atom; a lower alkyl group such as methyl and ethyl;

Specific examples of styrene monomers include styrene, 2.4
-dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene, p-divinylbenzene, p-(chloromethoxy)-styrene, α-methylstyrene, 0-methyl-α-methylstyrene, m- Examples include methyl-α-methylstyrene, p-methyl-α-methylstyrene, and p-methoxy-α-methylstyrene. These can be used alone or in combination of two or more.

Among these, styrene is preferably used.

As component (b) in the present invention, a modified propylene polymer obtained by copolymerizing a mixture of a styrenic monomer or a monomer that can be copolymerized with a styrenic single fluid is used. By appropriately selecting the monomer to be obtained and blending it with the propylene polymer by graft copolymerization,
Thermoplastic resins possessing high mechanical properties can be obtained.

Here, specific examples of monomers that can be copolymerized with the styrene monomer include acrylonitrile, glycidyl methacrylate, glycidyl acrylate, methacrylate trile,
Derivatives of fumaric and maleic acid, vinyl ketones, maleic anhydride, acrylic acid, methacrylic acid, vinylidene chloride, maleic esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate , propyl acrylate, butyl acrylate, vinyl chloride, vinyl acetate, divinylbenzene, ethylene oxide, vinylidene chloride, maleate ester, isobutyne, alkyl vinyl ether, anethole, indene, coumaron, benzofuran, 1,2-dihydronaphthalene, acenaphthylene,
Isoprene, chloroprene, 2-aminoethyl methacrylate, 2-hydroxyethyl methacrylate, trioxane, 1,3-dioxolane, propylene oxide,
β-propiolactone, vinylbiphenyl, 1,1-diphenylethylene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-vinylpyridine, 4-vinylpyridine, 2,3-dimethylbutadiene, ethylene, propylene, allyltrimethyl Examples include silane, 3-butenyltrimethylsilane, vinylcarbazole, N,N-diphenylacrylamide, and fumaronitrile.

Further, derivatives of these monomers can also be used.

In the present invention, these monomers and their derivatives can be used alone or in combination of two or more.

Among the above monomers, glycidyl methacrylate, glycidyl acrylate, methyl methacrylate, 2-aminoethyl methacrylate, 2-hydroxyethyl methacrylate and the like are preferably used.

In the present invention, the mixing ratio of the styrenic monomer and the monomer copolymerizable with it can be arbitrarily changed depending on the purpose, but the styrenic monomer accounts for 1 to 100% by weight. It is preferable.

The styrenic monomer and the monomer copolymerizable with the styrenic monomer can be graft-copolymerized with the propylene polymer by a well-known appropriate method.

For example, a method in which a propylene polymer, a graft monomer, and a peroxide are mixed and grafted by melt-kneading in a melt-kneading device, or a method in which a propylene polymer is dispersed together with a graft monomer in water, and then a peroxide is mixed in a nitrogen atmosphere. In addition, a grafted propylene polymer is obtained by heating and reacting with stirring, cooling after the reaction, washing and filtration, and drying.Other methods include irradiating the propylene polymer with ultraviolet rays or radiation in the presence of a graft monomer, or with oxygen or ozone. There are ways to make contact with.

In addition, when graft copolymerizing a mixture of a styrene monomer and an acrylic acid ester to a propylene polymer, anionic polymerization is used. A modified propylene polymer can be obtained by first producing a copolymer of a styrene monomer and an acrylic ester, and then melt-kneading this copolymer and a propylene polymer together with a peroxide.

Here, the peroxide used in producing the modified propylene polymer is not particularly limited, and compounds (E) to (K
) A desired one can be appropriately selected and used from the various peroxides explained in the section for producing a modified polyphenylene ether.

Component (b) in the thermoplastic resin composition of the present invention includes:
Furthermore, antioxidants, heat stabilizers, light stabilizers, antistatic agents, inorganic or organic colorants, rust preventives, crosslinking agents,
Six additives such as blowing agents, lubricants, plasticizers, fluorescent agents, surface smoothing agents, and surface gloss improvers can be added during the manufacturing process or in subsequent processing steps.

Component (c) in the present invention is a modified ethylene-α-olefin copolymer rubber and/or a modified ethylene-α-olefin copolymer rubber obtained by graft copolymerizing a styrene monomer and an unsaturated dicarboxylic acid anhydride. It is a conjugated diene copolymer rubber.

The raw material ethylene-α-olefin copolymer rubber mentioned here includes ethylene and other α-olefins, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. ethylene-propylene-1-butene copolymer, etc., and terpolymer rubbers such as ethylene-propylene-1-butene copolymer.
Propylene copolymer rubber, ethylene-1-butene copolymer rubber, etc. are preferably used.

The nonconjugated diene content of the raw material ethylene-α-olefin-nonconjugated diene copolymer rubber in component (c) of the present invention is preferably 20% by weight or less. If the non-conjugated diene content exceeds 20% by weight, it is not preferable because fluidity deteriorates due to gelation during kneading.

Moreover, as the non-conjugated diene in the ethylene-α-olefin-non-conjugated diene copolymer rubber, ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, etc. are preferable.

The ethylene content in these raw material copolymer rubbers is 15 to 85
% by weight, preferably 40 to 80% by weight. In other words, highly crystalline copolymers with an ethylene content of more than 85% by weight are difficult to process under normal rubber molding conditions, and those with an ethylene content of less than 15% by weight have a high glass transition temperature (Tg).
This is not preferable because it increases the rubber properties and deteriorates the rubbery properties.

Further, the number average molecular weight of the raw material copolymer rubber is preferably such that it can be kneaded in a normal extruder, and to, 0
00 to 100.000. If the molecular weight is outside this range,
If the molecular weight is too small, it will be difficult to handle when feeding it to an extruder, and if the molecular weight is too large, the fluidity will be low and processing will be difficult.

The styrenic monomer in component (c) of the present invention is represented by the above-mentioned general formula (n), and among them, styrene is preferably used.

The monomer copolymerizable with the styrenic monomer in component (c) of the present invention refers to the above-mentioned monomers excluding unsaturated dicarboxylic acid anhydrides such as maleic anhydride.

Examples of the unsaturated dicarboxylic anhydride used in component (c) of the present invention include maleic anhydride, fumaric anhydride, citraconic anhydride, etc. Maleic anhydride, which has particularly high reactivity, is advantageously used. be done.

Ethylene-α-olefin copolymer rubber, ethylene-α
- As a method for producing the graft copolymer of olefin-nonconjugated diene copolymer rubber, any conventionally known method can be used.

Examples include maleic anhydride and styrene graph I.
- A method for producing ethylene-α-olefin copolymer rubber is, for example, adding maleic anhydride, styrene, and a radical initiator to ethylene-α-olefin copolymer rubber in a hydrocarbon solvent, and heating at 60°C. ~A few minutes at 150℃~
A solution containing the modified rubber is obtained by carrying out the reaction for several hours. At this time, maleic anhydride may be converted into a half ester or a half amidation by appropriately adding alcohol, amine, etc., if necessary. The solution thus obtained is poured into a large amount of methanol, acetone, etc. to recover the modified rubber.

Modified rubber can also be obtained by kneading maleic anhydride, styrene, and a radical initiator with ethylene-α-olefin copolymer rubber in an extruder. For example, maleic anhydride is added to 100 parts by weight of rubber. 0.5 to 15 parts by weight, 0.2 to 20 parts by weight of styrene,
Using 0.005 to LO parts by weight of a radical initiator, 15
A modified copolymer can be obtained by kneading at 0°C to 300°C for several minutes to several tens of minutes. At this time, a gelling inhibitor, for example, a phenolic antioxidant such as BIT, may be used in combination, if necessary.

A modified rubber of ethylene-α-olefin-nonconjugated diene copolymer rubber can also be produced in the same manner.

In the present invention, in addition to the maleic anhydride and styrene-modified ethylene-α-olefin copolymer rubber and their modified ethylene-α-olefin-nonconjugated diene copolymer rubber, other modified ethylene-α- Olefin copolymer rubber, ethylene-α-olefin-nonconjugated diene copolymer rubber can be used, and for example, in addition to the above maleic anhydride, methyl acrylate, methyl methacrylate, allyl glycidyl ether, glycidyl methacrylate-1, The above copolymer rubber modified with a monomer selected from glycidyl acrylate and the like and a styrene monomer is used.

Furthermore, a graft copolymer rubber in which two or more of these monomers are used simultaneously can also be used.

Furthermore, two or more rubbers selected from modified ethylene-α-olefin copolymer rubber and modified ethylene-α-olefin non-conjugated diene copolymer rubber on a platform scale can also be used at the same time.

In addition, modified ethylene-α-olefin copolymer rubber grafted with a styrene monomer and a monomer copolymerizable with the styrene monomer, modified ethylene-α-olefin-
In addition to the method described above, the non-conjugated diene copolymer rubber can also be obtained by the following method.

That is, shredded pieces or pellets of raw material ethylene-α-olefin copolymer rubber or ethylene-α-olefin-nonconjugated diene copolymer rubber are dispersed in pure water together with a dispersant, and then a styrene monomer is added. After impregnating the copolymer rubber, using a radical initiator, the
By reacting at a temperature of 1 to 5 hours, a modified copolymer rubber grafted with a styrene monomer is obtained.

Next, this copolymer rubber was put into an extruder together with maleic anhydride and a radical initiator under the same mixing conditions as described above.
By kneading, the target component (c) modified ethylene-α-olefin copolymer rubber, modified ethylene-α
-Olefin-nonconjugated diene copolymer rubber can also be obtained.

The amount of the styrenic monomer or the mixture of the styrenic monomer and the monomer copolymerizable with the styrenic monomer and the unsaturated dicarboxylic acid anhydride used as component (c) in the present invention is as follows: 0.1 to 150 parts by weight of a styrenic monomer, or a mixture of a styrene monomer and a monomer copolymerizable with the styrene monomer, per 100 parts by weight of rubber;
It is preferable that the unsaturated dicarboxylic anhydride is 0.1 to 15 parts by weight, and the sum of the weights of each monomer and the unsaturated dicarboxylic anhydride polymer in the modified rubber is 2 parts by weight or more. .

In the modified rubber of component (c), if the polymer of a styrene monomer or a mixture of a styrenic monomer and a monomer copolymerizable with the styrene monomer is less than 0.1 part by weight, it is classified as The impact resistance, falling weight strength, etc. of the composition decrease, and
If it exceeds 50 parts by weight, the chemical resistance of the composition will decrease, which is not preferable.

In addition, if the unsaturated dicarboxylic acid anhydride used in the modified rubber is less than 0.1 part by weight, the impact resistance and falling weight strength of the composition will decrease, and if it exceeds 15 parts by weight, it will remain unreacted. This is undesirable because the amount of unsaturated dicarboxylic acids increases.

In the modified rubber, if the sum of the weights of the styrene monomer and the unsaturated dicarboxylic acid anhydride used in the modified rubber is less than 2 parts by weight, the impact resistance and falling weight impact strength of the composition will be improved. is not recognized.

In the present invention, the desired thermoplastic resin composition can be obtained by setting the composition ratio of component (a) and component (b) within a specific range.

The ratio of component (a) and component (b) in the present invention is such that component (a) is 1 to 99% by weight and component (b) is 99 to 99% by weight.
It is 1% by weight.

The ratio of component (a) to component (b) is such that if component (a) is less than 1% by weight, the heat resistance of the composition will be insufficient;
If it exceeds 9% by weight, the processability and chemical resistance of the composition will be insufficient.

In the present invention, the weight sum of component (a) and component (b) is 1
00 parts by weight, component (c) is 1 to 60 parts by weight.

If component (c) is less than 1 part by weight, no effect of improving the impact resistance of the composition will be observed, and if it exceeds 60 parts by weight, the excellent heat resistance of the composition will be lost.

In the present invention, rubber-like substances other than component (c) may be blended as desired.

Specific examples include natural rubber, butadiene polymers, butadiene-styrene copolymers (including random copolymers, block copolymers, graft copolymers, etc.).
, or its hydrogenated product, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester copolymer, ethylene -propylene copolymer,
Ethylene-butene copolymer, ethylene-propylene-styrene copolymer, styrene-isoprene (stripe polymer, or its hydrogenated product, styrene-butylene copolymer, styrene-ethylene-propylene copolymer, perfluororubber, fluorine Rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-nonconjugated diene copolymer, thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (e.g. propylene oxide),
epichlorohydrin rubber, polyester elastomer,
Examples include polyamide elastomers and epoxy group-containing copolymers.

The epoxy group-containing copolymer referred to herein is a copolymer consisting of an unsaturated epoxy compound and an ethylenically unsaturated compound.

Although there is no particular limitation on the composition ratio of the epoxy group-containing copolymer,
Preferably, the unsaturated epoxy compound is copolymerized with O'' to 50% by weight, preferably 1 to 30% by weight.

Specifically, the above-mentioned unsaturated epoxy compound is a compound having an unsaturated group copolymerizable with an ethylenically unsaturated compound and an epoxy group in the molecule.

For example, unsaturated glycidyl esters and unsaturated cricidyl ethers as shown in the following general formulas (III) and (IV) can be mentioned.

R-C-0-CH-CH-CH2 11\/'(III) OO (wherein, R has 2 to 2 carbon atoms and has an ethylenically unsaturated bond)
18 hydrocarbon groups. ) (wherein, R has 2 to 2 carbon atoms containing an ethylenically unsaturated bond)
18 hydrocarbon group, and X is ■-・' Specific examples of compounds represented by the above general formula include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl ether, Styrene-p
-glycidyl ether and the like.

On the other hand, examples of ethylenically unsaturated compounds include olefins, vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms,
Esters of saturated alcohol components having 1 to 8 carbon atoms and acrylic acid or methacrylic acid, maleic esters, methacrylic esters, and fumaric esters, vinyl halides, styrenes, nitriles,
Examples include vinyl ethers and acrylamides.

More specifically, ethylene, propylene, butene-1,
Examples include vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, dimethyl maleate, diethyl fumarate, vinyl chloride, vinylidene chloride, styrene, acrylonitrile, isobutyl vinyl ether, and acrylamide.

Among these, ethylene is particularly preferred.

Also, by polymerizing other components such as vinyl acetate and/or methyl acrylate along with ethylene,
The glass transition temperature of the epoxy group iq'h copolymer as a rubber-like substance is lowered, and the impact resistance of the resin composition of the present invention at low temperatures can be further improved.

These rubber-like substances can be produced by any manufacturing method (e.g. emulsion polymerization method, solution polymerization method, etc.) or by any catalyst (e.g. peroxide,
Trialkylaluminum, lithium halide, nickel-based catalysts, etc.) may be used.

Further, rubber particles having various degrees of crosslinking, microstructures in various proportions (for example, cis structure, trans structure, vinyl group, etc.), or rubber particles having various average rubber particle sizes are also used.

Furthermore, various types of copolymers such as random copolymers, block copolymers, and kraft copolymers can be used as the rubber-like material of the present invention. Furthermore, modified products of these copolymers other than component (c) of the present invention can also be used as the rubber-like material of the present invention.

Examples of such modified products include styrene, maleic anhydride, glycidyl methacrylate, and those modified with one or more of carboxylic acid-containing compounds.

These rubber-like substances (including modified substances) can be used alone or in combination of two or more.

When carrying out the present invention, reinforcing agents such as glass fibers and carbon fibers, carbon black, phosphoric acid, TiO
It is also possible to add and knead other inorganic and organic fillers, plasticizers, stabilizers, flame retardants, dyes and pigments.

To explain in more detail about reinforcing agents, reinforcing agents are:
By blending it, mechanical or thermal properties such as stiffness strength, bending elastic modulus, tensile strength, tensile elastic modulus, and heating deformation temperature are increased. For example, alumina fiber, carbon fiber, glass fiber , high modulus polyamide fibers, high modulus polyester fibers, silicon carbide fibers, titanate whiskers, and the like.

It is sufficient that the amount of these reinforcing agents is at least effective for reinforcing, but generally it is preferably in the range of about 5 to 100 parts by weight based on 100 parts by weight of the composition of the present invention.

A particularly preferred reinforcing agent is glass, with the use of glass fiber filaments of lime-aluminum borosilicate glass having a relatively low sodium content being preferred. This is known as "Σ" glass. but,
Other glasses are also useful when electrical properties are less important, such as glasses with low sodium contents known as "C" glasses. Filaments are made by common methods such as steam or air blowing, fire blowing and mechanical stretching. Preferred filaments for plastic reinforcement are created by mechanical tension. The filament diameter is in the range of about 2μ to 20μ, but this is not critical in the present invention. Lengths of glass filaments and collecting them into aggregate fibers, and further collecting these aggregate fibers into threads, ropes or rovings;
Also, in the present invention, there is no strict requirement that the fabric be woven into a mat or the like.

However, when preparing the composition in the present invention, about 0
, 3 cm to about 3 cm in length, preferably about 0.5 cm.
It is convenient to use glass filaments in the form of short cut strands with a length of 6 cm or less.

To further discuss flame retardants, flame retardants useful in the present invention include a group of compounds that are well known to those skilled in the art.

Generally, the more important compounds among these are used, such as bromine, chlorine, antimony, phosphorus and nitrogen, which contain these elements which can impart flame retardancy.

For example, halogenated organic compounds, antimony oxide, antimony oxide and halogenated organic compounds, antimony oxide and phosphorus compounds, phosphorus alone or phosphorus compounds, phosphorus compounds or compounds with phosphorus-nitrogen bonds and halogen-containing compounds, or two of these. A mixture of the above is used.

The amount of flame retardant additive is not critical, as long as it is sufficient to impart flame retardancy. It is not a good idea to add too much because it will impair physical properties such as lowering the softening point. The appropriate amount of the flame retardant is 0.5 to 50 parts by weight, preferably 1 to 25 parts by weight, and more preferably 3 parts by weight per 100 parts by weight of the polyphenylene ether or polyphenylene ether-containing resin composition of component (a). ~1
5 parts by weight is blended.

Halogen-containing compounds useful as flame retardants include those represented by the following formula.

In the above formula, n is 1 to 10, R1° is alkylene,
Alkylidene or alicyclic bonds (such as methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, etc.), ether, carbonyl, amine, sulfur-containing bonds (for example, sulfide , sulfoxide, sulfone), carbonate, phosphorous-containing bonds, etc.

Moreover, R12 is aromatic, amino, ether, ester,
It may also consist of two or more alkylene or alkylidene linkages linked by groups such as carbonyl, sulfide, sulfoxide, sulfone, phosphorus-containing linkages, and the like.

Ar and Ar 2 are monocyclic or polycyclic carbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like.

Ar and Ar 2 may be the same or different.

Y is a substituent selected from the group consisting of organic, inorganic, or organometallic groups. The substituent represented by Y is (1) a halogen such as chlorine, bromine, iodine or fluorine, (2) a general formula -OE (wherein E is a monovalent hydrocarbon group similar to XI below) ether group, (3)
-0H group, (4) monovalent hydrocarbon group, or (5) other substituents such as nitro group, cyano group, etc. d is 2
In the above cases, Y may be the same or different.

Xl is, for example, the following monovalent hydrocarbon group.

Alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, decyl; aryl groups such as phenyl, naphthyl, biphenyl, xylyl, tolyl, etc.; aralkyl groups such as benzyl, ethylphenyl, etc.; cyclopentyl, cyclohexyl, etc. cycloaliphatic groups such as; as well as monovalent hydrocarbon groups containing inert substituents therein.

When two or more Xl's are used, they may be the same or different.

d represents an integer from 1 to a maximum value equal to the maximum number of substitutable hydrogens on the aromatic ring consisting of Ar or Ar'.

e represents an integer from 0 to the maximum value determined by the number of substitutable hydrogens on R12.

a, b and C represent integers including 0. When b is not 0, neither a nor C is O. Otherwise a or C
Either one of them may be 0. When b is 0, the aromatic groups are bonded to each other through direct carbon-carbon bonds.

The hydroxyl group or substituent Y on the aromatic groups Ar and Ar' can take any of the ortho (0), meta (m) and para (p) positions of the aromatic ring.

” Specific examples of the two-legged type include the following.

2.2-bis-(3,5-dichlorophenyl)-propane, bis-(2-chlorophenyl)-methane, 1.2-bis-(2,6-dichlorophenyl)-ethane 1.1-bis-(4- iodophenyl)-ethane, 1.1-bis-(2-chloro-4-iodophenyl)-
Ethane, 1.1-bis-(2-chloro-4-methylphenyl)-
Ethane, 1.1-bis-(3,5-dichlorophenyl)ethane, 2.2-bis-(3-phenyl-4-bromophenyl)
-ethane, 2.3-bis-(4,6-dichloronaphthyl)-propane, 2.2-bis-(2,6-dichlorophenyl)-pentane, 2.2-bis-(3,5-dichlorophenyl) xane, bis-(4-chlorophenyl)-phenylmethane, bis-(3,5-dichlorophenyl)-cyclohexylmethane, bis-(3-nitro-4-bromophenylphenyl)-
Methane, bis-(4-oxy-2,,6-dichloro-3-methoxyphenyl)-methane, 2,2-bis-(3,5-dibromo-4-oxyphenyl)-propane, 2,2-bis -(3,5-dichloro-4-oxyphenyl)-propane, 2,2-bis-(3-bromo-4-oxyphenyl)-
Propane, as well as bisaromatic compounds using sulfide, sulfoxy, etc. in place of the two aliphatic groups in the above specific examples, such as tetrabromobenzene, hexabromobenzene, hexabromobenzene, 2,2'-dichlorobiphenyl , 2.4'-dibromobiphenyl, 2.4'-dichlorobiphenyl, hexabromobiphenyl, octabromobiphenyl, decabromobiphenyl, halogenated diphenyl ether containing 2 to 10 halogen atoms, 2.2-bis-(3 ,5-dibromo-4-oxyphenyl)-propane and phosgene with a polymerization degree of 1 to
20 oligomers and the like.

Preferred halogen compounds as flame retardants used in the present invention include chlorinated benzene, brominated benzene, chlorinated biphenyl, chlorinated terphenyl, brominated biphenyl,
Aromatic halogen compounds such as brominated terphenyl, or compounds containing two phenyl nuclei separated by a divalent alkylene group and having at least two chlorine or bromine atoms per phenyl nucleus, or at least two It is a mixture of the above. Particularly preferred are hexabromobenzene and chlorinated biphenyls or terphenyls or mixtures thereof with antimony oxide.

Typical phosphorus compounds preferred as flame retardants used in the present invention are compounds represented by the following general formula G and nitrogen analogous compounds.

1 Q-0-P-0-Q In the above formula, each Q is the same or different group, and is a hydrocarbon group such as alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-substituted alkyl; halogen: Including hydrogen as well as combinations thereof.

Representative examples of suitable phosphoric acid esters include:

Phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenylethylene hydrogen phosphate, phenylbis-(3,5,5'-trimethylhexyl) nonate, ethyldiphenyl phosphate, 2-ethylhexyl diphosphate (p-tolyl), diphenyl hydrogen phosphate, bis-(2-ethylhexyl)-p-tolyl phosphate, tritolyl phosphate, bis-(2-ethylhexyl)-phenyl phosphate, tri(nonylphenyl) phosphate, phosphorus phenylmethyl oxyhydrogen, di(dodecyl)-p-tolyl phosphate, triphenyl phosphate, halogenated triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p-tolylbis-(2) phosphate , 5,5' l-ly, methylhexyl), 2-ethylhexyldiphenyl phosphate, diphenyl hydrogen phosphate.

The most preferred phosphoric acid ester is triphenyl phosphate. It is also preferred to use triphenyl phosphate in combination with hexabromobenzene or l.liphenyl phosphate in combination with antimony oxide.

Other flame retardant additives include phosphorus nitride chloride, phosphorus ester amide, phosphoric acid amide, phosphine amide, l.
There are compounds containing a phosphorus-nitrogen bond, such as lis(aziridinyl)phosphine oxyto or tetrakis(oxymethyl)phosphonium chloride.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and any conventional known method can be used. If the materials are grown, it is effective to mix them in a solution state and evaporate the solvent or precipitate them in a non-solvent, but from an industrial standpoint, it is actually preferable to knead them in a molten state. Single-screw or twin-screw extruders commonly used for melt kneading,
A kneading device such as a platform scale kneader can be used. In particular, a twin-screw high kneader is preferred.

When kneading, it is preferable that each resin component be uniformly mixed in advance in the form of powder or pellets using a device such as a tumbler or Henschel mixer.
If necessary, a method may be used in which mixing is omitted and the components are individually supplied in fixed amounts to the kneading device.

The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but instead of going through the kneading process in advance, it is triblended during injection molding or extrusion molding, and then kneaded during the melt processing operation. The resin composition of the present invention can also be used to directly obtain molded products.

In the present invention, there is no particular restriction on the kneading order, and the components (
a), component (b) and component (c) may be kneaded together, or components (a) and component (b) may be kneaded in advance and then component (c) may be kneaded. Furthermore, other kneading orders are also possible.

[Applications] The thermoplastic resin composition of the present invention has excellent processability, iJ impactability,
It is a resin composition with excellent heat resistance, rigidity, dimensional stability, paintability, uniformity of appearance, and smoothness. Taking advantage of these properties, it can be made into molded products, sheets, laminates, etc. by injection molding and extrusion molding. It is the power that is used.

Especially automotive parts such as bumpers, glove boxes, console boxes, brake oil tanks, radiator grills, cooling fans, lamp housings, etc.
Air cleaner, instrument panel, fender
It is used in interior and exterior materials such as door trims, door panels, wheel covers, side protectors, air intakes, garnishes, trunk lids, bonnets, scirocco fans, and roofs, as well as mechanical parts that require heat resistance. It is also used as parts for motorcycles, such as covering shrines, muffler covers, leg shields, etc. Furthermore, it is used as electrical and electronic components such as housings, chassis, connectors, printed circuit boards, pulleys, and other parts that require strength and heat resistance.

[Example] The present invention will be described below with reference to examples, but these are merely illustrative and the present invention is not limited thereto.

In addition, the load deflection temperature test (H, D) in the examples.

T,) is JIS K7207, Izot impact strength (
Thickness 3.2mm) is A according to JIS K7110.
t determined.

Further, the reduced viscosity (ηSp/C) of the polyphenylene ether in the examples is a value measured at 25°C in 1/1 ml of chloroform solution of 0.5 g/di solution.

Also, the melt flow index (M
I) according to JIS K6758, temperature 23
Measurement was performed at 0° C. and a load of 2.18 kg.

Kneading is done using Japanese W4 made TEX44SS-30BW-2v
It was carried out using a twin-screw extruder at a temperature of 260 to 290°C and a screw rotation speed of 300 to 350 revolutions/min.

The physical properties were measured using an IS 150E-V injection molding machine manufactured by Toshiba Kijo Co., Ltd. at a molding temperature of 260°C to 280°C and a mold cooling temperature of 70°C.

Falling weight impact strength is determined by fixing a molded test piece of 120 x 90 x 3 mm on support table L and dropping a weight equipped with a stress detection device according to the usual method, and measuring the impact required for the test piece to break. The energy value was calculated.

Component (a): Polyphenylene ether The polyphenylene ethers used in the Examples and Comparative Examples of the present invention are as follows.

(1) η8 obtained by polymerization in the laboratory. /C=0.40
polyphenylene ether (hereinafter abbreviated as A-1).

) (11) In an autoclave, 1100 parts by weight of polyphenylene ether A-1 was mixed with 21 parts by weight of hestylene monomer and a dispersant (Metrose 90SH-100).

(Product name) 3 parts by weight, and Perbutyl PV (Product name) 1
105 parts by weight and while blowing in nitrogen.
After reacting for about 1 hour at °C, the mixture was cooled to obtain modified polyphenylene ether. Hereinafter, this polymer will be abbreviated as A-2.

(Iiii) η /C=0.6 obtained by polymerization in the laboratory
6 p polyphenylene ether. (Hereinafter, it will be abbreviated as A-3.

) (Iv) The polyphenylene ether A-1100
Sumira Nisbrite 500H as polystyrene by weight
13 parts by weight of G (trade name, manufactured by Sumira Chemical Co., Ltd.), 2.8 parts by weight of glutaric acid, 3 parts by weight of maleic anhydride, and 0.2 parts by weight of Perbutyl PV were mixed in a Henschel mixer, and then mixed in a twin screw mixer. The mixture was melted in an extruder at a temperature of 290°C to obtain a modified polyphenylene ether. Hereinafter, this modified polyphenylene ether will be abbreviated as A-4.

Component (b) modified propylene polymer (i) propylene polymer Sumira Noblen AV66
4B (Product name, Sumira Chemical Co., Ltd., MI-5,0) 1
00 parts by weight of pure water, 350 parts by weight of pure water, 1.3 parts by weight of tertiary calcium phosphate, and 5.3 parts by weight of Pluronic F68 (trade name, manufactured by Asahi Denka Kogyo ■) were added, and the mixture was sufficiently replaced with nitrogen while stirring.

Thereafter, 42 parts by weight of styrene, 6 parts by weight of glycidyl methacrylate, and Zamperox T as a radical initiator were added.
1.2 parts by weight of O (trade name, manufactured by Sansei Kako ■) were added.

After raising the temperature to 110°C over 90 minutes, the reaction was continued for 1 hour. After cooling, the modified propylene polymer was taken out by filtration, thoroughly washed with pure water, and then vacuum dried.

Hereinafter, this polymer will be abbreviated as B-1.

(11) A modified propylene polymer was obtained in exactly the same manner as above except that 1.6 parts by weight of 2-aminoethyl methacrylate, 18 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used instead of 42 parts by weight of styrene. .

Hereinafter, this modified polymer will be abbreviated as B-2.

(Iff) Sumira Noblen AX as a propylene polymer
574 (trade name, manufactured by Sumira Chemical Industries, Ltd., MI=45) was used.

For 100 parts by weight of raw material propylene polymer, 2.0 parts by weight of maleic anhydride, 9.6 parts by weight of styrene, and 3.0 parts by weight of glycidyl acrylate. i parts by weight as a radical initiator,
1.3-bis(t-butylperoxyisopropyl)benzene (manufactured by Sansoku Kako ■, Sanberotux-TYI・3;
1.2 parts by weight of 6% by weight of propylene homopolymer (trade name) supported by propylene homopolymer and 0.3 parts by weight of Irganox 101.0 (trade name, manufactured by Ciba Geigy) as a stabilizer were uniformly mixed in a Henschel mixer. After that, the mixture was melt-kneaded in a twin-screw extruder at a temperature of 245° C. and a rotation speed of 400 rpm to obtain a modified propylene polymer. Hereinafter, this modified polymer will be abbreviated as B-3.

<1v) A modified propylene polymer was obtained in exactly the same manner as above except that 7.3 parts by weight of 2-hydroxyethyl methacrylate was used instead of 2 parts by weight of maleic anhydride.

Hereinafter, this modified polymer will be abbreviated as B-4.

Other propylene polymers used in Examples and Comparative Examples and their abbreviations are as follows.

B-5: Sumira Noblen, AV664B [Product name, manufactured by Sumira Chemical Industry ■, MI = 5.0] B-6: Sumira Noblen, AX574 [Product name, manufactured by Sumira Chemical Industry ■, MI = 45 ] B-7: Sumira Noblen, FL8111C [Product name, manufactured by Sumira Chemical Industries ■, MI = 1.0] B-8 = Sumitomo Noblen, GHH4B [Product name, manufactured by Sumira Chemical Industries ■, MI =
4.5] (1) Nisprene E201 as ethylene-α-olefin copolymer rubber (trade name, manufactured by Sumira Chemical Co., Ltd.,
EPM, ethylene content 47% by weight, number average molecular weight 55,
000, ML 121°C=32) 100 (+4 parts by weight of 1,1-bis(t-butylperoxy)3
, 3.5-4 A sample prepared by mixing 0.08 parts by weight of 4-limethylcyclohexane and 5 parts by weight of styrene using a mixing roll was mixed with 6 parts by weight of maleic anhydride.
mmφ twin screw extruder (screw rotation speed 450 rp
m) under a nitrogen atmosphere, at a kneading temperature of about 250°C,
A modified copolymer rubber was obtained by extruding at an extrusion rate of 18 kg/hour.

The amount of maleic anhydride added to the obtained modified copolymer rubber was 2
．． 8% by weight, the amount of styrene added is 1.3% by weight,
ML 121°C was 50, and no gel formation was observed. Roll processability was also good. Hereinafter, this modified rubber will be abbreviated as C-1.

(Ii) A modified copolymer rubber was obtained in exactly the same manner as in (1) above, except that the amount of styrene was 1 part by weight and the amount of maleic anhydride was 2 parts by weight.

The amount of maleic anhydride added to this modified copolymer rubber is 0.3
The amount of styrene added was 0.4% by weight. Hereinafter, this modified rubber will be abbreviated as C-2.

(III) Ethylene-α in an autoclave with a stirrer
- As an olefin-nonconjugated diene copolymer rubber, Nisprene E502 (trade name, manufactured by Sumira Chemical Co., Ltd., EPD
M, number average molecular weight 60.000) 100 parts by weight (shredded material), 350 parts by weight of pure water, tertiary calcium phosphate 4.0
4.0 parts by weight of Pluronic F-68 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.) were added, and the mixture was sufficiently replaced with nitrogen while stirring.

Thereafter, 20 parts by weight of styrene monomer was added as a radical initiator to Sanperox To (trade name, manufactured by Sanken Kako ■).
1,0 parts by weight were added. After raising the temperature to 110°C over 80 minutes, the reaction was continued for 1 hour. After cooling, the styrene graft copolymer rubber was taken out by filtration, thoroughly washed with pure water, and then vacuum dried. Hereinafter, this copolymer rubber will be abbreviated as C-3.

100 parts by weight of this styrene graft copolymer rubber C-3 and 3.3.5 parts of 1.1-bis(t-butylperoxy)
After mixing with 0.08 parts by weight of dimethylcyclohexane using a mixing roll, the mixture was kneaded and reacted with 5 parts by weight of maleic anhydride in a twin-screw extruder to obtain a modified copolymer rubber. Hereinafter, this modified rubber will be abbreviated as C-4.

(1v> Ethylene-propylene-nonconjugated diene copolymer rubber Sumira Nisprene E532 (trade name, manufactured by Sumira Chemical Co., Ltd., number average molecular weight 63.000) 100 parts by weight, 21 parts by weight of styrene, glycidyl acrylate 1.8
Parts by weight, 5 parts by weight of methyl methacrylate, 4.0 parts by weight of tertiary calcium phosphate, and 3.1 parts by weight of Pluronic F68 (trade name, manufactured by Asahi Denka Kogyo ■) were added, and while stirring under a nitrogen atmosphere, a radical initiator was added. As Samberox To
(trade name, manufactured by Sansoku Kako W) was added, and the temperature was raised to 110° C. over 80 minutes, and then the reaction was continued for 1 hour. After cooling, the copolymer was collected by filtration.

Next, to 100 parts by weight of this modified rubber, 3.2 parts by weight of maleic anhydride, 8.2 parts by weight of styrene, 5.1 parts by weight of glycidyl acrylate, and 1 part by weight as a radical initiator were added.
, 3-bis(t-butylperoxyisopropyl)benzene (manufactured by Sanken Kako Co., Ltd.; Sanpex-TY1B, trade name) (, 4 parts by weight and Irganox 10 as a stabilizer)
After uniformly mixing 0.3 parts by weight of 10 (trade name, manufactured by Ciba Geigy) in a Henschel mixer, the mixture was melt-kneaded in a 44 mmφ twin screw extruder (screw rotation speed 450 rpm) at a temperature of 240°C under a nitrogen atmosphere. , a modified rubber was obtained.

Hereinafter, this modified rubber will be abbreviated as C-5.

The above components were blended in the proportions shown in Tables 1 to 3, and the respective blends were mixed and injection molded to measure their physical properties.

The results are shown in Tables 1-3.

As is clear from Tables 1 to 3, (a) polyphenylene ether or a composition containing polyphenylene ether, (b) styrene and/or a styrenic monomer and a monomer copolymerizable with the styrenic monomer. A propylene polymer and/or a propylene polymer obtained by graft copolymerizing the mixture, and (c) a styrenic monomer and/or a monomer copolymerizable with the styrenic monomer, and an unsaturated dicarboxylic acid anhydride. Graft copolymerized modified ethylene-α-olefin copolymer rubber and/or
Alternatively, a composition made from a modified ethylene-α-olefin copolymer-nonconjugated diene copolymer rubber has excellent heat resistance, impact resistance, and drop weight strength, and is good without peeling of injection molded products. I understand that.

Claims (1)

[Claims] 1) (a) polyphenylene ether or a composition containing polyphenylene ether, (b) a mixture of styrene and/or a styrenic monomer and a monomer copolymerizable with the styrenic monomer A propylene polymer and/or a propylene polymer graft-copolymerized with (c) a styrenic monomer and/or
Or a modified ethylene-α-olefin copolymer rubber and/or a modified ethylene-α-olefin copolymer rubber made by graft copolymerizing a monomer copolymerizable with a styrene monomer and an unsaturated dicarboxylic acid anhydride. Made of conjugated diene copolymer rubber, the ratio of component (a) and component (b) is
Component (a) is 99 to 1% by weight, component (b) is 1 to 99% by weight, and component (c) is 1 to 60% by weight per 100 parts by weight of the total weight of component (a) and component (b). Parts by weight of thermoplastic resin composition.