JPH03181555A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition composed of a polyphenylene ether, a modified propylene polymer having a specific grafting efficiency and grafted with chains having a specific molecular weight and a rubbery substance at specific ratios, having excellent heat-resistance, impact resistance and chemical resistance and moldable by injection molding, etc. CONSTITUTION:The objective composition is composed of (A) 1-99wt.% of a polyphenylene ether or a composition containing the same, (B) 1-99wt.% of a modified propylene polymer and/or a mixture of the modified propylene polymer and a propylene polymer and (C) 0-60wt.% (based on the sum of the components A and B) of a rubbery substance. The modified propylene polymer is produced by the graft copolymerization of a styrene monomer and/or a mixture of styrene monomer and a monomer copolymerizable with styrene monomer to a propylene polymer. The grafting efficiency of the modified propylene polymer defined by [(weight of grafting chain part)/(weight of homopolymer of said monomer + weight of grafting chain part)] X 100 is >=30% and the grafting chain of the modified propylene polymer has a molecular weight of 1,000-200,000.

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 HoIJ styrene resin is known as a method of lowering the melt viscosity and improving molding processability while maintaining the excellent properties of polyphenylene ether, but chemical resistance is still not improved. .

On the other hand 1. 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 has traditionally been used as a material for various molded products, films, and sheets. Widely used.

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 and impact resistance are strongly desired.

[Problems to be Solved by the Invention] From this point of view, if polyphenylene ether and propylene polymer are blended to obtain a resin composition that has the features of both and has improved moldability and impact resistance. The possibility of a wide range of new applications is expected.

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 propylene polymer, resulting in extremely poor appearance. It has poor mechanical properties and is not suitable 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.

As a method for improving the compatibility between polyphenylene ether and propylene polymer, as described in JP-A-1-207349, there is a method of blending polyphenylene ether with a propylene polymer obtained by graft copolymerizing a styrene monomer. There is.

A composition with excellent heat resistance and mechanical properties can be obtained by blending polyphenylene ether with a propylene polymer, rubber, etc. obtained by graft copolymerizing styrene and/or a mixture of styrene and a monomer copolymerizable with styrene. JP-A-1-207349 and JP-A-1-2344
It is disclosed in No. 82, etc.

However, in some cases, molded products using this composition may not always have sufficient impact resistance, heat resistance, or moldability, or may have insufficient chemical resistance. In some cases, it is difficult to use these materials, and there has been a strong demand from the market for improvements in these physical properties.

[Means for Solving the Problems] The present inventors have conducted extensive research with the aim of obtaining a composition that has excellent heat resistance and mechanical strength, as well as excellent moldability and chemical resistance. , arrived at the present invention.

That is, the present invention provides: 1) (a) a polyphenylene ether or a composition containing polyphenylene ether; (b) a propylene polymer copolymerized with a styrene monomer and/or a styrene monomer and a styrene monomer; It is a modified propylene polymer obtained by graft copolymerizing a mixture with a monomer that can weight quantum graft chain partial weight)}×100 (%)] is 33% or more, and the graft chain of the modified propylene polymer has a molecular weight of LOOO to 2.
00000 and/or a mixture of the modified propylene polymer and a propylene polymer,
and (c) a rubber-like substance, in which the ratio of component (a) to component (b) is 99 to 1% by weight, and 1 to 1% by weight of component (b).
99% by weight, and the sum of the weights of component (a) and component (b) is 1
The present invention relates to a thermoplastic resin composition in which component (c) is contained in an amount of 0 to 60 parts by weight based on 00 parts by weight.

In the modified propylene polymer obtained by graft copolymerizing a styrenic monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrenic monomer in the present invention, the graft copolymer The grafting efficiency in the copolymerization reaction to obtain the modified propylene polymer is 30% or more, and the molecular weight of the graft chain of the modified propylene polymer is L.
000 to 200000.

If the obtained modified propylene polymer does not satisfy these conditions, the heat resistance, mechanical properties, chemical resistance, etc. of the composition will deteriorate, which is undesirable.

The polyphelene ether of component (a) used in the present invention has the general formula
They may be different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group or substituted hydrocarbon group, a hydrocarbon oxy group or a substituted hydrocarbon oxy group. However, R-R5
One of them is always hydrogen. ) It can be obtained by oxidative polymerization using oxygen or an oxygen-containing gas using one or more of the phenolic compounds represented by the following and an oxidative coupling catalyst.

R1, R2, R3, R4 and R5 in the above general formula
Specific examples include hydrogen atom, chlorine atom, bromine atom, fluorine atom, iodine atom, methyl, ethyl, n- or 1
so-propyl, prl-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, 2,6-12.5-2,4- or 3,5-dimethylphenol, 2-methyl -6-phenylphenol,
2.6-diphenylphenol, 2,6-ethylphenol, 2-methyl-6-ethylphenol, 2.3°5-12,3.6- or 2,4.6-drimethylphenol, 3-methyl -6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like.

Furthermore, phenol compounds other than the above general formula, such as bisphenol-A1 tetrabromobisphenol-A,
Copolymerization of a polyhydric hydroxy aromatic compound such as resorcinol, hydroquinone, or novolac resin and a phenol compound of the above general formula may also be used.

Among these compounds, 2.6-dimethylphenol (2,6-xylenol) or 2.6-dimethylphenol (2.6-xylenol) or 2.6-dimethylphenol (2.6-xylenol) is preferred among these compounds.
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 2.3.6-1 trimethylphenol 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 such as cuprous chloride-triethylamine and cuprous chloride-pyridine and tertiary amines; cupric chloride-pyridine-
Catalyst consisting of cupric salt such as potassium hydroxide-amine-alkali metal hydroxide; Catalyst consisting of manganese salt such as manganese chloride-ethanolamine, manganese acetate-ethylenediamine and primary amines; Manganese chloride-sodium methane Catalysts consisting of manganese salts such as manganese salts, manganese chloride-sodium phenolates, and alcoholades or phenolates; catalysts consisting of a combination of cobalt salts and tertiary amines; and the like.

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 in the present invention also includes modified products obtained by grafting other polymers onto the above polymers or copolymers.

For example, poly3 (each symbol in the formula has the same meaning as above) is 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. Symbols have the same meanings as above.) Polyphenylene ether polymers or copolymers containing styrene and/or
or organic peroxide graft copolymerized with other polymerizable monomers (Japanese Patent Publication No. 47-47862, Japanese Patent Publication No. 12197-1988, Japanese Patent Publication No. 5628-1976, Japanese Patent Publication No. 38596-1972, Japanese Patent Publication No. 1987-1982) -30991 etc.)
, the above-mentioned polyphenylene ether electropolymer or copolymer and polystyrene polymer are kneaded and reacted together with a radical generator (peroxide, etc.) in an extruder (Japanese Unexamined Patent Application Publication No. 1989-1999)
2 (No. 42799), etc.

In the present invention, the preferred intrinsic viscosity of the polyphenylene ether (measured at 30°C in chloroform) is from 0.2 to
The intrinsic viscosity is 0.5 dl/g, and 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 carboxylic 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 (1> carbon-carbon double bond or carbon-carbon triple bond and (1, j,) carboxylic acid group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group, epoxy Compounds (F) having one or more types of groups, amino groups, or hydroxyl groups are mentioned.

Specific examples of compound (F) include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, for example (where R13 represents an aliphatic or aromatic group). ), methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, linseed oil, hempseed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil , natural oils and fats such as olive oil, coconut oil, and sardine oil, epoxidized natural oils and fats such as epoxidized soybean oil, 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, 10-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, te)-lacosenoic acid, mycolipenic acid, 2,4-pentadienoic acid, 2,4-hexadiene 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, linuric acid, Octadecatrienoic acid, icosadienoic acid, icosatrienoic acid, icosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, icosapentaenoic acid, erucic acid,
Unsaturated carboxylic acids such as docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapene citric acid, tetraenoic acid, hexacosenoic acid, hexacosenoic acid, oftacosenoic acid, traacontenoic acid, or esters, acid amides, and anhydrides of these unsaturated carboxylic acids or allyl alcohol, crotyl alcohol, methylvinylcarbinol, allylcarbinol, methylpropenylcarbinol, 4-penten-1-ol, 10-undecen-1-ol, propagyl alcohol, 1,4-pentadiene- 3=ol, 1,4-hexadien-3-ol, 3,5-hexadien-2-ol, 2,4-hexadien-1-ol, general formula CnH2n-50H1
CoH2n, OH, C6H5, -90H (where n is a positive integer) alcohol, 3-butene-1゜2-
Diol, 2,5-dimethyl-3-hexene-2,5-
Diol, 1,5-hexadiene-3゜4-diol,
Unsaturated alcohols such as 2,6-octanonine-4,5-diol, or -
Unsaturated amines in which the OH group is replaced with N H2 groups, or low polymers such as butadiene and isoprene (for example, those with an average molecular weight of about 500 to 10,000) or high molecular weight polymers (for example, those with an average molecular weight of 1. 0000
Examples include those in which maleic anhydride or phenols are added to the above-mentioned substances, or those in which an amine group, a carboxylic acid group, a hydroxyl group, an epoxy group, etc. are introduced.

Other preferred polyfunctional compounds (E) have the general formula [
■Co (R, 50), R14 (c00R18). (cONR
1□R18) Aliphatic carboxylic acids, acid esters and acid amides represented by 5[V] (wherein R14 is a linear or branched aliphatic saturated hydrocarbon having 2 to 20 carbon atoms) 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 carbon atom. A group independently selected from the group consisting of 1 to 20 alkyl groups and aryl groups, each of R and R18 being a hydrogen atom and 7 carbon atoms, independently selected from the group consisting of 1 to 10 alkyl groups and aryl groups m, n and S are integers greater than or equal to 0, and 1, 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-dimethylpencunic acid,
3-oxypropionic acid, β-oxybutyric acid, β-oxyisoacetic acid, β-oxy-n-valeric acid, β-oxyisovaleric acid, 2-oxymethylbutanoic acid, oxybivalic acid, 3
-oxy-2-methylpentanoic acid, 1,1-oxytetradecanoic acid, yarapinoleic 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, malic 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-dioxyglutaric acid, α,γ-dioxy-β-methylglutaric acid, α,γ-
Dioxy-β-methyl-β-ethylglutaric acid, α, γ
-Dioxy-alpha.

γ-dimethylglutaric acid, α, δ-dioxyadipic acid, β, γ-dioxyadipic acid, 6,7 dioxydodecanoic acid, 7,8-dioxyoctadecanoic acid, furionic acid, trioxybutyric acid, trioxyisobutyric acid , trioxyglutaric acid, succinic acid, glutaric acid, adipic acid, α-
Examples include methylglutaric acid and dobucanic acid.

Further, the above-mentioned derivatives of general formula [V] include lactones, acid anhydrides, alkali metal salts, alkaline earth metal salts, salts with amines, etc., and specific examples include β-propiolactone. , glycolide, lactide, β-methylpropiolactone, β, β-dimethylpropiolactone, β-
n-propylpropiolactone, β-isopropylpropiolactone, β-methyl-β-ethylpropiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε~caprolactone, 1,5 -oxypentadecanoic acid, γ-butyrolactone-α-carboxylic acid, paraconic acid, α-methylparaconic acid, β-methylparaconic acid, α-ethylparaconic acid, α-isopropylparaconic acid, γ-methylvalaconic acid, γ-Ethylvalaconic acid, α,γ-dimethylvalaconic acid, β,γ-dimethylparaconic acid, α,α,β-trimethylparaconic acid, γ,γ-dimethylparaconic acid, nephrosteranic 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-
Methyladipic acid-γ-lactone, α-(δ′-carboxy n-butyl)-γ-butyrolactone, α-methylisocitric acid lactone, cinchonic acid, α-oxy-γ-
Butyrolactone, β-oxy-γ-butyrolactone, δ
-oxy-γ-valerolactone, pantolactone, 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 types 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
-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 (1) 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 (J) 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. say.

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 Sumitomo Chemical Co., Ltd.], and Union Carbide's phenoxy resin, etc.), condensates of resorcinol and shrimp chlorohydrin, condensates of hydroquinone and shrimp chlorohydrin, tetrabromobisphenol A and Condensates with shrimp chlorohydrin, glycidyl etherified phenol novolacs or cresol novolacs (e.g. Sumiepoxy ESCN-220
[Product name, manufactured by Sumitomo Chemical Co., Ltd., j 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, trinotyrolethane, 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 Sumitomo 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 includes (1) at least one silicon atom bonded to a carbon atom via an oxygen atom in the molecule, (Ii) carbon- carbon double bond or carbon-carbon triple bond, and ([1) amino group, mercapto group, carboxylic acid group, acid anhydride group, acid amide group,
It is an organosilane compound having at least one functional group selected from a carboxylic acid ester group, an imide group, and a hydroxyl group.

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- Examples include mercaptopropyltrimethoxysilane.

In the present invention, compounds (E), (F) (G), (H)
, (J) and (K) are selected depending on the purpose, but in general, they are 200 parts by weight or less, preferably 80 parts by weight or less, and more preferably 20 parts by weight, based on 100 parts by weight of polyphenylene ether. The most preferred amount is 0.01 to 10 parts by weight.

The various compounds (E), (F), (G), (
When modifying polyphenylene ether with H), 0), and (K), a radical generator may be used depending on the case. Examples of the radical generator used include known organic peroxides and diazo compounds.

If kept, azo compounds such as 2,2'-azobisisobutyronitrile, 2.2'-azobis(2,4,4)-trimethylvaleronitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3.3. 5-trimethylcyclohexanone peroxide, 2.2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2.5-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-)limethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl Peroxyisobutyrate, t-butyloxybivalate, t-butyl-oxy-2-ethylhexanoate, t-butylperoxy-3,5,5-)limethylhexanoate, 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 penzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, azobisisobutyronitrile, and the like. can be mentioned.

The amount of radical generator used is polyphenylene ether 1
The amount is in the range of 0.0t to 10 parts by weight, preferably 0.1 to 5 parts by weight.

In the polyphenylene ether modified product in the present invention, the above various compounds and polyphenylene ether may be chemically reacted, or physical interaction (for example, physical adsorption to polyphenylene ether) may occur. .

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.

Namely, aromatic vinyl or vinylidene compounds such as α-methylstyrene, oSm and p-methylstyrene, chlorostyrene, bromostyrene, divinylbenzene, hydroxystyrene, aminostyrene; olefins such as ethylene; (meth)acrylics; Examples include methyl acid, 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.
One species or two or more 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.The temperature varies slightly depending on the type and amount of the compound, but is generally in the range of (=150 to 350°C).

The melt-kneading device may be any method as long as it handles (obtains) 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, and a kneader.

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 ester ( For example, Unitika's U
polymers), polyphenylene sulfide; polyamides such as 6-nylon, 6,6-nylon, and 12-nylon; and condensation polymer compounds such as polyacetal. Furthermore, various thermosetting resins such as silicone resin, fluororesin, polyimide, polyamideimide, phenol resin, alkyd resin, unsaturated polyester resin, epoxy resin, and davon resin are also included.

In the thermoplastic resin composition used in the present invention, it is possible to copolymerize with a styrene monomer and/or a styrene monomer and a styrene monomer as a component (b) in addition to the component (a) as described above. It is a modified propylene polymer obtained by graft copolymerizing a mixture with a monomer, and the graft efficiency in the copolymerization reaction to obtain the graft copolymer is
(graft chain partial weight/(homopolymer weight + graft chain partial weight))X100I is 30% or more, and the graft chain of the modified propylene polymer has an average molecular weight of 1000.
200,000 and/or a mixture of the modified propylene polymer and a propylene polymer.

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-■-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene- 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.
．． Those having a weight of 82 to 0.92 g/cm3 are 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 0.970 or more, or the isotactic pentad fraction of the boiling hebutane insoluble part of the homopolymer part of the propylene polymer is 0.970 or more, and the content of the boiling hebutane soluble part is 5.0% by weight or less, and the content of the xylene soluble portion at 20°C is 2.0%.
% by weight or less.

Such highly crystalline propylene polymers are disclosed in, for example, JP-A-60-28405, GO-228504, and JP-A-61.
．． -218606 and 81-287917.

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. 1738/1983).

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 contains 0.00% vinylcycloalkane unit.
Propylene polymer compositions containing 05 wtppm - 10000 wtppm exhibit 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 polymerization (*(propylene homopolymer and propylene copolymer)) can be used alone or in combination of two or more types.

In the component (b) of the present invention, the styrenic monomer used to modify the propylene polymer by graft copolymerization with the propylene polymer has the general formula [II] (wherein R6, R7, R8 , R9 and Rlo are the same or different, and each represents a hydrogen atom, a halogen atom,
It represents a hydrocarbon or a substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group, and R1 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. ).

Specific examples of R6, R7, R8, R9 and Rlo in the above general formula [II] include hydrogen atoms; halogen atoms such as chlorine, bromine, and iodine; methyl, ethyl, propyl,
Included are hydrocarbon groups such as vinyl, allyl, benzyl, and methylbenzyl; substituted hydrocarbon groups such as chloromethyl and bromomethyl; 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 the graft copolymer component for preparing the modified propylene polymer as component (b) of the thermoplastic resin composition used in the present invention, in addition to the above-mentioned styrenic monomer, the above-mentioned styrenic monomer and Mixtures with monomers copolymerizable therewith can be used.

A monomer that can be copolymerized with a styrene monomer can be appropriately selected, graft copolymerized with a propylene polymer, and blended into polyphenylene ether or a composition containing polyphenylene ether.

Here, specific examples of monomers that can be copolymerized with the styrene monomer include acrylonitrile, methacrylate trile,
Fumaric and maleic acids, vinyl ketones, maleic anhydride, acrylic acid, methacrylic acid, vinylidene chloride, maleic esters, methyl methacrylate, ethyl methacrylate, propyl methacrylate, glycidyl acrylate, glycidyl methacrylate, butyl methacrylate,
Methyl acrylate, 2-aminoethyl methacrylate,
2-hydroxyethyl methacrylate, 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, 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, allyltrimethylsilane, 3-butenyltrimethylsilane, vinylcarbazole, N,N-diphenylacrylamide, fumaronitrile, and the like. Further, derivatives of these monomers can also be used.

These can be used alone or in combination of two or more.

Preferred among these monomers are maleic anhydride,
These include methyl methacrylate, 2-aminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and acrylonitrile.

The grafting efficiency of the modified propylene polymer as component (b) in the present invention refers to the grafting efficiency of the polymer of a styrenic monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrenic monomer. Of these, it refers to the efficiency with which a propylene polymer becomes a graft chain, and the graft efficiency can be determined from the following formula.

[Graft chain partial weight/(homopolymer weight of the monomer +
Graft chain partial weight)] Of these, it means a free polymer that is not grafted.

The grafting efficiency of component (b) of the present invention can be determined by a well-known method. For example, when styrene is used as a monomer, polystyrene is extracted and removed from the modified propylene polymer using methyl ethyl ketone. However, the grafting efficiency can be determined by weighing the weight of the polystyrene portion and the graft chain portion, respectively.

The solvent for extracting and removing the homopolymer of the monomer used from the modified propylene polymer can be appropriately selected depending on the monomer used in the graft copolymerization.

In the modified propylene polymer obtained by graft copolymerizing a styrenic monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrenic monomer as component (b) of the present invention, It is necessary that the grafting efficiency in the copolymerization reaction for obtaining the modified propylene polymer is 30% or more, and that the graft chain of the modified propylene polymer has a molecular weight of 1,000 to 200,000.

Even if the grafting efficiency in the copolymerization reaction to obtain the modified propylene polymer is 30% or more, if the molecular weight of the graft chain portion of the modified propylene polymer is less than 1000, the compatibility between the polyphenylene ether and the propylene polymer will be poor. In order to be insufficient, the heat resistance, impact resistance,
Falling weight strength, mechanical strength, etc. decrease, which is undesirable. Moreover, if the molecular weight of the graft chain portion exceeds 200,000, the molding processability of the composition will deteriorate, which is not preferable.

If the grafting efficiency is less than 30%, the composition will not exhibit sufficient physical properties, and the presence of a large amount of the homopolymer in the composition will deteriorate the chemical resistance and impact resistance of the composition. This is not preferable because it significantly reduces the temperature.

Although it is possible to extract the ungrafted free homopolymer from a modified propylene polymer with a grafting efficiency of less than 30% using a solvent, this method results in the -6 homopolymer being extracted with a solvent. Even if it were possible to remove it from the modified propylene polymer, the process would be complicated and it would require a large amount of cost, which is not practical.

In order to obtain the modified propylene polymer of component (b) of the present invention, it is preferable to select conditions for the graft copolymerization reaction such that the grafting efficiency is 30% or more.

In the present invention, the grafting efficiency of component (b) is 30% or more, and the molecular weight of the graft chain portion is 1000 to 200%.
The method for producing a modified propylene polymer having a molecular weight of 0.000 is not particularly limited, and examples include suspension polymerization, emulsion polymerization,
Any well-known method such as a solution polymerization method or a bulk polymerization method (including a method using an extruder in addition to a method using a polymerization tank) can be employed.

Specifically, for example, a copolymer of styrene and acrylonitrile is first produced by anionic polymerization, and then this copolymer and a propylene polymer are melt-kneaded together with a peroxide as shown below to obtain a modified propylene copolymer. Examples include a method of obtaining a polymer, or a method of copolymerizing a propylene polymer with a styrene monomer, glycidyl methacrylate, etc. by radical polymerization.

Specifically, as described in the example of JP-A-1-207349, a propylene polymer, styrene, a dispersant, an organic peroxide, etc. are added to an aqueous phase, and the temperature is raised to convert styrene into a propylene polymer. Examples include a suspension polymerization method of graft copolymerizing.

Another method is to first produce a copolymer of styrene and acrylonitrile by anionic polymerization, and then melt-knead this copolymer and propylene polymer with a peroxide as shown below to obtain a modified propylene copolymer. Examples include a method of copolymerizing a styrene monomer, glycidyl methacrylate, etc. to a propylene polymer by copolymerization, or by radical polymerization. is not particularly limited, and a desired one can be appropriately selected and used.

Examples of such organic peroxides include the various organic peroxides exemplified as those applicable to the preparation of the polyphenylene ether modified product described above.

This component (b) may include antioxidants, heat stabilizers, light stabilizers, nucleating agents, antistatic agents, inorganic or organic colorants, rust preventives, crosslinking agents, foaming agents, lubricants, Various additives such as plasticizers, fluorescent agents, surface smoothing agents, and surface gloss improvers can be blended.

In the resin composition of the present invention, a rubber-like substance may be used as component (c) if desired, especially for the purpose of improving impact resistance.

As used herein, rubber-like materials refer to natural and platform polymeric materials that are elastic at room temperature.

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 -α-olefin copolymer, styrene-isoprene copolymer or its hydrogenated product, styrene-ethylene-butylene copolymer, styrene-butylene copolymer, styrene-ethylene-propylene copolymer, perfluororubber, Fluororubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-α
-Olefin-nonconjugated diene copolymer, thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (
Examples include propylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and epoxy group-containing copolymer.

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,
Unsaturated epoxy compound is 0. It is preferable that the copolymerization amount is 1 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 glycidyl ethers as shown by the following general formulas (III) and (IV) can be mentioned.

OO (wherein, R has 2 to 2 carbon atoms and has an ethylenically unsaturated bond)
18 hydrocarbon groups. (In the formula, R is carbon having an ethylenically unsaturated bond. 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.

In addition, by copolymerizing other components such as vinyl acetate and/or methyl acrylate with ethylene, the glass transition temperature of the epoxy group-containing copolymer as a rubber-like substance is lowered, and the resin composition of the present invention can be used at low temperatures. Impact resistance 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.

Furthermore, rubber particles having various degrees of crosslinking, microstructures of various proportions (for example, cis structure, trans structure, vinyl groups, etc.), or rubber particles having various average particle diameters are also used.

Moreover, various polymers such as random copolymers, block copolymers, and graft copolymers can all be used as the rubber-like substance of the present invention. Furthermore, modified products of these copolymers can also be used as the rubber-like material of the present invention. Examples of such modified products include those modified singly or with two or more of styrene, maleic anhydride, glycidyl methacrylate, glycidyl acrylate, or carboxylic acid-containing compounds.

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

To further explain the rubber-like material, an ethylene-α-olefin copolymer such as an ethylene-propylene copolymer or a modified product thereof can be used in the present invention.

Ethylene-α-olefin copolymers include copolymers of ethylene and other α-olefins, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. Coalescence or ethylene-
Examples include terpolymer rubbers such as propylene-1-butene copolymers.

The ethylene content in these ethylene-α-olefin copolymers is 15 to 85% by weight, preferably 40 to 80% by weight.
It is. 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 an elevated glass transition point (Tg) and are difficult to process under normal rubber molding conditions. This is undesirable because the physical properties deteriorate.

Further, in the ethylene-α-olefin-nonconjugated diene copolymer, it is desirable for the nonconjugated diene content to be 20% by weight or less. Non-conjugated diene content is 20% by weight
Exceeding this is not preferable because fluidity deteriorates due to gelation during kneading.

Preferred non-conjugated dienes include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene.

The number average molecular weight of these copolymers is preferably in the range of LOOOO to 100,000 in order to facilitate kneading in an extruder. If the molecular weight is too small, it will be difficult to handle when fed to an extruder, and if the molecular weight is too large, fluidity will be low and processing will be difficult. In addition, Mooney viscosity (ML1
+4121°C) is preferably 5 to 120.

Preferred rubber-like substances as component (c) of the thermoplastic resin used in the present invention include ethylene-α-olefin copolymers and modified products thereof, ethylene-propylene-unsaturated diene rubber and modified products thereof, butadiene −
Examples include styrene copolymers and hydrogenated products thereof, epoxy group-containing copolymers, and styrene-ethylene-propylene copolymers.

In the present invention, the desired thermoplastic resin composition can be obtained by setting the composition ratio of component (a) and component a (b) within a specific range. The ratio of component (a) and component (b) in the present invention is that component (a) is 99 to 1% by weight, component (b) is 1 to 99% by weight, and component (a)
and component (b) to 100 parts by weight, component (c)
is 0 to 60 parts 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.

Further, if the amount of component (c) exceeds 60 parts by weight per 100 parts by weight of the total weight of components (a) and (b), the heat resistance of the composition decreases, which is not preferable.

In the thermoplastic resin composition used in the present invention, an inorganic filler may be used if desired, particularly for the purpose of improving the rigidity, dimensional stability, etc. of the molded article.

Examples of such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, and gypsum, among which talc and calcium carbonate are preferably used.

Such an inorganic filler preferably has an average particle size of 0.05 to 10 μm.

If the particle size is less than 0.05μ, the effect of improving the dimensional stability and rigidity of the molded product will be small, and if it exceeds 10μ, the surface gloss of the molded product will be significantly impaired, making it impossible to achieve the object of the present invention. . Moreover, glass fiber can also be used as the inorganic filler.

In addition to the above-mentioned components, a melt flowability improver can be used in the thermoplastic resin composition used in the present invention, if necessary.

Well-known melt fluidity improvers can be used, but preferred ones include white oil, liquid paraffin, low molecular weight hydrocarbon resins, and low molecular weight polyolefins, and modified products of these can also be used. can do.

White oil here refers to a highly refined petroleum fraction, which is a mixture of paraffinic and naphthenic saturated hydrocarbons, and does not contain impurities such as aromatic compounds, acids, sulfur-containing compounds, etc. It is something.

Liquid paraffin refers to crude oil that is distilled under normal pressure or under vacuum to remove unsaturated, aromatic, and sulfur contents.

These white oils and liquid paraffin are JIS
Viscosity < 37.8°C based on K2283 (SUSSec
ond) of 40 to 400 is preferably used.

If the viscosity is outside this range, it is not suitable because the melt flowability of the composition is insufficient or the mechanical properties of the composition are significantly deteriorated.

Furthermore, the low molecular weight hydrocarbon resins mentioned here are generally known as petroleum resins, terpene phenolic resins, terpene resins, rosin resins, coumaron-indene resins, aromatic hydrocarbon resins, alicyclic saturated hydrocarbon resins, etc. It also includes hydrogenated products and modified products with acids.

The above-mentioned petroleum resins are unsaturated hydrocarbon fractions obtained by cracking petroleum, such as LPG, light or heavy naphtha, kerosene or gas oil fractions, heavy oil or crude oil. By-product oil with a boiling point range of 20 to 280°C obtained when producing ethylene, propylene, butadiene, etc. by cracking by thermal cracking methods such as steam cracking, gas phase pyrolysis, and sand cracking or catalytic cracking methods. It is a resin obtained by polymerizing an unsaturated hydrocarbon fraction.

The aromatic hydrocarbon resin is obtained from cracked naphtha obtained by cracking petroleum, and its main component is unsaturated aromatic hydrocarbons represented by mixed vinyl toluene and mixed vinyl xylene. An aromatic hydrocarbon oligomer obtained by polymerizing a hydrogen mixture.

The coumaron-indene resin is derived from an unsaturated polycyclic aromatic hydrocarbon mixture contained in light oil produced by carbonization of coal.

The terpene phenolic resin and terpene resin are derived from petroleum naphtha.

The rosin resin is a rosin polymer whose main components are abietic acid, dextropylic acid, etc., which are obtained by steam distilling turpentine from plants of the Pinaceae family.

The molecular weight of the low molecular weight hydrocarbon resin varies depending on the type of resin, but is generally in the range of 200 to 5000, preferably 3.
The range is preferably from 00 to 3000, more preferably from 350 to 2500.

As the melt fluidity improver, the ones exemplified above can be used alone or in combination of two or more kinds.

When carrying out the present invention, additional antioxidants, heat stabilizers, light stabilizers, flame retardants, lubricants, antistatic agents, inorganic or organic colorants, rust preventives, crosslinking agents, foaming agents, etc. Various additives such as a coating agent, a fluorescent agent, a surface smoothing agent, and a surface gloss improver can be added during the manufacturing process or in subsequent processing steps.

More specifically regarding 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 these. A mixture of two or more types 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, R12 is alkylene,
alkylidene or alicyclic bonds (e.g., methylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, etc.), ether, carbonyl, amine, sulfur-containing bonds (e.g., sulfide, sulfoxide, etc.) , sulfone), carbonate, and phosphorus-containing bonds.

Moreover, Rt2 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' are monocyclic or polycyclic carbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, and the like.

Ar and Ar' 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 (L) a halogen such as chlorine, bromine, iodine or fluorine, (2) general formula -OE (wherein E is a monovalent hydrocarbon group similar to X1 below) ether group, (3)
-〇H group, (4) a monovalent hydrocarbon group, or (5) other substituents, such as a 21·mouth group and a cyano group. When d is 2 or more, 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 Xts 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 0. 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 on the aromatic ring.

Specific examples of the above formula 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)-bentane, 2.2-bis-(3,5-dichlorophenyl)- /\xane, bis-(4-terphenyl)-phenylmethane, bis-(3,5-dichlorophenyl)7cyclohexylmethane, bis-(3-nitro-4-7'romophenyl phenyl)
-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, hexachlorobenzene, hexabromobenzene, 2,2'-dichlorobiphenyl, 2.4'-dibromobiphenyl, 2.4'-dichlorobiphenyl 1 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 those having the following general formula and nitrogen analogous compounds.

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; hydrogen; and combinations thereof.

Typical benefits of suitable phosphate esters include:

Phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl bis-(3,5,5'-1-limethylhexyl) phosphate, ethyldiphenyl phosphate, 2-phosphate Ethylhexyl di(p-tolyl), diphenyl hydrogen phosphate, bis(2-ethylhexyl)-p-1lyl phosphate, tritolyl phosphate, bis(2-ethylhexyl)-phenyl phosphate, tri(nonyl phosphate) phenyl), phenylmethyl hydrogen phosphate, di(dodecyl)-p-tolyl phosphate, triphenyl phosphate, halogenated triphenyl phosphate, dibutylphenyl phosphate, 2-chloroethyldiphenyl phosphate, p- phosphate ) Ryl bis(2,5,5'-1-limethylhexyl), 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 to use triphenyl phosphate in combination with antimony oxide.

Other flame retardant additives include compounds containing phosphorus-nitrogen bonds such as phosphorous nitride chloride, phosphorus esteramide, phosphoric acid amide, phosphine amide, tris(aziridinyl)phosphine oxyto or tetrakis(oxymethyl)phosphonium chloride. There is.

There are no particular limitations on the method for producing the thermoplastic resin composition in the present invention, and any conventional known method can be used. For example, a method of mixing in a solution state and evaporating the solvent or precipitating it in a non-solvent is effective, but from an industrial standpoint, a method of kneading in a molten state is actually preferable.

For melt-kneading, commonly used mixing devices such as single-screw or twin-screw extruders and various types of kneaders can be used. In particular, a twin-screw high kneader is preferred.

When mixing and purifying, it is preferable to uniformly mix each component in advance using a device such as a tumbler or a Henschel mixer, but if necessary, mixing may be omitted and a method may be used in which each component is individually fed quantitatively to a kneading device. I can do it.

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 component (a) and component (b) may be kneaded in advance and then component (c) may be kneaded. Furthermore, other cross-talk orders are also possible.

[Applications] The thermoplastic resin composition obtained by the method of the present invention is a resin composition with excellent heat resistance, melt flowability, processability, chemical resistance, impact resistance, appearance, and gloss. Taking advantage of its properties, it can be molded into sheets, tubes, films, fibers, laminates, coating materials, etc. by injection molding or extrusion molding.

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 for interior and exterior materials such as door trims, rear end trims, door panels, wheel covers, side protectors, air intakes, garnishes, trunk lids, bonnets, scirocco fans, and roofs, as well as for mechanical parts that require heat resistance. It is also used as parts for two-wheeled vehicles, such as covering materials, 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.

[Examples] 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, ) JIS K7207, Izot impact strength (thickness 3.2mm) is JIS K7110
Measured according to the following.

Further, the reduced viscosity (η, p/C) of polyphenylene ether in the examples is a value measured at 25° C. for a 0.5 g/dl chloroform solution.

Also, the melt flow index (M
I) was measured according to JIS K6758 at a temperature of 230°C and a load of 2.16 kg.

The physical properties were measured by kneading the composition using a twin-screw extruder and then using a Toshiba Machine Is 150E-V injection molding machine at a molding temperature of 260°C to 280°C and a mold cooling temperature of 70°C. The tests were conducted on injection molded products.

Grafting efficiency was measured by treating samples with methyl ethyl ketone. Furthermore, the average molecular weight of the graft chain portion was determined by GPC measurement.

Further, the shredded molded product of the composition was immersed in methyl ethyl ketone at 23° C. for one week, and then dried, and the methyl ethyl ketone eluted bone (weight %) of the composition was measured.

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

(1) η6 obtained by polymerization in the laboratory. /C=0.46
polyphenylene ether (hereinafter abbreviated as A-1).

) (11) Polyphenylene ether with η sp / C = 0.28 obtained by polymerization in the laboratory (hereinafter abbreviated as A-2) (citl) 100 parts by weight of polyphenylene ether A-2 was added to 22 parts by weight of hestyrene monomer in an autoclave. 1 part, 2 parts by weight of glycidyl acrylate, dispersant (Metrose 9
5 parts by weight of 0SH-100 (trade name) and 1.3 parts by weight of Perbutyl PV (trade name) were added together with water, reacted at 112°C for about 1.5 hours while blowing nitrogen, and then cooled to perform graft copolymerization. The resulting composition was recovered. Hereinafter, this composition will be abbreviated as A-3.

(J) As a fluoropyrene polymer, Sumitomo Noblen A
V664B' [Product name, manufactured by Sumitomo Chemical ■, MT=5.
0] (7) 100 parts by weight of pellets, 95 parts by weight of styrene monomer, 5 parts by weight of glycidyl methacrylate, 7 parts by weight of dispersant (Metrose 90SH-100; trade name), peroxide (perbutyl PV; trade name). ) and 300 parts by weight of water into an autoclave, and while blowing nitrogen, the temperature was raised to 100 °C over 1 hour to react. After further reacting at 100 °C for about 1 hour, it was cooled and denatured. Propylene polymer was recovered.

The graft efficiency in this graft copolymerization was 53%, and the average molecular weight of the graft chain portion was 21,500.

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

(II) Sumitomo Noblen C as a propylene polymer
WA51 [Product name, manufactured by Sumitomo Chemical, MI-9,0
], 100 parts by weight of the pellets were mixed with 8 parts by weight of acrylonitrile, 39 parts by weight of styrene monomer, 4 parts by weight of a dispersant (Metrose 90SH-100, trade name), 1 part by weight of peroxide (Perbutyl PV; trade name), and 300 parts by weight of water.
The mixture was put into an autoclave along with parts by weight, and while blowing nitrogen, the temperature was raised to 90°C for 1 hour to react.
After further reacting at 90° C. for about 1 hour, the reaction mixture was cooled and the modified polymer was recovered.

Next, 100 parts by weight of the obtained modified polymer, 8 parts by weight of styrene, 3 parts by weight of acrylonitrile, 1°1-bis(t-
butylperoxy')3,3.5-trimethylcyclohexane0. After mixing i parts by weight with a Henshil mixer, a twin-screw extruder (screw rotation speed 30 rpm), kneading temperature 2
A modified propylene polymer was obtained by extrusion at 80° C. under a nitrogen atmosphere.

As a result of analysis, the grafting efficiency of this graft copolymer was 7.
2%, and the average molecular weight of the graft chain portion was 3,800.

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

(iii) Sumitomo Noblen AV as a propylene polymer
664B [Product name, manufactured by Sumira Chemical Industries, Ml=5.0
A sample prepared by mixing 110 parts by weight of pellets with 0.08 parts by weight of 1,1bis(t-butylperoxy)3,3.5-trimethylcyclohexane and 5 parts by weight of styrene using a mixing roll. A twin screw extruder (
A modified propylene polymer was obtained by extrusion at a kneading temperature of about 270° C. under a nitrogen atmosphere. As a result of analysis, it was found that the amount of styrene in the obtained modified propylene polymer was as low as 0.31% by weight, the grafting efficiency was 26%, and the average molecular weight of the graft chain portion was 490. .

Hereinafter, this modified propylene polymer will be abbreviated as B-3.

(1,v) As a propylene polymer, Sumira Noblen CWA51 [trade name, manufactured by Sumira Chemical Industries ■, MI=9.
0] was added to 42 parts by weight of styrene monomer.
parts by weight, 500 parts by weight of toluene, dispersant (Metrose 9
5 parts by weight of 0SH-100 (trade name) and 0.08 parts by weight of Sanperox To [trade name, manufactured by Sansei Kako ■] were placed in an autoclave, and reacted at 110°C for about 2 hours while blowing nitrogen. After cooling, the modified copolymer was recovered by reprecipitating with methanol and then drying. As a result of analysis, the grafting efficiency of this modified copolymer was 20%, and the average molecular weight of the graft chain portion was 87.
It was 00.

This modified copolymer is hereinafter abbreviated as B-4.

Component (c): Rubber-like substance (1) 100 parts by weight of Sumira Nisprene E301, an ethylene-propylene-nonconjugated diene copolymer rubber [trade name, manufactured by Sumira Chemical Co., Ltd., ML1+4100°C=55], and 300 parts by weight of water. parts by weight, 51 parts by weight of styrene monomer, 3 parts by weight of glycidyl acrylate, dispersant (Metrose 90
4 parts by weight of SH-100 (trade name) and 0.07 parts by weight of peroxide (perbutyl Pv; trade name) were placed in an autoclave, and while blowing nitrogen,
After reacting at 95° C. for about 1 hour, the mixture was cooled and the grafted modified rubber was recovered.

Next, to 100 parts by weight of this modified rubber, 12.8 parts by weight of maleic anhydride, 9.5 parts by weight of styrene, and 1,3-bis(t-butylperoxyisopropyl)benzene ( Sansoku Kako ■; Sanberotux-TY13; trade name) was added to propylene homopolymer.
After uniformly mixing 0.3 parts by weight of Irgano Nox 1.010 (trade name, manufactured by Ciba Geigy) as a stabilizer with a Henschel mixer, the mixture was subjected to twin-screw extrusion. Extrusion was performed using a machine at a kneading temperature of 240° C. under a nitrogen atmosphere to obtain a modified rubber copolymer.

Hereinafter, this modified rubber copolymer will be abbreviated as C-1.

(1j> After internally purging the glass reactor with nitrogen gas, 100 parts by weight of purified and dried styrene, 800 parts by weight of sufficiently purified, dried and degassed cyclohexane, and n-butyllithium as an initiator in hexane. Add 2.1 mmol to 1 mol of styrene as a solution and add 60
The temperature was raised to .degree. C., and polymerization was carried out for 2 hours. The polymerization liquid became a red viscous liquid. A portion (approximately 1 ml) of the polymerization solution was collected.

Next, 66 parts by weight of purified and dried isoprene was added.
The reaction continued for 2 hours at 0°C. The polymerization liquid became a yellow viscous liquid. After a total of 4 hours of polymerization reaction, 6 parts by weight of 2,
10 parts by weight of methanol in which 6-di-t-butyl-p-cresol was dissolved was added to stop the polymerization. The polymer solution was gradually dropped into a large amount of methanol, and the resulting copolymer slurry was filtered, washed three times with methanol, and then vacuum-dried at 40°C.

This polymer was dissolved in toluene and introduced into an SUS (stainless steel) autoclave equipped with a jacket and a stirrer, and after the gas phase was thoroughly degassed using a vacuum pump, it was heated to 5 kg/c♂ with hydrogen gas. After repeating the pressurization and depressurization operations up to G twice, 20 mmol of nickel-2-ethylhexoate was added to 100 parts by weight of the polymer.
215 mO1 of cyclohexene and 645 mmol of triethylaluminum were added, and the temperature of the system was raised to 80°C. Hydrogen gas until the internal pressure reaches 50 kg/cd.
The mixture was introduced into an autoclave and reacted for 7 hours. This polymer solution was poured into hot water, toluene was distilled off by vacuum steam distillation, and the resulting polymer slurry was filtered and dried for 48 hours in a flow-through hot air dryer at 80°C. The body was recovered. Infrared absorption spectroscopy revealed that approximately 90% of the isoprene moieties were hydrogenated. Also, G
By PC measurement, it was found that the molecular weight distribution of the copolymer was narrow, and the number average molecular weight of the copolymer was about 100,000.
Furthermore, the molecular weight of the styrene polymer collected during the synthesis reaction of the styrene-isoprene block copolymer was approximately 6,000.
Therefore, the styrene chain length of the polystyrene part is 577, and the chain length of the hydrogenated polyisoprene part is 1.1.
．． It was calculated as 76.

Hereinafter, this polymer will be abbreviated as C-2.

Other rubber-like substances used in Examples and Comparative Examples of the present invention are shown in the table below.

The above components were blended in the proportions shown in Tables 1 and 2, and the respective blends were kneaded and then injection molded to examine their physical properties. The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, (a) polyphenylene ether or a composition containing polyphenylene ether, (b) styrenic monomer and/or styrenic monomer and copolymerizable with styrenic monomer It is a modified propylene polymer obtained by graft copolymerizing a mixture with a monomer, and the graft efficiency in the copolymerization reaction to obtain the graft copolymer [(partial weight of graft chain/(homopolymer weight of the monomer) Quantum graft chain partial weight)l XIQ
O (%) is 30% or more, and the graft chain of the modified propylene polymer has a molecular weight of 1000 to 200000.
a modified propylene polymer and/or a mixture of the modified propylene polymer and a propylene polymer, and (c
) It can be seen that the composition made of the rubber-like substance is a thermoplastic resin composition with excellent heat resistance, impact resistance, chemical resistance, etc.

Claims (1)

[Claims] 1) (a) polyphenylene ether or a composition containing polyphenylene ether; (b) a propylene polymer copolymerized with a styrene monomer and/or a styrene monomer and a styrene monomer; It is a modified propylene polymer obtained by graft copolymerizing a mixture with a monomer that can combined weight + graft chain partial weight)}×100 (%)] is 30% or more, and the graft chain of the modified propylene polymer has a molecular weight of 1000 to 20
0000 and/or a mixture of the modified propylene polymer and a propylene polymer, and (c) a rubber-like substance, wherein the ratio of component (a) to component (b) is 99. ~1% by weight, component (b) ~1
99% by weight, and the sum of the weights of component (a) and component (b) is 1
00 parts by weight, a thermoplastic resin composition containing 0 to 60 parts by weight of component (c).