JPH03273054A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To improve heat resistance, mechanical properties, moldability, resistance to chemicals and oils, etc., by compounding a (compsn. contg.) polyphenylene ether with a (mixture of a) specific modified propylene polymer (with a propylene polymer). CONSTITUTION:A styrenic monomer and, if necessary, a monomer copolymerizable therewith are graft copolymerized onto a propylene polymer comprising 90-10wt.% propylene homopolymer part and 10-90wt.% random copolymer part consisting of 85-10wt.% propylene and 15-90wt.% ethylene and/or 4-6C alpha-olefin to give a modified propylene polymer which has a grafting efficiency {[wt. of graft chain part/(wt. of homopolymers of the monomers + wt. of graft chain part)]X100} of 30% or higher and mol.wt. of graft chain of 1000-200000. The modified propylene polymer is mixed with a propylene polymer to give a polymer mixture. 99-1wt.% said mixture is compounded with 1-99wt.% (compsn. contg.) polyphenylene ether.

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,
This resin has excellent properties such as dimensional stability and mechanical and electrical properties, but on the other hand, due to its high melt viscosity, it has poor moldability, poor chemical resistance, poor oil resistance, and low impact resistance. It has the following disadvantages.

A mixture of polyphenylene ether and polystyrene resin is known as a method to lower the melt viscosity and improve moldability while maintaining the excellent properties of polyphenylene ether, but it is still difficult to improve chemical resistance and oil resistance. Not done.

On the other hand, propylene polymer has excellent properties such as moldability, toughness, water resistance, chemical resistance, and oil resistance.
Furthermore, because it has a low specific gravity and is inexpensive, it has been widely used in various molded products, films, and sheets.

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 a significantly poor appearance due to phase separation between polyphenylene ether and propylene polymer. , and its mechanical properties are also poor, making it unsuitable for practical use.

However, in the market, there is a demand for resin compositions that have high impact resistance, excellent weather resistance, etc. 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 do not necessarily exhibit sufficient weld strength, impact resistance, and surface impact resistance, and it may be difficult to use this composition depending on the application. 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 properties, as well as excellent moldability, chemical resistance, oil resistance, etc. As a result, we have arrived at the present invention.

That is, the present invention provides (a) polyphenylene ether or a composition containing polyphenylene ether, and (b) a propylene homopolymer portion and at least one type selected from propylene, ethylene, and an α-olefin having 4 to 6 carbon atoms. A random copolymer portion consisting of a copolymerization component of
0% by weight, and the ratio of propylene to at least one copolymer component selected from ethylene and α-olefin having 4 to 6 carbon atoms in the random copolymer portion is 85 to 10% by weight/15 to 90 A modified propylene polymer obtained by graft copolymerizing a styrene monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrene monomer to a raw material propylene polymer of % by weight. Grafting efficiency in the graft copolymerization reaction to obtain the graft copolymer [(graft chain partial weight/(homopolymer weight of the monomer + graft chain partial weight))} x 100 (%) ] is 30% or more, and the molecular weight of the graft chain of the modified propylene polymer is 10%.
00 to 200,000 and/or a mixture of the modified propylene polymer and a propylene polymer, the ratio of component (a) to component (b) is 99
The present invention relates to a thermoplastic resin composition characterized in that the content is 1% by weight/1 to 99% by weight.

The thermoplastic resin composition of the present invention has excellent heat resistance, impact resistance, surface impact resistance, weld strength, chemical resistance, oil resistance, and processability.

The polyphelene ether of component (a) used in the present invention has the general formula [■] Represents a halogen atom, a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group.However, R-
One of R5 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 in the above general formula. R2, R3, R4 and R5
Specific examples include hydrogen atom, chlorine atom, bromine atom, fluorine atom, iodine atom, methyl, ethyl, n~ or 1
so-propyl, prfsec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxylethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl groups, etc. can be mentioned.

Specific examples of the 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-dimethylphenyl, 2-methyl-6-ethylphenol, 2,3゜5
-2.3.6- or 2.4.6-dolimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like.

Furthermore, the phenol compound having the above general formula may be copolymerized with a phenol compound other than the above general formula, for example, a polyhydric hydroxy aromatic compound such as bisphenol-A1 tetrabromobisphenol-A russorcin, hydroquinone, or novolak resin.

Among these compounds, 2,6-dimethylphenol (2,6-xylenol) or 2,6-dimethylphenol (2,6-xylenol) is preferred.
A homopolymer of 6-diphenylphenol and a large amount of 2,6-xylenol and a small amount of 3-methyl-6-t-
Mention may be made of copolymers of butylphenol or 2.3.64-dimethylphenol.

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.

Representative examples include catalysts consisting of cuprous salts and tertiary amines such as cuprous chloride-triethylamine and cuprous chloride-pyridine; cupric chloride-pyridine-hydroxide; Catalyst consisting of cupric salt such as potassium-amine-alkali metal hydroxide; Catalyst consisting of manganese salts and primary amines such as manganese chloride-ethanolamine, manganese acetate-ethylenediamine; Manganese chloride-sodium methylate, Catalysts consisting of manganese salts such as manganese chloride-sodium phenolate 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, phenols represented by the general formula (each symbol in the formula has the same meaning as above) are oxidatively polymerized in the presence of an ethylene-propylene-polyene terpolymer; (Each symbol in the formula has the same meaning as above.) A product obtained by oxidative polymerization of the phenols represented by
or organic peroxide graft copolymerized with other polymerizable monomers (Japanese Patent Publication No. 47-47862, Japanese Patent Publication No. 12197-1987, Japanese Patent Publication No. 5623-1973, Japanese Patent Publication No. 38596-1972, -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 (Japanese Patent Laid-open No. 5
2-142799), etc.

In the present invention, the preferred reduced viscosity of the polyphenylene ether (measured in chloroform at 25°C) is 0.2 to 0.
．． 6 dl/g, and the optimum reduced 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) a carbon-carbon double bond or a carbon-carbon triple bond and (11) a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an epoxy group,
Compounds having one or more amino groups or hydroxyl groups at the same time (
F) is 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, such as 0 0 111 (However, R13 is an aliphatic or aromatic 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, etc. oil, natural oils and fats such as camellia oil, 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, tetracosenoic acid, mycolibenic acid, 2,4-pentadienoic acid, 2.4-hexadienoic acid, diallyl 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, octadecatriene Acid, icosadienoic acid, icosatrienoic acid, icosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, icosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, Unsaturated carboxylic acids such as tetracosenoic acid, hexadienoic acid, hexacosenoic acid, oftacosenoic acid, and traacontenoic acid, or esters, acid amides, and anhydrides of these unsaturated carboxylic acids, or allyl alcohol, crotyl alcohol, methylvinyl carbinol, and allyl. Carbinol, methylpropenylcarbinol, 4-penten-1-ol, 10-undecen-1-ol, propagyl alcohol, 1,4-pentadien-3-ol, 1,4-hexadien-3-ol, 3 .5-hexadien-2-ol, 2,4-hexadien-1-ol, general formula CnH2n-50H1
CHOH, C, H2n, OH (where 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,
Unsaturated alcohols such as 2,6-octadiene-4,5-diol, unsaturated amines in which the 10H group of such unsaturated alcohols has been replaced with -NH2 groups, or lower alcohols such as butadiene and isoprene. Polymers (e.g.
Those with an average molecular weight of about 500 to 10,000) or those with maleic anhydride or phenols added to high molecular weight substances (for example, those with an average molecular weight of too much or more), 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 [
■Co(R150)mR14(COOR16)n(COOR1
□R18).

[Aliphatic carboxylic acids, acid esters and acid amides represented by V (where R14 is a linear or branched aliphatic saturated hydrocarbon group having 2 to 20 carbon atoms, R1 , 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 carbonyl dioxy group having 1 to 10 carbon atoms. A group independently selected from the group consisting of an alkyl group and an aryl group, and each of R and R18 is a hydrogen atom and a group independently selected from the group consisting of an alkyl group having 7 to 10 carbon atoms and an aryl group. , m, n and S are integers greater than or equal to 0, and m+n+s≧
It is 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, 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 α.

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

Further, the derivatives of the above general formula [V] are -, 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- Dimethylpiolactone, 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-isopropyl paraconic acid, γ-methylparaconic acid, γ-ethylparaconic acid, α,γ-dimethylvalaconic acid, β,γ-dimethylvalaconic acid, α,α,β-trimethylparaconic acid, γ,γ-dimethylparaconic acid, Nefrosteranic 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, 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 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 (J) 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, Sumima Kagaku Kogyo Co., Ltd. and Union Carbide's phenoxy resin, etc.], condensate of resorcinol and shrimp chlorohydrin, condensate 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, made by Sumima Kagaku Kogyo ■] 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 Sumitomo Chemical Industry 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 copolymer and ethylene-glycidyl (meth)acrylate copolymer 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 (1) 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 (if) an amino group,
It is an organosilane compound having at least one functional group selected from 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.

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 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. 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), 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.

For example, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4,4)-trimethylvaleronitrile, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3.3.5 -4-limethylcyclohexanone peroxide, 2.2-bis(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2.5-dimethylhexane-2,5 -cybidroba-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, 3.3.54limethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl Peroxyisobutyrate, t-butyloxypivalate, t-butyl-oxy-2-ethylhexanoate, t-butylperoxy-3,5,5-1-limethylhexanoate, t-butylperoxy Laurate, t-7' tyl peroxybenzoate, di t-butyl peroxy isophthalate, 2,5-dimethyl-2,5-
These are various organic peroxides such as di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxypropyl carbonate, and polystyrene peroxide.

Preferred specific examples include benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, tert-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.

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. 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) a method in which polyphenylene ether is dissolved; Alternatively, the above compound is added to a swollen solution, dissolved or swollen, and heated while stirring. (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, a roll, a kneader, and the like.

There are no particular restrictions 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, O-chlorophenol, and the like. 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 Sen's U
polymers), 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 of the present invention, in addition to component (a) as described above, component (b) includes a propylene homopolymer portion, and at least one component selected from propylene, ethylene, and an α-olefin having 4 to 6 carbon atoms. It has a random copolymer part consisting of different types of copolymer components, and the ratio of the propylene homopolymer part to the random copolymer part is 90 to 10% by weight/10 to 90% by weight, and the random copolymer part has a The ratio of propylene and at least one copolymer component selected from ethylene and α-olefin having 4 to 6 carbon atoms in the combined portion is 85 to 10% by weight/1
It is obtained by graft copolymerizing a styrenic monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrene monomer to a raw material propylene polymer having a content of 5 to 90% by weight. Grafting efficiency in a graft copolymerization reaction for obtaining the graft copolymer of a modified propylene polymer [(graft chain partial weight/(homopolymer weight of the monomer + graft chain partial weight')) X100
(%)] is 30% or more, and the molecular weight of the graft chain of the modified propylene polymer is 1000 to 200000.
A modified propylene polymer and/or a mixture of the modified propylene polymer and a propylene polymer are used.

In component (b) of the present invention, the raw material propylene polymer that is the raw material for the modified propylene polymer is usually obtained by two-step polymerization, and the first segment of propylene polymerized in the first step of polymerization is A random copolymer consisting of a homopolymer portion and at least one copolymer component selected from propylene, ethylene, and an α-olefin having 4 to 6 carbon atoms, which is the second segment polymerized in the second step of polymerization. It has a combined part.

Here, the propylene homopolymer which is the first segment can be obtained by homopolymerizing propylene in the first step, or can be obtained by homopolymerizing propylene in the first step. - The content of the copolymer component in the copolymer obtained by copolymerizing at least one type of copolymer component selected from olefins with propylene is 6 mol%
The following propylene copolymers can also be used.

The copolymerization component randomly copolymerized with propylene in the second step of polymerization is at least one type selected from ethylene and α-olefins having 4 to 6 carbon atoms.

Here, examples of the α-olefin having 4 to 6 carbon atoms include butene-1, pentene-1, hexene-1,4-methylpentene-1,8-methylbutene-1, and the like.

These copolymerizable components can be used alone or in combination of two or more kinds to be randomly copolymerized with propylene, and among them, ethylene and butene-1 are particularly preferred.

In the present invention, the raw material propylene polymer for the modified propylene polymer may be one obtained by copolymerizing polyene in addition to propylene and the above-mentioned copolymerization components. Specific examples of such polyenes include butadiene, cyclopentadiene, 1,9-decadiene, 1,5-hexadiene, 1,4
-hexadiene, 1,3.7-octatriene, vinylcyclohexane, 5-ethylidene-2-norbornene,
Examples include 5-isopropenyl-2-norbornene. Among these, non-conjugated dienes are particularly preferred.

In component (b) of the present invention, the raw material propylene polymer that is the raw material for the modified propylene polymer has a ratio of propylene homopolymer portion to random copolymer portion of 90 to 10.
wt%/10 to 90 wt%, preferably 70 to 10 wt%/30 to 90 wt%, and at least selected from propylene and ethylene and α-olefins having 4 to 6 carbon atoms in the random copolymer portion. The ratio with one type of copolymerization component is 85-10% by weight/15-90% by weight
, preferably 80-20% by weight/20-80% by weight.

In this raw material propylene polymer, if the proportion of the random copolymer portion exceeds 90% by weight, the heat resistance of the composition will be significantly lowered, and the oil resistance will also be lowered, which is not preferable.

Furthermore, if the proportion of the random copolymer portion is less than 10% by weight, the impact resistance of the composition will decrease, which is not preferable.

Furthermore, if the propylene content of the random copolymer portion exceeds 85% by weight, the low temperature properties and rubbery properties will be impaired, and if it is less than 10% by weight, the rubbery properties will be impaired, which is not preferable.

In the present invention, the raw material propylene polymer for the modified propylene polymer can be produced by a slurry polymerization method, a gas phase polymerization method, or the like. When used for applications requiring particularly high impact resistance, it is preferable to increase the amount of the second segment, and gas phase polymerization is preferred.

High impact resistant propylene polymers produced by gas phase polymerization are disclosed in, for example, JP-A-61-287917 and JP-A-1-986.
It can be manufactured by the method exemplified in Japanese Patent No. 04.

At this time, the amount of the polymer produced in the second step is about 10 to 70% by weight based on the total polymerization amount.

In the slurry polymerization method, the second segment amount is 10 to 25
By weight%, gas phase polymerization can produce products in the range of 10 to 90% by weight, both of which are preferred.

A propylene polymer having a large amount of second segments in a gas phase polymerization method can be produced by the method exemplified in Japanese Patent Application No. 62-256015, and is suitably used for applications requiring ultra-high impact resistance.

In component (b) of the present invention, the intrinsic viscosity of the second segment of the raw material propylene polymer in a 135°C tetralin solution varies depending on the productivity during manufacturing, the properties of the polymer powder, or the intrinsic viscosity of the first segment, and cannot be generalized. However, in the slurry polymerization method, it is approximately 3 to 8 dll/g, and in the gas phase polymerization method, it is in the range of 1 to 5 d, Q/g.

When the thermoplastic composition of the present invention is used for applications that particularly require heat resistance, rigidity, scratch resistance, etc., as the raw material propylene polymer for the modified propylene polymer of component (b),
The isotactic pentad fraction of the boiling heptane insoluble portion of the propylene homopolymer portion, which is the first segment polymerized in the first step, is 0.970 or more, and the content of the boiling heptane soluble portion is 5.0. % by weight or less, and 2
It is preferable to use a highly crystalline propylene polymer having a content of 0° C. xylene soluble portion of 2.0% by weight or less.

The isotactic pentad fraction of the boiling heptane insoluble part, the content of the boiling heptane soluble part and 20
The content of xylene soluble polymer at °C is determined as follows.

After completely dissolving 5 g of propylene polymer in 1 ml of boiling xylene 50C, the temperature was lowered to 20°C and left for 4 hours.

Thereafter, this is filtered to separate the xylene-insoluble portion at 20°C. The filtrate is concentrated to dryness to evaporate xylene, and further dried under reduced pressure at 60°C to obtain a polymer soluble in xylene at 20°C. The value obtained by dividing this dry weight by the weight of the prepared sample and expressing it as a percentage is the content of the xylene soluble portion at 20°C.

The xylene-insoluble portion at 20°C is dried and then subjected to Soxhlet extraction with boiling n-heptane for 8 hours.

This extraction residue is called the boiling heptane insoluble portion, and the value obtained by subtracting this dry weight from the weight of the prepared sample (5 g) divided by the weight of the prepared sample, expressed as a percentage, is the content of the boiling heptane soluble portion. be.

Isotactic-pentad fraction is A, Zam
Macromolecules by bell et al.
6゜925 (Isotactic chain of pentad units in the propylene polymer molecular chain measured using the method published in 19L, that is, using 13C-NMR, in other words, five consecutive propylene monomer units) This is the fraction of propylene monomer units at the center of meso-bonded chains.However, regarding the assignment of NMR absorption peaks, refer to Macromo!ecules published subsequently.
8.687 (1975).

Specifically, the isotactic-pentad fraction is measured as the area fraction of the 111111ml11 peak among all absorption peaks in the methyl carbon region of the 13C-NMR spectrum. By this method British NATIONAL PHYSI
CALLABORATION's NPL standard material CRMl
! 1M19-14Polypropylene P P
/ MW D / 2 was measured and found to be 0.944.

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

Furthermore, in fields where high rigidity is required, it is preferable to incorporate a nucleating agent into the propylene polymer as a raw material for the modified propylene polymer in the present invention. For example, aluminum or sodium salts of aromatic carboxylic acids (JP-A-5
8-80829), aromatic carboxylic acids, aromatic phosphate metal salts, sorbitol derivatives (Japanese Patent Publication No. 12460/1982)
It is known that by adding substances such as JP-A No. 58-129036), 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 Unexamined Patent Publication No. 1738/1986).

That is, a composition obtained by blending a vinylcycloalkane polymer having 6 or more carbon atoms with a propylene polymer as a raw material for the modified propylene polymer in the present invention, wherein 0.05 wtpp of vinylcycloalkane units are added to the composition.
A propylene polymer composition containing m to 110,000 vtpp has higher crystallinity.

In the component (b) of the present invention, the styrenic monomer used to obtain the modified propylene polymer by graft copolymerizing the raw material propylene polymer has the general formula [n] (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 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 R10 in the above general formula [■] include hydrogen atom; halogen atom such as chlorine, bromine, iodine, methyl, ethyl, propyl, vinyl, allyl, benzyl, methyl Hydrocarbon groups such as benzyl; 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. -divinylbenzene, p-(chloromethoxy)-styrene, α-methylstyrene, 0-methyl-α-methylstyrene, m-methyl-α-methylstyrene, p-methyl-α-methylstyrene, p-methoxy-α -Methylstyrene, etc. 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 raw material 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 modified propylene polymer as component (b) in the present invention has a grafting efficiency of 30% or more in the graft copolymerization reaction for obtaining the modified propylene polymer, and has a molecular weight of the graft chain of the modified propylene polymer. 10
A modified propylene polymer having a molecular weight of 00 to 200,000 is preferably used.

The grafting efficiency mentioned here refers to the styrenic monomer and/or
Alternatively, it refers to the efficiency with which a mixture of a styrene monomer and a monomer copolymerizable with the styrene monomer becomes a graft chain to a propylene polymer, and the grafting efficiency is calculated from the following formula: You can ask for it.

[Graft chain partial weight/(homopolymer weight of the monomer +
Graft chain partial weight) Co 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.

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,
Mechanical strength etc. decrease, which is not preferable. 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 does not allow the homopolymer to be extracted. 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 preferred grafting efficiency for component (b) is 30% or more, and the molecular weight of the graft chain portion is 10%.
The method for producing a modified propylene polymer having a molecular weight of 0.00 to 200,000 is not particularly limited, and examples include suspension polymerization,
Any known method such as emulsion polymerization, solution polymerization, or bulk polymerization (including methods using an extruder in addition to methods 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 raw material propylene polymer are melt-kneaded with a peroxide such as the one shown below to undergo modification. Examples include a method of obtaining a propylene polymer, and a method of copolymerizing a raw material propylene polymer with a styrene monomer, glycidyl methacrylate, etc. by radical polymerization.

Specifically, as described in the example of JP-A-1-207349, raw material propylene polymer, styrene, dispersant, organic peroxide, etc. are added to the aqueous phase, and then the raw material propylene is heated. One example is a suspension polymerization method in which styrene is graft copolymerized onto a polymer.

In addition, a copolymer of styrene and acrylonitrile is first produced by anionic polymerization, and then this copolymer and a raw material propylene polymer are melt-kneaded together with an organic peroxide.
Examples include a method of obtaining a modified propylene polymer, or a method of copolymerizing a raw material propylene polymer with a styrene monomer, glycidyl methacrylate, etc. by radical polymerization.

Here, the peroxide used in producing the above-mentioned modified propylene polymer 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.

In the present invention, as component (b), in addition to the above-mentioned modified propylene polymer, a mixture of the modified propylene polymer and a propylene polymer can be used as necessary.

Here, the propylene polymer in component (b) of the present invention means a propylene homopolymer or a propylene copolymer, and the propylene copolymer refers to propylene and other polymers having from 2 to 18 carbon atoms. It means a random or block copolymer with α-olefin. Of course, this propylene polymer also includes the same propylene polymer as the raw material propylene polymer for the modified propylene polymer described above.

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.

The propylene polymer may be a highly crystalline propylene polymer, a propylene polymer blended with a nucleating agent, or a propylene polymer with a carbon number of 6 or more, in the same way as the raw material propylene polymer for the modified propylene polymer is produced as needed. A propylene polymer containing a vinylcycloalkane polymer as a nucleating agent, or a propylene polymer containing a highly crystalline propylene polymer containing a nucleating agent, etc. can be used.

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

In the present invention, when producing the raw material propylene polymer for the modified propylene polymer of component (b) by slurry polymerization or gas phase polymerization, the reactor is not particularly limited, and a known stirring mixing tank type reactor is used. , a fluidized bed reactor, a fluidized bed reactor with a stirrer, etc. can be used.

Polymerization can be carried out continuously by connecting two or more reactors in series, by batchwise polymerizing in one or more reactors, or by a combination of both.

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 99
~1% by weight, component (b) from 1 to 99% by weight, preferably component (a) from 80 to 1% by weight, component (b) from 20% by weight.
~99% 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.

The present invention is achieved by blending the above-mentioned modified propylene polymer and/or a mixture of the modified propylene polymer and a propylene polymer as component (b) into the polyphenylene ether or polyphenylene ether-containing composition of component (a). The major feature is that a thermoplastic resin composition having excellent heat resistance, mechanical properties, etc. can be obtained without using any rubber-like substances used in conventional thermoplastic resin compositions.

However, if particularly high impact resistance and surface impact resistance are required in the market, a rubber-like substance may be used as necessary.

As used herein, rubber-like materials refer to natural and synthetic 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 -propylene copolymer,
Ethylene-butene copolymer, ethylene-propylene-styrene copolymer, styrene-isoprene copolymer, or its hydrogenated product, styrene-butylene copolymer, styrene-ethylene-propylene copolymer, perfluororubber, fluororubber , chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-nonconjugated diene copolymer, thiol rubber, polysulfide rubber, polyurethane rubber,
Examples include polyether rubber (eg, propylene oxide, etc.), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and epoxy group-containing copolymer.

In addition to the above-mentioned components, the thermoplastic resin composition of the present invention includes:
A melt fluidity improver can be used 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
Based on S K2283 < 37.8 °C viscosity (SU
SSecond) 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 additives, fluorescent agents, surface smoothing agents, and surface gloss improvers, 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, /\ rogenated organic compound, antimony oxide, antimony oxide and 10 genated organic compound, antimony oxide and phosphorus compound, phosphorus alone or phosphorus compound, phosphorus compound or compound with phosphorus-nitrogen bond and /''% rogen-containing A compound or a mixture of two or more of these can be 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.

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, amidino, cyclohexylene, cyclopentylidene, etc.), ether, carbonyl, amine, sulfur-containing bonds (e.g. sulfide, sulfoxide) , sulfone), carbonate, and phosphorus-containing bonds.

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' 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 (1) a halogen such as chlorine, bromine, iodine or fluorine, (2) a general formula -OE (wherein E is a monovalent hydrocarbon group similar to X1 below) ether group, (3)
-〇H 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 XIs 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 O. 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)-pentane, 2.2-bis-(3,5-dichlorophenyl)- Hexane, 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, hexachlorobenzene, hexabromobenzene, 2,2'-dichlorobiphenyl, 2.4'-dibromobiphenyl, 2.4'-dichlorobiphenyl, hexabromobiphenyl, octabromobiphenyl, decabromobiphenyl, halogenated diphenyl ethers containing 2 to 10 halogen atoms, 2.2-bis-(3, Polymerization degree of 1 to 5-dibromo-4-oxyphenyl)-propane and phosgene
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.

In the above formula, each Q is the same or different and includes hydrocarbon groups such as alkyl, cycloalkyl, aryl, alkyl-substituted aryl and aryl-substituted alkyl; halogen; hydrogen and combinations thereof.

Representative examples of suitable phosphoric acid esters include:

Phenyl bisdodecyl phosphate, bisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl bis-(3,5,5'-)limethylhexyl phosphate), ethyldiphenyl phosphate, 2-phosphate Ethylhexyl di(p-tolyl), diphenyl hydrogen phosphate, bis-(2-ethylhexyl)-p-)lyl phosphate, tritolyl phosphate, bis-(2-ethylhexyl)-phenyl phosphate, tri(nonyl phosphate) phenyl), phenylmethyl hydrogen phosphate, di(dodecyl)-p-)lyl phosphate, triphenyl phosphate, halogenated triphenyl non-acid, dibutylphenyl non-acid, 2-chloroethyldiphenyl non-acid, p-non acid -tolylbis-(2,5,5'-trimethylhexyl), 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, 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 fed in a fixed amount to the kneading device separately. can.

The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but instead of going through the cross-mixing 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.

[Applications] The thermoplastic resin composition of the present invention has excellent heat resistance, melt flowability,
It is a resin composition with excellent processability, chemical resistance, impact resistance, appearance, and gloss. Taking advantage of these properties, it can be used to mold products, sheets, tubes, films, fibers, laminates, etc. by injection molding and extrusion molding. It is used as a coating material, etc.

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 (HoD) in the examples.

T,) is JIS K7207, Izot impact strength (
The thickness (L2 mm) was measured according to JIS KmO.

In addition, oil resistance is determined by testing the injection molded product in commercially available gasoline at 25°C.
After 100 hours of immersion, the appearance of the molded product was evaluated based on the following criteria.

○: No change observed in appearance. ×: Rough skin and change in color tone are observed on the surface.

The flexural modulus was measured for each of the welded and non-welded parts of the injection molded product according to ASTM D790.

Surface impact strength is H1gh manufactured by Rheometrics (USA)
Rate Impact Te5ter (RfT-
Using a 578 inch (spherical tip 5716
Using an impact probe of inch R), apply the impact probe to the test piece at a speed of 1.5 m/sec at 23 ° C.,
evaluated.

Joule (J) is the energy value required for a material to break.
It was displayed in

Further, the reduced viscosity (η8./C) of the polyphenylene ether in the examples is a value measured at 25° C. for 0.5 g/old solution solution and loloform solution.

In addition, the physical properties were measured using a twin-screw extruder at 260°C to 280°C.
After kneading the composition at ℃, Is 150 manufactured by Toshiba Machine ■
Using an E-V injection molding machine, the molding temperature is 260°C to 28°C.
The test was performed on a molded product injection molded at 0°C and a mold cooling temperature of 70°C.

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.

Polyphenylene ether as component (a) 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. (Polyphenylene ether of No. 2 (hereinafter abbreviated as A-1).

(11) Polyphenylene ether with ηSp/C=0.47 obtained by polymerization in the laboratory (hereinafter abbreviated as A-2).
.

Modified propylene polymer of component (b) (1) Raw propylene polymer A raw propylene polymer was produced according to the method exemplified in Example 1 of JP-A-1-98604.

Specifically, predetermined amounts of catalyst solid components, phenyltrimethoxysilane, and triethylaluminum are placed in an autoclave, hydrogen is added, and in the first step, liquefied propylene is pressurized into the autoclave and heated to 75°C to separate propylene alone. After polymerization and purging of unreacted monomers, a predetermined amount of a mixed gas of propylene and ethylene was injected into the autoclave in a second step, and random copolymerization of propylene and ethylene was carried out at 70°C.

Table 1 shows the abbreviations and compositions of the raw material propylene polymer thus obtained.

(1i) Modified propylene polymer 100 parts by weight of raw material propylene polymer, a predetermined amount of styrene monomer, and 350 parts by weight of water were put into an autoclave together with a dispersant and a radical generator, and the temperature was raised to 108°C while blowing nitrogen. After reacting for 2 hours, cool
The modified propylene polymer was recovered, and the graft efficiency in graft copolymerization and the average molecular weight of the graft chain portion were determined.

Abbreviation of the modified propylene polymer thus obtained (B-1
~B-5 and B-9) and the compositions are shown in Table 2.

In addition, instead of styrene monomer, a mixed monomer consisting of styrene monomer and glycidyl methacrylate, or styrene monomer and methyl methacrylate was used at a monomer ratio of styrene monomer: glycidyl methacrylate (or methyl methacrylate) = 92:8 (weight ratio). produced a modified propylene polymer in the same manner as described above.

Abbreviation of the modified propylene polymer thus obtained (B-6
~B-8) and the composition are shown in Table 2.

Examples 1 to 3 and Comparative Examples 1 to 8 The above components were blended in the proportions shown in Tables 3 and 4, and the respective blends were kneaded and then injection molded to examine their physical properties. The results are shown in Tables 3 and 4.

[Effects of the Invention] As is clear from Tables 3 and 4, (a) polyphenylene ether or a composition containing polyphenylene ether, and (b) a propylene homopolymer portion, propylene, ethylene, and α having 4 to 6 carbon atoms. - a random copolymer portion consisting of at least one type of copolymer component selected from olefins, and the ratio of the propylene homopolymer portion to the random copolymer portion is 90 to 10% by weight/10 to 9
0% by weight, and the ratio of propylene to at least one copolymer component selected from ethylene and α-olefin having 4 to 6 carbon atoms in the random copolymer portion is 85 to 10% by weight/15 to 90 A modified propylene polymer obtained by graft copolymerizing a styrene monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrene monomer to a raw material propylene polymer of % by weight. Graft efficiency in the graft copolymerization reaction for obtaining the graft copolymer [(graft chain partial weight/(homopolymer weight of the monomer + graft chain partial weight')) X100 (%) ] is 30% or more and the molecular weight of the graft chain of the modified propylene polymer is 1,000 to 200,000, and/or a composition containing a mixture of the modified propylene polymer and a propylene polymer is heat-resistant. It can be seen that the thermoplastic resin composition has excellent properties such as hardness, impact resistance, surface impact resistance, weld strength, and oil resistance.

Claims (1)

[Scope of Claims] 1) (a) polyphenylene ether or a composition containing polyphenylene ether, and (b) a propylene homopolymer portion and at least one selected from propylene, ethylene, and an α-olefin having 4 to 6 carbon atoms. It has a random copolymer portion consisting of one type of copolymerization component, and the ratio of the propylene homopolymer portion to the random copolymer portion is 90 to 10% by weight/10 to 9
0% by weight, and the ratio of propylene to at least one copolymer component selected from ethylene and α-olefin having 4 to 6 carbon atoms in the random copolymer portion is 85 to 10% by weight/15 to 90 A modified propylene polymer obtained by graft copolymerizing a styrene monomer and/or a mixture of a styrenic monomer and a monomer copolymerizable with the styrene monomer to a raw material propylene polymer of % by weight. Graft efficiency in the graft copolymerization reaction to obtain the graft copolymer [{graft chain partial weight/(homopolymer weight of the monomer + graft chain partial weight)} x 100 (%) ] is 30% or more, and the molecular weight of the graft chain of the modified propylene polymer is 10%.
00 to 200,000 and/or a mixture of the modified propylene polymer and a propylene polymer, and the ratio of component (a) to component (b) is 99 to 1% by weight/1 to 1%.
99% by weight of a thermoplastic resin composition. 2) Reduced viscosity of component (a) polyphenylene ether (
25. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a temperature of 0.20 to 0.60 (in chloroform at 25°C). 3) The monomer copolymerizable with styrene in component (b) is selected from at least one of maleic anhydride, methyl methacrylate, glycidyl acrylate, glycidyl methacrylate, 2-aminoethyl methacrylate, and 2-hydroxyethyl methacrylate. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a monomer containing a monomer. 4) A claim characterized in that the raw material propylene polymer for the modified propylene polymer in component (b) is a highly crystalline propylene polymer in which the isotactic pentad fraction of the boiling heptane insoluble portion is 0.970 or more. Item 1. Thermoplastic resin composition according to item 1. 5) The raw material propylene polymer for the modified propylene polymer in component (b) has an isotactic pentad fraction of the boiling heptane insoluble part of 0.970 or more and a content of the boiling heptane soluble part of 5.0. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is a highly crystalline propylene polymer having a xylene soluble content of 2.0% by weight or less at 20°C. 6) The raw material propylene polymer for the modified propylene polymer in component (b) is a composition obtained by blending a propylene polymer with a vinylcycloalkane polymer having 6 or more carbon atoms, wherein the vinylcycloalkane unit is 2. The thermoplastic resin composition according to claim 1, wherein the composition contains a propylene polymer in an amount of 0.05 wtppm to 10000 wtppm.