JPH055034A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition suitable for parts requiring strength and heat resistance such as parts of automobile, having excellent heat resistance, chemical resistance, impact resistance and appearance. CONSTITUTION:A thermoplastic resin composition comprising a modified polyphenylene ether subjected to graft copolymerization with an amino group- containing monomer such as aminostyrene and a propylene polymer modified with a compound containing a functional group to be reacted with amino group in the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel thermoplastic resin composition which can be used for molded articles by injection molding or extrusion molding.

[0002]

2. Description of the Related Art Generally, polyphenylene ether is a resin having excellent properties such as heat resistance, hot water resistance, dimensional stability and mechanical and electrical properties, but has a high melt viscosity.
It has drawbacks such as poor moldability, poor chemical resistance, and low impact resistance.

A composition of polyphenylene ether and polystyrene resin is known as a composition for reducing the melt viscosity and improving the molding processability while maintaining the excellent properties of polyphenylene ether, but the chemical resistance is still high. Not improved.

On the other hand, propylene polymer is
Since it has excellent toughness, water resistance, chemical resistance, etc., and has a low specific gravity and is inexpensive, it has been widely used as various molded products, films and sheets.

However, propylene polymers have drawbacks in heat resistance, rigidity, impact resistance, paintability, adhesiveness, etc., or require improvement, and these prevent development of new applications. In particular, improvement in heat resistance and impact resistance is strongly desired.

[0006]

From such a point of view,
If a resin composition having a combination of polyphenylene ether and a propylene polymer and having both characteristics and improved molding processability, impact resistance, etc. is obtained, a wide range of new application possibilities are expected. By the way.

However, in practice, the compatibility is poor even when the propylene polymer is blended with the polyphenylene ether, and the molded product obtained by injection molding or the like undergoes phase separation between the polyphenylene ether and the propylene polymer, resulting in a markedly poor appearance. However, they are inferior in practical use because they are inferior in mechanical properties. However, in the market, a resin composition having high impact resistance and excellent weather resistance while maintaining the excellent heat resistance of polyphenylene ether is required.

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

A composition excellent in heat resistance and mechanical properties can be obtained by blending polyphenylene ether with a propylene polymer obtained by graft-copolymerizing styrene or a mixture of styrene and a monomer copolymerizable with styrene, rubber and the like. What is obtained is disclosed in, for example, JP-A-1-207349 and 1-234462. A resin composition containing an amino group-containing polyolefin and a polar group-containing polyphenylene ether is disclosed in JP-A-2-173137.

However, in some cases, a molded article using the composition does not have sufficient impact resistance, heat resistance, molding processability or the like, or has insufficient elongation, tensile strength or chemical resistance. In some cases, it may be difficult to use the composition depending on the application due to insufficient mechanical properties of the welded part of the injection-molded product, or it may be expensive and the physical properties are low. There was a strong demand from the market for various compositions.

[0011]

The present inventors have found that heat resistance,
The present invention has been achieved as a result of extensive research conducted for the purpose of obtaining a composition having excellent mechanical strength and excellent moldability and chemical resistance.

That is, the present invention provides (A) the following (a)
To (d) a modified polyphenylene ether graft-copolymerized with at least one monomer or a combination of monomers selected from the group consisting of monomers and combinations of monomers, and (B) an amino group It is composed of a propylene polymer modified with a compound having a functional group capable of reacting in the molecule, the component (A) is 99 to 1% by weight, and the component (B) is 1 to 9
It relates to a thermoplastic resin composition of 9% by weight. (A) Amino group-containing styrene-based monomer. (B) Styrene-based monomer and amino group-containing monomer. (C) Amino group-containing styrene-based monomer and styrene-based monomer. (D) Amino group-containing styrene-based monomer and amino group-containing monomer. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.)

The polyphenylene ether as a raw material for the modified polyphenylene ether of the component (A) in the present invention is represented by the general formula 1

[0014]

[Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and at least one of them is a hydrogen atom. The polymer obtained by oxidatively polymerizing at least one of the phenol compounds represented by the formula (1)) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst.

R ₁ , R ₂ , R ₃ , R in the above general formula
Specific examples of ₄ and R ₅ are hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl. , Hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl groups and the like.

Specific examples of the above general formula include phenol, o-, m- and p-cresol, 2,6-, 2,
5-, 2,4-, and 3,5-dimethylphenol,
2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3,5-, 2,3.
6- and 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like can be mentioned. further,
A copolymer of a phenol compound other than the above-mentioned general formula, for example, a polyhydric aromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone, and novolak resin with the above general formula can also be used.

Preferred among these compounds are homopolymers of 2,6-dimethylphenol and 2,6-diphenylphenol, and a large amount of 2,6-xylenol and a small amount of 3-methyl-6-. Examples thereof include copolymers with t-butylphenol or 2,3,6-trimethylphenol.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include cuprous chloride-trimethylamine chloride and catalysts described in JP-A-2-160856 and the like.

There are differences in the physical properties of the polymer obtained when the oxidative polymerization for obtaining polyphenylene ether is carried out at a temperature higher than 40 ° C. (high temperature polymerization) and at 40 ° C. or lower (low temperature polymerization). It is known that either high temperature polymerization or low temperature polymerization can be employed in the present invention.

Component (A) of the thermoplastic resin composition of the present invention
In the above, as the monomer to be graft-copolymerized with the above polyphenylene ether, at least one monomer or a monomer selected from the group consisting of the following monomers (a) to (d) and a combination of monomers. Examples include a combination of monomers. (A) Amino group-containing styrene-based monomer. (B) Styrene-based monomer and amino group-containing monomer. (C) Amino group-containing styrene-based monomer and styrene-based monomer. (D) Amino group-containing styrene-based monomer and amino group-containing monomer. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.)

Here, the amino group-containing styrene-based monomer can be graft-copolymerized with polyphenylene ether,
It means a styrene-based monomer containing an amino group. As the monomer, a styrene-based monomer having a primary or secondary amino group in the molecule is preferably used. In particular,
Aminostyrene and aminomethylstyrene are preferably used. The amino group-containing styrene-based monomer can be used alone or in combination of two or more kinds.

Next, the styrene-based monomer means a compound represented by the general formula 2 except the amino group-containing styrene-based monomer.

[0023]

[Chemical 2] (In the formula, R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and each is a hydrogen atom, a halogen atom, a hydrocarbon or a substituted hydrocarbon group, a hydrocarbon oxy or a substituted hydrocarbon oxy group. And R ₁₁ represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms.).

R ₆ , R ₇ , R ₈ and R _{9 in the} above general formula
And specific examples of R ₁₀ include a hydrogen atom; chlorine, bromine,
Halogen atom such as iodine; Hydrocarbon group such as methyl, ethyl, propyl, vinyl, allyl, benzyl, methylbenzyl; Substituted hydrocarbon group such as chloromethyl, bromomethyl; Hydrocarbon oxy such as methoxy, ethoxy, phenoxy, monochloromethoxy Groups or substituted hydrocarbonoxy groups and the like. In addition, specific examples of R ₁₁ include a hydrogen atom and a lower alkyl group such as methyl and ethyl.

Specific examples of the styrene type monomer include styrene, 2,4-dichlorostyrene, p-methoxystyrene, p-methylstyrene, p-phenylstyrene and p-.
Divinylbenzene, p- (chloromethoxy) -styrene, α-methylstyrene, o-methyl-α-methylstyrene, m-methyl-α-methylstyrene, p-methyl-
Examples include α-methylstyrene and p-methoxy-α-methylstyrene. These may be used alone or in combination of two or more. Of these, styrene is preferably used.

Next, the term "amino group-containing monomer" means a monomer containing an amino group, which can be graft-copolymerized with polyphenylene ether together with a styrene-based monomer. It excludes the body. As the monomer, a monomer having a primary or secondary amino group and a carbon-carbon double bond or triple bond in the molecule is preferably used. Specifically, allylamine, diallylamine, vinylimidazole, allylaniline, acrylamide, methacrylamide, N-phenylmethacrylamide, etc. are preferably used. The amino group-containing monomer may be used alone or in combination of two or more.

As the copolymer component for preparing the modified polyphenylene ether of the component (A) of the thermoplastic resin composition used in the present invention, the above-mentioned monomers or monomers (a) to (d) are used. In addition to the body combination, a monomer copolymerizable with the styrene-based monomer may be used.

Specific examples of the monomer copolymerizable with the styrene-based monomer include acrylonitrile, methacrylonitrile, fumaric acid and maleic acid, vinyl ketone, maleic anhydride, acrylic acid, methacrylic acid, and chloride. Vinylidene, maleic acid ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, glycidyl acrylate, glycidyl methacrylate, butyl methacrylate, methyl acrylate, 2-hydroxyethyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Vinyl chloride, vinyl acetate,
Divinylbenzene, ethylene oxide, vinylidene chloride, maleic acid ester, isobutene, alkyl vinyl ether, anethole, indene, coumarone, benzofuran,
1,2-dihydronaphthalene, acenaphthylene, isoprene, chloroprene, trioxane, 1,3-dioxolane, propylene oxide, β-propiolactone, vinylbiphenyl, 1,1-diphenylethylene, 1-vinylnaphthalene, 2-vinylnaphthalene, 2,3-dimethyl butadiene, ethylene, propylene, allyl trimethyl silane, 3-butenyl trimethyl silane, vinylcarbazole, fumarnitrile, etc. can be mentioned. Further, derivatives of these monomers can also be used. These may be used alone or in combination of two or more.

The method for producing the modified polyphenylene ether in the component (A) of the present invention is not particularly limited, and examples thereof include suspension polymerization method, emulsion polymerization method, solution polymerization method, and bulk polymerization method (in addition to the method using a polymerization tank, Any known method such as a method using an extruder is also applicable.

Specific examples of the method for producing these include Japanese Patent Publication No. 47-47862, Japanese Patent Publication No. 48-12197, Japanese Patent Publication No. 49-5623,
As shown in JP-B-52-38596 and JP-B-52-30991, in the presence of polyphenylene ether,
A method of graft-polymerizing a styrenic monomer and / or another polymerizable monomer can be mentioned.

Alternatively, a method of obtaining a modified polyphenylene ether by melt-kneading a polyphenylene ether, an amino group-containing monomer and the like with a radical initiator as shown below can be mentioned.

Here, the radical initiator used for producing the modified polyphenylene ether is not particularly limited, and a desired one can be appropriately selected and used. For example, various radical initiators such as those described in JP-A-2-160856 can be mentioned, including azo compounds such as 2,2′-azobisisobutyronitonyl.

If desired, an unmodified polyphenylene ether may be blended with the modified polyphenylene ether of the component (A) in the thermoplastic resin composition of the present invention.

The propylene polymer modified with the compound having a functional group capable of reacting with the amino group of the component (B) in the present invention is specifically the compounds (a) to (c) shown below. Examples thereof include those obtained by reacting one or more compounds selected from the group with a propylene polymer.

(A) In the molecule, (I) carbon-carbon double bond or carbon-carbon triple bond and (II) carboxyl group, acid anhydride group, acid amide group, imide group, epoxy group,
A compound having a carboxylic acid ester group, an isocyanate group, a methylol group, a group having an oxazoline ring or a hydroxyl group at the same time.

Specific examples thereof include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic hydrazide, and reaction products of maleic anhydride and diamine, for example,

[0037]

[Chemical 3]

[0038]

[Chemical 4]

(Wherein R represents an aliphatic or aromatic group) and the like, methylnadic acid anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil , Linseed oil, hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil,
Natural oils and fats such as 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, bentenoic acid,
Angelica acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexenoic acid, 2-methyl-2.
-Bentenoic acid, 3-methyl-2-pentenoic acid, α-ethyl crotonic 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-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycoribene acid, 2,4-pentadienoic acid, 2,4-hexadienoic acid, diallylacetic acid, geranium acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9,12-hexadecadienoic acid, 9,12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linolenic acid, octadecatrienoic acid, eicosadienoic acid ,
Eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid Unsaturated carboxylic acids such as hexacodienoic acid, octacocenoic acid and traacontenoic acid, or esters of these unsaturated carboxylic acids, acid amides, anhydrides or allyl alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol, methyl propenyl Carbinol, 4-pentene-
1-ol, 10-undecen-1-ol, propargyl alcohol, 1,4-pentadiene-3-ol,
1,4-hexadiene-3-ol, 3,5-hexadiene-2-ol, 2,4-hexadiene-1-ol, 3-butene-1,2-diol, 2,5-dimethyl-3-hexene- 2,5-diol, 1,5-hexadiene-3,4-diol, 2,6-octadiene-4,
An unsaturated alcohol such as 5-diol, or an unsaturated amine in which an OH group of such an unsaturated alcohol is replaced with a —NH ₂ group, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, or the like can be given.

Among them, maleic anhydride, fumaric acid, itaconic acid, hymic acid anhydride, glycidyl acrylate,
Glycidyl methacrylate and allyl glycidyl ether are preferred.

Further, two or more functional groups of the (I) group, (I
It is also possible to use a compound containing two or more (same or different) functional groups of group I), and it is also possible to use two or more of these compounds. (B) Formula (R ¹ O) m R (COOR ² ) n (CONR ³
R ⁴ ) s [wherein R: alkyl group (carbon number: 2 to 20, preferably 2 to 10) R ¹ : hydrogen, alkyl group, acyl group or carbonyldioxy group (carbon number: 1 to 10, preferably Is 1 to 6, more preferably 1 to 4, and particularly preferably hydrogen), or an aryl group (carbon number: 6 to 20) R ² : hydrogen, an alkyl group (carbon number: 1 to 20, preferably 1 to 10) Or an aryl group (carbon number: 6 to 20) R ³ and R ⁴ : hydrogen, an alkyl group (carbon number: 1 to 1)
0, preferably 1 to 6, more preferably 1 to 4), or an aryl group (carbon number: 6 to 20) m = 1 n + s ≧ 2, preferably 2 or 3 n ≧ 0 s ≧ 0 (R ¹ O) Is located at the α-position or β-position of the carbonyl group,
There are 2-6 carbon atoms in a set of adjacent carbonyl groups. ] The saturated aliphatic polycarboxylic acid represented by these and its derivative compound.

Specific examples thereof include ester compounds, amide compounds, anhydrides, hydrates and salts of saturated aliphatic polycarboxylic acid. Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like. Examples of the acid ester compound include acetyl ester of citric acid, mono- or distearyl ester and the like. As the acid amide compound, citric acid N, N′-diethylamide,
N, N'-dipropylamide, N-phenylamide,
N-dodecylamide, N, N'-di dodecylamide,
Further, N-dodecylamide of malic acid and the like can be mentioned.

(C) General formula X-Z-Y [wherein X is a formula:

[0044]

[Chemical 5] (In the formula, X'is Cl, Br, I, OH, OR, or-
In ^{O-CO-R 5, R} 5 is a group represented by H, an alkyl group or an aryl group), Y is a carboxyl group, acid anhydride group, acid amide group, an imide group, a carboxylic acid ester group Or a hydroxyl group, and the X and Y groups are covalently bonded via a bond Z which is a hydrocarbon].

Specific examples include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride, acetic anhydride, terephthalic acid chloride and the like. Among the compounds listed in (a) to (c) and containing these functional groups in the molecule, particularly preferred are:
An unsaturated dicarboxylic acid anhydride is mentioned.

In the present invention, the amount of the compounds (a) to (c) having at least one functional group in the molecule used for modification is 100 parts by weight of the propylene polymer.
0.01 to 20 parts by weight, preferably 0.1 to 1
0 parts by weight. When the amount of the compound used is less than 0.01 part by weight, the mechanical strength of the thermoplastic resin composition according to the present invention is not sufficient, and when it exceeds 20 parts by weight, the resin composition is colored or the fluidity is deteriorated. It is not preferable because

Regarding the method of reacting the propylene polymer with the modifying compound, a known solvent is used in the presence or absence of a radical initiator, or
There is a method of efficiently performing the reaction by melt-kneading at a temperature at which the propylene polymer is melted in the absence of a solvent, and any method may be used.

In producing the modified propylene polymer of the component (B) of the present invention, a styrene-based monomer can be used together with the compound having at least one kind of functional group in the molecular chain. As the styrene-based monomer, the same styrene-based monomer as used in the production of the component (A) of the present invention can be used. The radical initiator used for producing the modified propylene polymer of the component (B) of the present invention may be the same as the peroxide used for producing the component (A) of the present invention.

Here, the propylene polymer which is a raw material of the modified propylene polymer is a propylene homopolymer or a predominant amount of propylene and other α-carbons having 2 to 18 carbon atoms.
Means random or block copolymers with olefins. Specific examples of the propylene copolymer include ethylene-propylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene. -1
-Octen copolymer etc. can be mentioned.

If necessary, the propylene polymer may be blended with an ethylene-α-olefin copolymer and / or a styrene-modified product of the copolymer.
As the ethylene-α-olefin copolymer to be blended,
Those having a density of 0.82 to 0.92 g / cm ³ are preferably used.

As the propylene polymer, a highly crystalline propylene polymer can be used if necessary. The term "highly crystalline propylene polymer" as used herein means a propylene homopolymer or a block copolymer which is a first segment of propylene polymerized in the first step as described in JP-A 1-247457. The homopolymer part has a boiling heptane-insoluble part with an isotactic pentad fraction of 0.970 or more.

In the field where high rigidity is required, it is preferable to add a known nucleating agent to the propylene polymer. In addition, it is known that a vinyl cycloalkane polymer having 6 or more carbon atoms also acts effectively as a nucleating agent. That is, a composition obtained by blending a propylene polymer with a vinylcycloalkane polymer having 6 or more carbon atoms, which is described in JP-A-1-234462, wherein vinylcycloalkane units are contained in the composition. To 0.
A propylene polymer composition containing 05 wtppm to 10000 wtppm has a higher crystallinity and is therefore preferable. Further, a highly rigid propylene polymer can be obtained by blending the vinyl cycloalkane polymer with the above-mentioned highly crystalline propylene polymer. The propylene polymers (propylene homopolymer and propylene copolymer) can be used alone or in combination of two or more kinds.

If necessary, the component (B) may include an antioxidant, a heat stabilizer, a light stabilizer, a nucleating agent, an antistatic agent, an inorganic or organic colorant, an anticorrosive agent, a crosslinking agent, and a foaming agent. , Various additives such as a lubricant, a plasticizer, a fluorescent agent, a surface smoothing agent, and a surface gloss improver can be added.

Modified polyphenylene ether graft-copolymerized with (A) at least one monomer or a combination of monomers selected from the specific group of the present invention, and (B) a functional group capable of reacting with an amino group. A propylene polymer modified with a compound having in the molecule, for example, a reaction product produced by melt-kneading, in various aspects such as heat resistance, mechanical properties, appearance, is simply a propylene polymer and a modified polyphenylene ether. Or the system in which the interface is formed only by the intermolecular force of the styrene chain in the modified propylene polymer and the modified polyphenylene ether. This action in the present invention is combined with the reaction of the functional group in the modified propylene polymer and the amino group in the modified polyphenylene ether and the intermolecular force of the styrene chain in the modified propylene polymer and the modified polyphenylene ether, and This is considered to significantly improve the binding force at the interface between the modified propylene polymer and the modified polyphenylene ether in the resin composition and the dispersibility of the modified polyphenylene ether.

In the present invention, the desired thermoplastic resin composition can be obtained by setting the composition ratio of the component (A) and the component (B) within a specific range. The ratio of the component (A) to the component (B) in the present invention is 99 to 1% by weight of the component (A) and 1 to 99% by weight of the component (B). If the ratio of the component (A) and the component (B) is less than 1% by weight, the heat resistance of the composition is insufficient,
If it exceeds 99% by weight, the processability and chemical resistance of the composition will be insufficient.

In the resin composition of the present invention, it is more preferable that the component (A) is the dispersed phase and the component (B) is the continuous phase. In this case, the chemical resistance and moldability of the composition are excellent, and the molded article of the composition has a good appearance, which is preferable. In order to realize such a form in the composition, the ratio of the component (A) to the component (B) is 8
It is preferable that the content is 0 to 1% by weight and the component (B) is 20 to 99% by weight. More preferably, the component (A) is 70-
1% by weight, and the component (B) is preferably 30 to 99% by weight.

In the resin composition of the present invention, if necessary, an unmodified polyphenylene ether can be blended with the modified polyphenylene ether of the component (A), and an unmodified polyphenylene ether of the component (B) can be unmodified. A propylene polymer can be blended. Here, the modified polyphenylene ether and the unmodified polyphenylene ether are sufficiently compatible with each other, and the modified propylene polymer and the unmodified propylene polymer are sufficiently compatible with each other. Also in these cases, it is preferable that the compatible polyphenylene ether portion is the dispersed phase and the compatible propylene polymer portion is the continuous phase for the same reason as described above.

When an unmodified propylene polymer is further added to the modified propylene polymer of the component (B) in the thermoplastic resin composition of the present invention, each of the component (A), the component (B) and the unmodified propylene polymer is The ratio of the component (A) is preferably 1 to 90% by weight, the component (B) is 94 to 1% by weight, and the propylene polymer is 5 to 98% by weight. More preferably, the component (A) is 1 to 80% by weight, the component (B) is 94 to 10% by weight, and the propylene polymer is 10 to 89% by weight.

In the resin composition of the present invention, a rubber-like substance is optionally used as the component (C) for the purpose of improving impact resistance. The term "rubber-like substance" as used herein refers to a natural or synthetic polymer material that is elastic at room temperature.

Specific examples thereof include natural rubber, butadiene polymers, butadiene-styrene copolymers (including all random copolymers, block copolymers and graft copolymers), or hydrogenated products thereof. 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 hydrogenated product thereof, styrene-ethylene-butylene copolymer, styrene-butylene copolymer, styrene-ethylene-propylene-copolymer, perfluoro rubber, fluororubber, chloroprene rubber, butyl rubber, Silicone rubber, ethylene-α-o Reffin-non-conjugated diene copolymer, thiochol rubber, polysulfide rubber, polyurethane rubber,
Examples thereof include polyether rubber (eg, propylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and epoxy group-containing copolymer.

The epoxy group-containing copolymer referred to here is
It is a copolymer composed of an unsaturated epoxy compound and an ethylenically unsaturated compound.

The composition ratio of the component (C) to the sum of the component (A) and the component (B) is 0 to 100 parts by weight of the component (A) and the component (B). 60 parts by weight is preferred. 100 by weight of component (A) and component (B)
When the amount of the component (C) exceeds 60 parts by weight based on parts by weight, the heat resistance of the composition is significantly reduced, which is not preferable.

In the thermoplastic resin composition used in the present invention, an inorganic filler is optionally used for the purpose of improving the rigidity and dimensional stability of the molded product. Examples of such an inorganic filler include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, and the like. Among them, talc,
Calcium carbonate is preferably used.

Such an inorganic filler has an average particle size of 0.05 to
Those having a thickness of 10 μm are preferably used. If the particle size is less than 0.05 μm, the effect of improving the dimensional stability and rigidity of the molded product becomes small, and if it exceeds 10 μm, the surface gloss of the molded product is significantly impaired, and the object of the present invention cannot be achieved. Glass fibers can also be used as the inorganic filler.

In the thermoplastic resin composition used in the present invention, a melt fluidity improver can be used, if necessary, in addition to the above components. As the melt fluidity improver, known ones can be used, but preferred examples include white oil, liquid paraffin, low molecular weight hydrocarbon resin, low molecular weight polyolefin and the like, and modified products thereof are also used. can do. As the white oil here, those described in JP-A-2-238051 are used. Liquid paraffin is obtained by distilling crude oil under atmospheric pressure and vacuum distillation, and then removing unsaturated components, aromatic components, sulfur components and the like. As the low molecular weight hydrocarbon resin referred to herein, those described in JP-A-2-160858 can be used. The melt flow improver is
The above-exemplified compounds may be used alone or in combination of two or more.

In carrying out the present invention, if necessary, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant,
Lubricants, antistatic agents, inorganic or organic colorants, rust inhibitors,
Various additives such as a crosslinking agent, a foaming agent, a fluorescent agent, a surface smoothing agent, and a surface gloss improving agent can be added during the manufacturing process or in the subsequent processing process.

To describe the flame retardants in more detail, the flame retardants useful in the present invention include a group of compounds well known to those skilled in the art. Generally, more important compounds among them, such as bromine, chlorine, antimony, phosphorus and nitrogen, which can impart flame retardancy such as those described in JP-A-2-160856, etc. A compound containing an element is used. For example, a halogenated organic compound, antimony oxide, antimony oxide and a halogenated organic compound, antimony oxide and a phosphorus compound, phosphorus alone or a phosphorus compound, a phosphorus compound or a compound having a phosphorus-nitrogen bond and a halogen-containing compound, or two kinds thereof. The above mixture and the like are used.

The method for producing the thermoplastic resin composition according to the present invention is not particularly limited, and a commonly known method can be used. For example, a method of mixing in a solution state and evaporating a solvent or precipitating in a non-solvent is effective, but from an industrial point of view, a method of actually kneading in a molten state is preferable. For melt kneading, generally used kneading devices such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.

At the time of kneading, it is preferable that the respective components are preliminarily uniformly mixed by a device such as a tumbler or a Henschel mixer, but if necessary, the mixing may be omitted, and a fixed amount may be separately supplied to the kneading device. Can be used. The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but without undergoing the kneading process in advance, it is dry-blended during injection molding or extrusion molding and kneaded during the melt processing operation. Alternatively, the resin composition of the present invention can be used to directly obtain a molded product. In the present invention, the kneading order is not particularly limited, and the components (A), (B) and (C) may be kneaded together, or after the components (A) and (B) are kneaded in advance, Then, the component (C) may be kneaded. In addition, other kneading orders are possible.

[0070]

The thermoplastic resin composition obtained by the method of the present invention is a resin composition excellent in heat resistance, melt flowability, processability, chemical resistance, impact resistance, appearance and gloss. It is used for molded articles, sheets, tubes, films, fibers, laminates, coating materials and the like by injection molding or extrusion molding by taking advantage of such characteristics.

In particular, automobile parts such as bumpers, glove boxes, console boxes, brake oil tanks, radiator grills, cooling fans, lamp housings, air cleaners, instrument panels,
Used for interior / exterior materials such as fenders, door trims, rear end trims, door panels, wheel covers, side protectors, air intakes, garnishes, trunk lids, bonnets, sirocco fans, roofs, and mechanical parts that require heat resistance. .. Further, it is used as a motorcycle component, for example, a covering material, a muffler cover, a leg shield and the like. Further, it is used for optical fiber cable coating materials, and also as electric and electronic parts for housings, chassis, connectors, printed circuit boards, pulleys, and other parts required to have strength and heat resistance.

[0072]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. In addition, polyphenylene ether is PPE,
The propylene polymer is sometimes abbreviated as PP.

(I) Method of measuring physical properties The physical properties were measured using a twin-screw extruder at a cylinder temperature of 260 to 33.
After kneading the composition at 0 ° C, use IS 150 manufactured by Toshiba Machine Co., Ltd.
Molding temperature 260 ℃ ～ 330 using EV type injection molding machine
C., mold temperature 70 to 140.degree. Deflection temperature test under load (HDT) is JIS K72
07, Izod impact strength (thickness 3.2 mm) is JIS K
Measured according to 7110. The reduced viscosity (η _SP / c) of polyphenylene ether is a value measured at 25 ° C. with a chloroform solution of 0.5 g / dl solution. The melt flow index (MI) of the propylene polymer was measured according to JIS K6758 at a temperature of 230 ° C. and a load of 2.16 kg. Flexural modulus was measured on injection molded articles according to ASTM D790. The appearance of the injection-molded product was evaluated according to the following criteria. ◯: The appearance is beautiful, and no flow mark or color tone change is observed. X: Flow marks and color tone changes are observed on the surface of the molded product.

The morphology of the composition was observed as follows.
The injection molded product is cut with a microtome and etched with carbon tetrachloride. It was observed using a scanning electron microscope and classified as follows. A: Polyphenylene ether part (modified PPE and unmodified PPE) is dispersed phase, propylene polymer part (modified PPE)
P and unmodified PP) are continuous phases. B: The polyphenylene ether portion is a continuous phase and the propylene polymer is a dispersed phase.

(II) Raw materials used The following is a radical initiator under the trade name of Perbutyl P
V (manufactured by Miyoshi Yushi Co., Ltd.) and a trade name, Metroze 90SH-100 (manufactured by Shin-Etsu Chemical Co., Ltd.) were used. (1) Modified polyphenylene ether as component (A) (i) η _SP /c=0.50 manufactured by Nippon Polyether Co., Ltd. Polyphenylene ether 100 parts by weight, diallylamine 4.3 parts by weight, and styrene 8 parts by weight as a radical initiator and a stabilizer. The resulting mixture was mixed with a Henschel mixer, and then granulated at a cylinder temperature of 303 ° C. using a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. to obtain modified polyphenylene ether. Hereinafter, the modified polyphenylene ether is abbreviated as A-1.

(Ii) 100 parts by weight of polyphenylene ether manufactured by Nippon Polyether Co., Ltd. having η _SP /c=0.30, 12 parts by weight of aminostyrene, 3 parts by weight of glycidyl methacrylate, and 400 parts by weight of water together with a radical initiator and a dispersant. The mixture was put into an autoclave and reacted at 97 ° C for about 1 hour to obtain a modified polyphenylene ether. Hereinafter, the modified polyphenylene ether is abbreviated as A-2.

(2) Modified propylene polymer of component (B) (i) 100 parts by weight of block polypropylene (MI = 8.8), 3 parts by weight of styrene, and 9 parts by weight of maleic anhydride together with a radical initiator and a stabilizer, together with a Henschel mixer. After mixing using the above, the mixture was charged into a twin-screw kneading extruder and kneaded at a cylinder temperature of 250 ° C. in a nitrogen atmosphere to obtain a modified propylene polymer. Hereinafter, the modified propylene polymer is abbreviated as B-1.

(Ii) Homopolypropylene (MI = 4.
5) 100 parts by weight, random polypropylene (MI = 12.
5) 12 parts by weight, 24 parts by weight of styrene, 9 parts by weight of glycidyl acrylate, and 400 parts by weight of water were put into an autoclave together with a radical initiator and a surfactant, and reacted at 92 ° C for 1 hour under a nitrogen atmosphere. After the composition obtained here is recovered and dried, 100 parts by weight of the composition, 5 parts by weight of citric acid, and 1 part by weight of styrene are charged into a twin-screw kneading extruder together with a radical initiator and a stabilizer, and the temperature of the cylinder is adjusted. Kneading was performed at 250 ° C. to obtain a modified propylene polymer. Hereinafter, the modified propylene polymer is abbreviated as B-2.

(3) Rubber-like substance of component (C) Abbreviation Content C-1: Maleic anhydride ethylene / propylene rubber obtained by reacting ethylene propylene rubber (EPR) with maleic anhydride C-2: Ethylene -Epoxy acrylate copolymer, trade name Bondfast 2B [Sumitomo Chemical Co., Ltd.] C-3: Styrene-butadiene-styrene block copolymer, trade name Clayton TR1102 [Shell Chemical Co., Ltd.] C-4 : Ethylene-propylene-diene rubber, trade name Sumitomo Esplen E301 [Sumitomo Chemical Co., Ltd., ML _{1 + 4} 100 ° C. = 56] C-5: styrene-ethylene-propylene block copolymer, trade name Kraton G1701X [shell Chemical Co., Ltd.]

Examples 1 to 5 and Comparative Examples 1 to 4 Each component was blended and kneaded with the compositions shown in Table 1 and Table 2 and the physical properties were measured. The obtained results are shown in Tables 1 and 2.

[0081]

[Table 1]

[0082]

[Table 2]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masashi Yamamoto 5-1 Anezaki Kaigan, Ichihara City, Chiba Sumitomo Chemical Co., Ltd.

Claims (1)

Claims: (A) At least one selected from the group consisting of the following monomers (a) to (d) and combinations of monomers.
One monomer or a combination of monomers is composed of a graft-copolymerized modified polyphenylene ether, and (B) a propylene polymer modified with a compound having a functional group capable of reacting with an amino group in the molecule. A) is 99-1
A thermoplastic resin composition containing 1% by weight to 1% to 99% by weight of component (B). (A) Amino group-containing styrene-based monomer. (B) Styrene-based monomer and amino group-containing monomer. (C) Amino group-containing styrene-based monomer and styrene-based monomer. (D) Amino group-containing styrene-based monomer and amino group-containing monomer. (However, the above-mentioned styrene-based monomer and amino group-containing monomer exclude amino group-containing styrene-based monomers.)