JPH0362849A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent heat resistance, mechanical and electric properties, moldability and chemical resistance, etc., by mixing polyphenylene ether with a specific styrene-modified propylene polymer or the mixture of said modified propylene polymer and propylene polymer. CONSTITUTION:(A) 1-98wt.% polyphenylene ether (composition) having 0.2-0.45 reduced viscosity, preferably single polymer of 2,6-diphenylphenol, etc., is mixed with (B) 99-2wt.% a composition having 10-100g/10min melt index (230 deg.C and 2-16kg load), composed of B1: modified polymer grafted of 0.2-200 pts.wt. styrenic monomer or mixture of said monomer and copolymerizable monomer to 100 pts.wt. propylene polymer or B2: mixture of B1 and propylene polymer. Then, 100 pts.wt. resultant mixture is mixed with (C) 0-50 pts.wt. rubbery substance (preferably ethylene-propylene rubber, etc.) to afford the objective composition.

Description

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

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

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

U.S. Pat.
189411@, described in British Patent No. 1344729.

Further, in order to reduce the melt viscosity of a polyphenylene ether resin composition, the addition of petroleum-derived low molecular weight resin, rosin resin, etc. is described in JP-A-55-118956.

A technique for reducing the melt viscosity of polyphenylene ether by blending an aromatic hydrocarbon resin derived from cracked naphtha with the polyphenylene ether was also published in Japanese Patent Publication No. 1983-
No. 13584.

These inventions are aimed at improving the fluidity of polyphenylene ether resin compositions, but on the other hand, they have the drawback of significantly lowering the heat resistance of polyphenylene ether resins.

Moreover, it did not improve the chemical resistance of the polyphenylene ether resin composition.

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

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

From this point of view, if a resin composition that has the characteristics of both polyphenylene ether and propylene polymer and has improved moldability and impact resistance can be obtained, it would have the potential for a wide range of new uses. This is expected.

However, in reality, even if propylene polymer is blended with polyphenylene ether, the compatibility is poor, and molded products obtained by injection molding, etc., have phase separation between polyphenylene ether and polypropylene, resulting in extremely poor appearance. , and its mechanical properties are also poor, making it unsuitable for practical use.

As a method for improving the compatibility between polyphenylene ether and propylene polymer, as described in JP-A-49-75663, a propylene polymer obtained by graft copolymerizing a styrene monomer with polyphenylene ether is blended. There is a way.

However, this method does not yield a composition that is excellent in both heat resistance and impact resistance.

Furthermore, as disclosed in Japanese Patent Application No. 63-33445, a composition with excellent mechanical properties can be obtained by blending a propylene polymer obtained by graft copolymerizing a styrene monomer with polyphenylene ether and a rubber-like substance. However, this method has problems such as color separation of injection molded products, which is thought to be due to insufficient melt flowability of the resin composition.

Furthermore, as a method for improving the melt fluidity of a polyphenylene ether composition, as described in Japanese Patent Application No. 63-314863, a low molecular weight hydrocarbon resin is added to a composition consisting of a polyphenylene ether, a modified propylene polymer, and a rubber-like substance. There are methods to improve melt fluidity by blending white oil, liquid paraffin, etc. as described in Japanese Patent Application No. 1-60319, but these methods This was not necessarily preferable because the mechanical properties of the composition deteriorated and bleeding phenomena occurred.

Another method of improving the flow properties of the composition is to lower the molecular weight of the modified propylene polymer.

However, simply lowering the molecular weight of the modified propylene polymer is undesirable because the heat resistance of the composition decreases.

[Means for Solving the Problems 1] In view of these points, the present inventors conducted extensive and detailed exploratory research in order to develop an effective technology, and as a result, the reduced viscosity (η3p/C) was found to be 0.20. ~0.45 polyphenylene ether at 230°C based on JIS K6758
, by blending a modified propylene polymer or a mixture of a modified propylene polymer and a propylene polymer at a load of 2.167<g from Null 1 to index 10 to 100 g/10 min, heat resistance, melt flowability, and processability can be improved. The present invention has been achieved by successfully obtaining a thermoplastic resin composition that has excellent chemical resistance, impact resistance, appearance, and gloss, and has a well-balanced heat resistance, mechanical properties, and moldability.

That is, the present invention provides: 1) (a) reduced viscosity (773,/C) of 0.20 to 0;
．． 45 polyphenylene ether or a composition comprising the polyphenylene ether, (b) 230°C according to J Is K6758
, the melt index at a load of 2.16 kg is 10.
~10Qg/10m1n (i) a modified propylene polymer obtained by graft copolymerizing a styrene monomer, and/
or a modified propylene polymer obtained by graft copolymerizing a mixture of a styrenic monomer and a monomer copolymerizable with the styrenic monomer, or (ii) a mixture of the modified propylene polymer and a propylene polymer, and (c) Consisting of a rubber-like substance, the ratio of component (a) to component (b) is
) is 1 to 98% by weight, component (b) is 99 to 2% by weight, and component (c) is 0 to 50 parts by weight based on 100 parts by weight of the total amount of components (a) and (b). 2) A thermoplastic resin composition characterized in that the polyphenylene ether of component (a) has the general formula (wherein R1, R2, R3, R4 and R5 are the same or different, each hydrogen atom , halogen atom,
Represents a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group. However (), R1
One of ~R5 is always hydrogen. The thermoplastic resin composition of 1) above is a polyphenylene ether obtained by oxidative coupling polymerization of one or more of the phenolic compounds represented by the following.

Reduced viscosity (η
8. /C) is 0.5! ? /d is the value measured at 25°C for a chloroform solution of Il solution, and is the melt index (hereinafter abbreviated as MI).
Based on S K675B 230℃, load 2.16
Value measured in Kg (unit: g/10 m1n)
It is.

The polyphelene ether of component (a) used in the present invention has the general formula [I] , halogen atom,
Represents a hydrocarbon group, a substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group. However, R1-
One of R5 is always hydrogen. It can be obtained by oxidative polymerization using oxygen or an oxygen-containing gas using one or more of the phenol compounds represented by the following and an oxidized Cup 1-Nong catalyst.

R1, R2, R3, R4 and R5 in the above general formula
Specific examples include hydrogen atom, chlorine atom, bromine atom, fluorine atom, iodine atom, methyl, ethyl, n- or 1
Examples include so-propyl, prSeC- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethylnylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl and allyl groups. .

Specific examples of the phenolic compounds represented by the above general formula include phenol, 〇-, m-, 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.

1 5-, 2,3.6- or 2.4.6-dolimethylphenol, 3-methyl-6-t-butylphenol, dimole, 2-methyl-6-allylphenol and the like.

In general, 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 rusorcin, hydroquinone, or novolac resin.

Among these compounds, 2 is preferred.

6-dimethylphenol (2,6-xylenol) or a homopolymer of 2,6-diphenylphenol and a major part of 2,6-xylenol and a minor part of 3-methyl-6
Copolymers of -t-butylphenol or 2,3,6-drimethylphenol can be mentioned.

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

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

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

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

For example, in the presence of an ethylene-propylene-polyene terpolymer, phenols represented by the general formula (each symbol in the formula has the same meaning as above) are oxidatively polymerized, or in the presence of polystyrene (the general formula) (Each symbol in the formula has the same meaning as above.) Oxidative polymerization of phenols represented by the formula, polyphenylene ether polymer or copolymer in the presence of styrene and/or
or organic peroxide craft 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, Japanese Patent Publication No. 52-1982) -30991 etc.>
, the above-mentioned polyphenylene ether polymer or copolymer and polystyrene-based polymer are kneaded and reacted together with a radical generator (peroxide, etc.) in an extruder (Japanese Patent Laid-Open No.
2-142799 @), etc.

The styrenic monomer used for graft copolymerization with polyphenylene ether has the general formula [n]5 (wherein R6, R7, R8, and RIO are the same or different, and each has a hydrogen atom, halogen atom,
It represents a hydrocarbon or substituted hydrocarbon group, a hydrocarbon oxy group, or a substituted hydrocarbon oxy group, and R11 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. ).

Specific examples of R6, R7, R8, R and R10 in the above general formula [II] 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 R11 include a hydrogen atom; a lower alkyl group such as methyl and ethyl;

Specific examples of styrene monomers include styrene, 62,4-dichlorostyrene, p-methoxystyrene, p-
-Methylstyrene, p-phenylstyrene, p-divinylbenzene, p-(chloromethoxy>-styrene, α-
Methylstyrene, ○-methyl-α-methylstyrene, m
-Methyl-α-methylstyrene, ρ-methyl-α-methylstyrene, p-methoxy-α-methylstyrene, and the like. These can be used alone or in combination of two or more.

Among these, styrene is preferably used.

The reduced viscosity of the component (a) in the present invention is in the range of 0.20 to 0.45.

If the reduced viscosity is less than 0.20, the heat resistance of the composition will be insufficient, and if it exceeds 0.45, the mechanical properties of the composition will deteriorate or the melt fluidity will be insufficient, which is not preferred.

The resin composition containing polyphenylene ether as component (a) in the present invention is a resin composition comprising the above-mentioned polyphelene ether, an alkenyl aromatic resin and/or a rubber-modified alkenyl aromatic resin.

The alkenyl aromatic resin in the present invention is defined by the general formula [wherein R13 represents a hydrogen atom, a lower alkyl group (for example, an alkyl group having 1 to 4 carbon atoms], or a halogen atom, and Z represents a hydrogen atom, a vinyl group, It represents a halogen atom, a hydroxyl group or a lower alkyl group, and p represents O or an integer of 1 to 5. ] is selected from those having at least 25% by weight of polymer units derived from monomers having the following.

Specific examples of alkenyl aromatic resins include homopolymers such as polystyrene, bo-1-chlorostyrene, and poly-α-methylstyrene, and copolymers thereof, styrene-containing copolymers, such as styrene-acrylonitrile copolymers, Examples include styrene-divinylbenzene copolymer, styrene-acrylonide 8lylu-α-methylstyrene copolymer, and the like.

Among these, preferred are homopolystyrene, styrene-α-methylstyrene copolymer, styrene-acrylonitrile copolymer, styrene-α-chlorostyrene copolymer, and styrene-methylmethacrylate copolymer. Particularly preferred is homopolystyrene.

The rubber-modified alkenyl aromatic resin in the present invention refers to one that forms a two-phase system in which rubber particles are dispersed in an alkenyl aromatic resin matrix.

This manufacturing method includes mechanical mixing of the rubber-like substance (c) and the alkenyl aromatic resin, which will be described later, or dissolving the rubber-like substance in the alkenyl aromatic monomer, and then polymerizing the alkenyl aromatic monomer. There is a way. The latter method is produced industrially as so-called i1 impact polystyrene. Furthermore, mixtures of rubber-like substances and/or alkenyl aromatic resins with those obtained by the latter method are also included in the rubber-modified alkenyl aromatic resins of the present invention.

The mixing ratio of polyphenylene ether and alkenyl aromatic resin and/or rubber modified alkenyl aromatic resin is, for example, 1 to 99% by weight of polyphenylene ether and 99 to 1% by weight of alkenyl aromatic resin and/or rubber modified alkenyl aromatic resin. It can be varied widely within a range. Within this range, the optimum composition is determined depending on each purpose and use.

In the thermoplastic resin composition of the present invention, in addition to component (a) as described above, component (b) has an MI of 10 to 100.
(1) a modified propylene polymer obtained by graft copolymerizing a styrenic monomer or a mixture of a styrenic monomer and a monomer copolymerizable with the styrenic monomer, or (ii) the above-mentioned A composition containing a modified propylene polymer and a propylene polymer is used.

The modified propylene polymer herein refers to styrenic monomer or styrene monomer and monomer copolymerizable with styrene monomer per 100 parts of propylene polymer. ~200 parts by weight, preferably 2~
It is obtained by graft copolymerization of 90 parts by weight.

If the amount of the monomer to be graft copolymerized is less than 0.2 parts by weight, no resin modification effect will be observed, and if it exceeds 200 parts by weight, the harmful chemical properties will decrease.

Here, the propylene polymer means a propylene homopolymer or a propylene copolymer, and the propylene copolymer means a random or block copolymer of propylene and another α-olefin having 2 to 18 carbon atoms. It means union.

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.

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

1 The highly crystalline propylene polymer referred to here refers to the isotactic pentad portion of the butane-insoluble portion of the propylene homopolymer, which is the first segment polymerized in the first step of the propylene homopolymer or block copolymer. The isotactic pentad fraction of the boiling hebutane insoluble part of the homopolymer part of the propylene polymer is 0.970 or more, and the content of the boiling hebutane soluble part is 5. .0% by weight or less, and the content of the xylene soluble portion at 20° C. is 2.0% by weight or less.

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

In particular, for fields where MI is high and high rigidity is required, the method described in JP-A-56-2307, JP-A-56-104909, JP-A-56-104910, JP-A-56-107407, etc. Preferably, a highly crystalline propylene polymer is used.

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

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. 1738/1988).

Of course, it is a composition obtained by blending a propylene polymer with a vinylcycloalkane polymer having 6 or more carbon atoms, and the vinylcycloalkane unit is contained in the composition at 0.0%.
A propylene polymer composition containing 5 Wtpp to 110,000 Wtpp has higher crystallinity.

Furthermore, a highly rigid propylene polymer can be obtained by blending the vinylcycloalkane polymer with the aforementioned highly crystalline propylene polymer.

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

In the component (b) of the present invention, the styrenic monomer used to modify the propylene polymer by graft copolymerization with the propylene polymer is represented by the above-mentioned general formula [n], One kind or a mixture of two or more kinds thereof can be used.

Among them, styrene is preferably used.

The graft copolymer component for preparing the modified propylene polymer as component (b) in the present invention includes, in addition to the above-mentioned styrenic monomer, the above-mentioned styrenic monomer and a monomer copolymerizable therewith. A mixture of can be used.

By appropriately selecting a monomer that can be copolymerized with a styrene monomer and graft-copolymerizing it with a propylene polymer, a thermally It is possible to obtain plastic resin.

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, butyl methacrylate,
Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl chloride, vinyl acetate, divinylbenzene, ethylene oxide, glycidyl acrylate, glycidyl methacrylate, vinylidene chloride, maleate ester, isobutyne, alkyl vinyl ether, anethole, indene, Coumarone, benzofuran, 1
, 2-dihydronaphthalene, acenaphthylene, isoprene, chloroprene, trioxane, 1,3-dioxolane, pyrene oxide, β-propiolactone, vinylbiphenyl, 1,1-diphenylethylene, 1-vinylnaphthalene, 2-vinyl naphthalene, 2-vinylpyridine,
4-vinylpyridine, 2゜3-dimethylbutadiene, ethylene, propylene, allyltrimethylsilane, 3-butenyltrimethylsilane, vinylcarbazole, N,N
- Diphenylacrylamide, fumaronitrile, etc. can be mentioned. 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 glycidyl methacrylate and glycidyl acrylate.

In the present invention, the mixing ratio of the styrene monomer and the monomer copolymerizable with the styrene monomer can be arbitrarily changed depending on the purpose, but the styrene monomer is 1 to 1
00% by weight is preferred.

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

For example, a method in which a propylene polymer, a graft monomer, and a peroxide are mixed and grafted by melt kneading in a melt mixing equipment, or a method in which a propylene polymer is dispersed in water together with a craft monomer, and then a peroxide is mixed in a nitrogen atmosphere. In addition, a grafted propylene polymer is obtained by heating and reacting with stirring, cooling after the reaction, washing and filtration, and drying, other methods in which the propylene polymer is irradiated with ultraviolet rays or radiation in the presence of a graft monomer, or oxygen. There are methods such as contacting with ozone.

Further, the styrene monomer and the monomer copolymerizable with the styrene monomer can be copolymerized by a known appropriate method, and then graft copolymerized with the propylene polymer.

For example, when graft copolymerizing a mixture of a styrenic monomer and an acrylic ester to a propylene polymer,
First, a copolymer of a styrene monomer and an acrylic ester is produced by anionic polymerization, and then a modified propylene polymer is obtained by melt-kneading this copolymer and a propylene polymer with peroxide. Alternatively, it can be obtained by copolymerizing a 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.

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 -trimethylcyclohexanone peroxide, 2,2-his(t-butylperoxy)butane, t-butyl hydroperoxide, 8 cumene hydroperoxide, diinpropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5 -cybidrobar oxide, di-t-butyl peroxide, 1,3-dos<t-butylperoxyisopropyl>benzene, 2,5-dimethyl-2,5-di(t-butylperoxy>hexane), 2. 5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, lauroyl peroxide, 3.3.5-trimethylhexanoyl peroxide, benzoyl peroxide, t-butyl peracetate, t-butyl peroxide Oxyisobutyrate, t-butyloxypivale-1~, t-butyl-oxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy Oxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxymaleic acid, t-butylperoxy Examples include various organic peroxides such as oxypropyl carbonate and polystyrene peroxide.

The MI of the modified propylene polymer or the mixture of the modified propylene polymer and the propylene polymer as component (b) in the present invention is in the range of 10 to 100.

If the MI is less than 10, the melt flowability of the composition is insufficient, the heat resistance and mechanical properties are not necessarily sufficient, and the MI
If it exceeds 100, the heat resistance of the composition will be insufficient, which is not preferable.

Component (b) in the resin composition of the present invention is a propylene polymer modified with the above-mentioned styrene monomer or a mixture of the styrene monomer and a monomer copolymerizable with the monomer. However, if necessary, an ethylene-α-olefin copolymer modified with a styrene monomer and/or an unmodified propylene polymer, or an ethylene-α-olefin copolymer is used at the same time as this modified propylene polymer. Coalescing can be combined.

Specific examples of unmodified propylene polymers include propylene homopolymers, ethylene-propylene copolymers and propylene-1-butene copolymers mentioned earlier in the explanation of modification with styrene monomers. , propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, propylene-1-octene copolymer, and the like.

In addition, α- which constitutes the ethylene-α-olefin copolymer
Specific examples of the olefin monomer include α-olefins (excluding propylene) corresponding to the above-mentioned propylene copolymers.

The density of the unmodified polymer of the ethylene-α-olefin copolymer to be blended is 0.82-0.
929/cm3 is preferably used.

The blending amount is 1 to 40 parts by weight per 100 parts by weight of the modified propylene polymer and/or propylene polymer of component (b).
Parts by weight.

By blending such components, the impact resistance of the resin composition can be improved.

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

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

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

Specific examples include natural rubber, butadiene polymer dipolymer, butadiene-styrene copolymer (including all random copolymers, block copolymers, graft copolymers, etc.), hydrogenated products thereof, and isoprene polymers. Union,
Chlorobutadiene polymer, butadiene-acryloni 1~
Lyle group type polymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic ester copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene-styrene copolymer Polymer, styrene-isoprene copolymer or its hydrogenated product, styrene-butylene copolymer, styrene-ethylene-propylene copolymer, perfluoro rubber, fluororubber, taloloprene rubber, butyl rubber, silicone rubber, ethylene-propylene-non- Examples include conjugated diene copolymers, thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (eg, propylene oxide, etc.), epichlorohydrin rubber, polyester elastomers, polyamide elastomers, and epoxy group-containing copolymers.

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

Although there is no particular limitation on the composition ratio of the epoxy group-containing copolymer,
Copolymerization of 0.1 to 50% by weight, preferably 1 to 30% by weight of an unsaturated epoxy compound is preferred.

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

For example, unsaturated glycidyl esters and unsaturated glycidyl ethers represented by general formulas (I [I) and (IV>) are listed below.

(In the formula, R has 2 to 2 carbon atoms and has an ethylenically unsaturated bond.
18 hydrocarbon groups. ) 4 (wherein, the number of carbon atoms having an ethylenically unsaturated bond is 2 to
18 hydrocarbon group, X is -C, -〇 Specific examples of compounds represented by the above general formula include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl esters, allyl glycidyl ether, 2-methylallyl glycidyl Examples include ether, styrene-p-glycidyl ether, and the like.

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

More specifically, ethylene, propylene, butylene-1, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, dimethyl maleate, diethyl fumarate, vinyl chloride, polypylene chloride, styrene,
Acrylonitrile, isobutyl vinyl ether, acrylamide and the like can be mentioned.

Among these, ethylene is particularly preferred.

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

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

Furthermore, rubber particles having various degrees of crosslinking, microstructures of various proportions (for example, cis structure, 6 cis structure, vinyl groups, etc.), or rubber particles having various average rubber particle sizes are also used.

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

The ethylene-α-olefin copolymer rubber includes ethylene and other α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, etc. copolymer rubber or terpolymer rubber such as ethylene-propylene-1-butene copolymer, among others, ethylene-propylene copolymer rubber is preferably used.

7 The ethylene content in these ethylene-α-olefin copolymer rubbers is 15 to 85% by weight, preferably 40 to 80% by weight. In other words, highly crystalline copolymers with an ethylene content of more than 85% by weight are difficult to process under normal rubber molding conditions, and those with an ethylene content of less than 15% by weight have an elevated glass transition point (Tg) and are difficult to process under normal rubber molding conditions. This is undesirable because the physical properties deteriorate. The preferred glass transition temperature is -10'
C or lower.

Ethylene-α-olefin-non-conjugated diene copolymer rubber is also preferred, but in this case the non-conjugated diene content is reduced to 2.
It is desirable that the content be 0% by weight or less. If the non-conjugated diene content exceeds 20% by weight, it is not preferable because fluidity deteriorates due to gelation during crosstalk. Preferred non-conjugated dienes include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene.

The number average molecular weight of these copolymer rubbers is preferably in the range of 1oooo to 1ooooo in order to facilitate kneading in an extruder. If the molecular weight is too small, it will be difficult to handle when feeding it to an extruder, and if the molecular weight is too large, fluidity will be low and processing will be difficult.

Also, Mooney viscosity (ML1+4121°C> or 5 to 1
Preferably, it is 20.

The molecular weight distribution is not particularly defined, but the preferred range is that the Q value (weight average molecular weight/number average molecule @) is 1.
-30, more preferably 2-20.

In the present invention, as a modified ethylene-α-olefin copolymer rubber preferable as the rubber-like substance of component (c), an unsaturated dicarboxylic acid is grafted using the above-mentioned ethylene-α-olefin copolymer rubber as a raw material. Examples thereof include unsaturated dicarboxylic acid-modified ethylene-α-olefin copolymer rubber.

The unsaturated dicarboxylic acid mentioned here is maleic anhydride,
Examples include maleic acid, fumaric anhydride, cylinic anhydride, and the like.

Any conventionally known method can be used to produce the modified ethylene-α-olefin copolymer rubber.

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

Modified rubber can also be obtained by kneading maleic anhydride and a radical initiator with ethylene-α-olefin copolymer rubber in an extruder. For example, 0% maleic anhydride is added to 100 parts by weight of rubber. .5~1
A modified rubber can be obtained by using 5 parts by weight and 0.005 to 1.0 parts by weight of a radical initiator and kneading at 150°C to 300°C for several minutes to several tens of minutes. At this time, a gelling inhibitor, for example a phenolic antioxidant such as BHT, may be used in combination, if necessary.

In the present invention, the maleic anhydride modified ethylene-α
- In addition to the olefin copolymer rubber, various other modified ethylene-α-olefin copolymer rubbers can be used, such as methyl acrylate, methyl methacrylate allyl glycidyl ether, glycidyl methacrylate, glycidyl It is also possible to use a modified ethylene-α-olefin copolymer rubber modified with a monomer compound selected from acrylates and the like.

Furthermore, a modified ethylene-α-olefin copolymer rubber containing two or more of these monomer compounds can also be used.

Furthermore, two or more rubbers selected from ethylene-α-olefin copolymer rubber and various modified ethylene-α-olefin copolymer rubbers can be used simultaneously.

Note that the modified tyrene-α-olefin copolymer rubber grafted with a styrene monomer can be obtained by the following method in addition to the method described above.

That is, after dispersing chopped ethylene-α-olefin copolymer rubber or pellets in pure water together with a dispersant, and impregnating the copolymer rubber with a styrene monomer, a radical initiator is used to disperse the ethylene-α-olefin copolymer rubber. 50'C~150'C,'l
By reacting for up to 5 hours, a modified ethylene-α-olefin copolymer rubber grafted with a styrene monomer is obtained.

Rubber-like substances preferably used as component (c) include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, styrene-modified copolymers thereof, butadiene-styrene copolymers, and hydrogenated copolymers thereof. Things, etc.

The rubber-like substance as component (c) can be used in an amount of 0 to 50 parts by weight based on 100 parts by weight of the total amount of components (a) and (b).

If the rubber-like substance exceeds 50 parts by weight, the excellent properties originally possessed by polyphenylene ether will be weakened, which is not preferable.

Other polymer compounds may be added to the thermoplastic resin composition of the present invention. Examples of other polymeric compounds include polyolefins such as polymethylpentene (excluding polypropylene and modified polypropylene).
Homopolymers and copolymers of various vinyl compounds such as polyvinyl chloride, polymethyl methacrylate, polyvinyl acetate, polyvinyl pyridine, polyvinyl carbazole, polyacrylamide, polyacrylonitrile, edylene-vinyl acetate copolymer, alkenyl aromatic resin; Polycarbonate, polysulfone, polyethylene terephthalate, polybutylene terephthalate, polyarylene ester (for example, trade name U Polymer (manufactured by Unitika)
), polyphelene sulfide; 6-nylon, 6,6-
Examples include polyamides such as 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.

When carrying out the present invention, reinforcing agents such as glass fiber and carbon fiber, carbon black, silica, Ti
It is also possible to add and knead inorganic and organic fillers such as 02, plasticizers, stabilizers, flame retardants, dyes and pigments.

To explain in more detail about reinforcing agents, what are reinforcing agents?
By blending it, mechanical or thermal properties such as flexural strength, flexural modulus, tensile strength, tensile modulus, and heating deformation temperature are increased. For example, alumina fiber, carbon fiber, glass fiber, high Examples include elastic polyamide fibers, high elastic polyester fibers, silicon carbide fibers, and titanate voice cars.

It is sufficient that the amount of these reinforcing agents is at least effective for reinforcing, but generally the composition 1 of the present invention
A range of about 5 to 100 parts by weight is preferred.

4 A particularly preferred reinforcing filler is glass, with the use of glass mu filaments consisting of lime-aluminum borosilicate glass having a relatively low sodium content being preferred. This is known as "Σ" glass. but,
Other glasses, such as low sodium content glasses known as rCJ glasses, are also useful when electrical properties are less important. Filaments are made by common methods such as steam or air blowing, flame blowing and mechanical stretching. Preferred filaments 1 for reinforcing plastics are produced by mechanical tension. The filament diameter ranges from about 2μ to 20μ, but this is not critical for the present invention. Regarding the length of the glass filaments and how they are bundled into aggregates fi/AM, and how these bundled aggregate fibers are further bundled as threads, lobes or rovings, or woven into mats etc.
In the present invention, this is not a strict matter. However, when making the compositions in the present invention, lengths of about 50.3 cm to about 3 cm, preferably about 0.6
It is convenient to use glass filaments in the form of short cut strands with a length of less than cm.

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

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

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

The amount of flame retardant additive is not critical, as long as it is sufficient to impart flame retardancy. It is not a good idea to add too much as this will impair physical properties such as lowering the softening point. The appropriate amount of these is
The flame retardant is 0.5 to 50 parts by weight, preferably 1 to 25 parts by weight, per 100 parts by weight of the polyphenylene ether or polyphenylene ether-containing resin composition of component (a).
More preferably, it is blended in an amount of 3 to 15 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., butylene, ethylene, propylene, isopropylene, isopropylidene, butylene, isobutylene, amylene, cyclohexylene, cyclopentylidene, etc.), ether, carbonyl, amines, sulfur-containing bonds (e.g., sulfide, sulfoxide, etc.) , sulfone>, carbonate, phosphorus-containing bond, and the like.

7 In addition, R12 is aromatic, amine, 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.

and ArI are monocyclic or polycyclic carbocyclic aromatic groups such as phenylene, biphenylene, terphenylene, naphthylene, etc.

8F 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) general formula 10E (wherein E is a monovalent hydrocarbon similar to the following x1). ether group of (31
(4) a monovalent hydrocarbon group, or (5) another substituent, such as a nitro group or a cyano group. When d is 2 or more, Y may be the same or different.

8 x1 is, for example, the following monovalent hydrocarbon group.

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

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

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

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

a, b and C represent integers including O. When b is not O, neither a nor C is O. Otherwise a or C
Either one of them may be O. When b is O, the aromatic groups are bonded to each other through direct carbon-carbon 9 bonds.

The hydroxyl group or substituent Y on the aromatic group Ar and octa'' can take any of the ortho (○), 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-iodo) phenyl)-ethane, 1.1-bis-(2-chloro-4-iodofer)-ethane, 1.1-bis-(2-chloro-4-methylfer>-ethane, 1.1-bis-(3 ,5-dichlorophenyl)ethane, 0 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-3methoxyphenyl)-methane, 2,2-bis-(3,5-dibromo-4-oxyphenyl)-propane, 2,2-bis- (3,5-dichloro-4-oxyphenyl>-propane, 1 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, 5-dibromo-4-oxyphenyl〉-polymerized by propane and phosgene, polymerization degree 1~
20 oligomers and the like.

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

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

■ Q-0-P-○-Q In the above formula, each Q is the same or different 3 groups, and is a hydrocarbon group such as alkyl, cycloalkyl, aryl, alkyl-substituted aryl, and aryl-substituted alkyl; halogen ; includes hydrogen as well as combinations thereof.

Representative examples of suitable phosphoric acid esters include:

Phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate, phenylethylene hydrogen phosphate, phenyl bis-(3,5,5'-trimethylhexyl) phosphate, ethyldiphenyl nonate, 2-ethyl nonate xyldi(p-tolylnonate hydrogendiphenyl, bis-(2-ethylhexyl)lyl nonate, tritolyl phosphate, bis-(2-ethylhexyl) phosphate, p-topheny4 tri(nonylphenyl) monononate, phosphoric acid phenylmethyl hydrogen, di-(dodecyl)-p-tolyl non-acid, triphenyl non-acid, 1-rifenyl non-acid halogen, dibutylphenyl non-acid, non-12-chloroethyldiphenyl, non-acid-tolylbis-(2, 5,5'-1~limethylhexyl), 2-ethylhexyldiphenyl phosphate, diphenyl hydrogen phosphate.

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

Other flame retardant additives include phosphorus-nitrogen bonds such as phosphorous nitride chloride, phosphorus esteramide, phosphoric acid amide, phosphine amide, tris(aziridinyl)phosphine oxyto or tetrakis(oxymethyl>phospho5ium chloride). There are compounds.

There are no particular limitations on the method for producing the thermoplastic resin composition of the present invention, and any conventional known method may 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 kneading 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 that each resin component is uniformly mixed in advance in the form of powder or pellets using a device such as a tumbler or Henschel mixer.
If necessary, a method may be used in which mixing is omitted and the components are individually supplied in fixed amounts to the kneading device.

The kneaded resin composition is molded by injection molding, extrusion molding, and various other molding methods, but it is not necessary to go through the mixing process in advance, and is triblended during injection molding or extrusion molding and then kneaded during melt processing. The resin composition of the present invention can also be used to directly obtain molded products.

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

[Applications] The thermoplastic resin composition 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 for coating shrines, etc.

Particularly automotive parts, such as interior and exterior materials such as bumpers, instrument panels, fenders, trims, door panels, wheel covers, side protector garnishes, trunk lids, bonnets, and five-room roofs, as well as machines that require heat resistance. Used for parts. It is also used as parts for two-wheeled vehicles, such as covering materials, muffler covers, leg shields, etc. In addition, housings are used as electrical and electronic components.
Used for chassis, connectors, printed circuit boards, pulleys, and other parts that require strength and heat resistance.

[Examples] Hereinafter, the present invention will be explained with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.

In addition, the load deflection temperature test (mouth, D, T
, ) JIS K7207, Izod impact strength (thickness 3.2M) was measured according to JIS K7110.

Reduced viscosity of polyphenylene ether in Examples (
η8. /C) is the value measured at 25°C for 0.5g/old solution solution loloform solution.

In the present invention, the melt fluidity of the propylene polymer and modified propylene polymer as component (b) is determined by the melt index (MI).
), but the temperature was 230°C based on the Ml beam i3 K6758 of Example and Comparative Example 8.
This is a value measured with a load of 2.16 kg.

In addition, when component (b) was a plurality of components, they were melt-kneaded in a Labo Plus 1-Mill (manufactured by Toyo Seiki ■), and then the MI was measured.

In addition, the appearance of the injection sheet was observed with the naked eye and evaluated based on the following criteria.

○: No pearl-like color separation, △: Pearl-like color separation.

Components (a>, (b) used in Examples and Comparative Examples
) and (c) are as follows.

Component (a) (polyphenylene ether>: η3./C=0.24.7) polymerized in the laboratory by a well-known method
/C=0. /13.773. /C=0.
51 and p η, p/C = 0.60 (hereinafter referred to as A-1, A-2, A-3 and A-4, respectively)
It is abbreviated as ).

Component (a) (Modified polyphenylene ether): Add 5 kg of the polyphenylene ether (A-1) described above into an autoclave, add 25 summers of water, 54 g of styrene monomer (1), 37 g of dispersant (Metrose 903 100: trade name), and peroxide. (Perbutyl P; trade name), reacted at 130'C for about 1 hour while blowing nitrogen, and then cooled to recover the graft copolymerized composition.Hereinafter, this composition was referred to as A-5. Abbreviated.

Component (b) (propylene polymer): The propylene polymers shown in (i) to (V) below were prepared in a laboratory according to a conventional method and used in the following examples and comparative examples.

Incidentally, P-5 shown in (V) was obtained by decomposing a propylene polymer with peroxide according to a known production method.

(i) Block polypropylene (hereinafter abbreviated as P-1) having an MI of 29, an ethylene content of 8.2% by weight, and an ethylene content of 41% by weight in the propylene-ethylene copolymer portion.

(ii) Block polypropylene (hereinafter abbreviated as P-2) having an MI of 71, an ethylene content of 3.1% by weight, and an ethylene content of 33% by weight in the propylene-ethylene copolymer portion.

(iii) Block polypropylene (hereinafter abbreviated as P-3) having an MI of 8, an ethylene content of 6.5% by weight, and an ethylene content of 51% by weight in the propylene-ethylene copolymer portion.

(iv) Homopolypropylene with M I of 43 (hereinafter referred to as P
It is abbreviated as -4. ).

(v) Homopolypropylene with an MI of 116 (hereinafter referred to as P-
It is abbreviated as 5. ).

Component (b) (modified propylene polymer): m-propylene polymer (P-1 > 6 kg) into a 50 summer autoclave, water 20 1, styrene monomer 1.1 kg, dispersant (Metrose 90S 100: trade name > 70 g , and peroxide (Perbutyl PV; trade name),
While blowing nitrogen, the mixture was reacted at 120° C. for about 1 hour, then cooled, and the grafted propylene polymer was recovered.

The MI of this modified propylene polymer was 13. Hereinafter, this modified propylene polymer will be abbreviated as 5P-1.

1 (ii) Styrene monomer 6109 as raw material monomer
A modified propylene polymer was obtained in exactly the same manner as in the case of 5P-1 except that 103 g of glycidyl acrylate was used. The MI of this polymer was 18. Hereinafter, this modified propylene polymer will be abbreviated as 5P-2.

(iii) Propylene polymer (P-2>5Kg, and Sumitomo Excelen CN which is an ethylene-butene copolymer)
1007 [Product name, manufactured by Sumitomo Chemical ■, density 0.88
g/cm3 and 0.7 kg into a 50 fJ autoclave containing 18 M water, 430 g of styrene monomer, 73 g of glycidyl methacrylate, and a dispersant (Metrose 90S Day-1).
00: trade name>70g and peroxide (Perbutyl P■: trade name) were charged together, and while blowing nitrogen, the reaction was carried out at 120'C for about 1 hour, and then cooled, and the grafted propylene polymer was recovered. The MI of this modified propylene polymer was 48. Hereinafter, this modified propylene polymer will be abbreviated as 5P-3.

(iv) A modified propylene polymer was obtained in exactly the same manner as in the case of 5P-3, except that styrene monomer 2 2409, 63 g of methyl methacrylate, 1 to 2 q of methyl acrylate, and 18 g of glycidyl acrylate were used as raw materials. The MI of this modified propylene polymer was 39. Below, this modified propylene polymer is 5P
It is abbreviated as -4.

(V) Propylene polymer (P-3>6Kg into a 501 autoclave with 20 fJ of water and styrene monomer = 1.
6Kg, dispersant (Metrose 90S mouth 100; product name>
80 g and peroxinide (Perbutyl PV; trade name), and heated for 120' while blowing nitrogen.
After reacting at C for about 1 hour, the mixture was cooled and the grafted propylene polymer was recovered. M of this modified propylene polymer
I was 2. Below, this modified propylene polymer is
It is abbreviated as P-6.

(vi) Propylene polymer (for P-4>100 parts by weight, 1.0 parts by weight of maleic anhydride, 1.3 parts by weight of styrene, 1,3-bis(t-butylperoxy 1.0 parts by weight of propylene homopolymer supported at 6% by weight of isoprobil) penzene 3 (manufactured by Sansei Kako ■, Sanperox-TY1/3; trade name) and Irganox 10 as a stabilizer.
After uniformly mixing 0.1 part by weight of 10 (trade name, manufactured by Ciba Geigy) with a Henschel mixer,
EX44SS-30BW2v type twin screw extruder, temperature 2
The mixture was melt-kneaded at 08° C. for an average residence time of 1.2 minutes to produce a maleic anhydride/styrene-modified propylene polymer with an added amount of maleic anhydride of 0.23% by weight and MI=32. Hereinafter, this modified propylene polymer will be abbreviated as 5P-7.

(vii) A modified propylene polymer with MT=81 was obtained in exactly the same manner as in the case of 5P-3 except that P-5 was used as the propylene polymer. Hereinafter, this modified propylene polymer will be abbreviated as SP'-5.

Component (c) (rubber-like substance): Production of modified ethylene-propylene rubber (i) Sumitomo Nisprene E201 as ethylene-propylene copolymer rubber [trade name, manufactured by Sumitomo Kagaku Kogyo ■, pellets of ML1+4121°C-271 For 100 parts by weight, 1.6 parts by weight of maleic anhydride, 3.0 parts by weight of styrene, and 1,3-bis(t-butylperoxyisopropyl)benzene (Sansei Kako) as a radical initiator. ■Made by Sanpero Tsukusu TY13
; trade name) supported on propylene homopolymer in an amount of 1.0% by weight using a Henschel mixer, and then TEX44SS manufactured by w4ftit made in Japan.
Melt-kneaded in a -30BW2v type twin-screw extruder in a nitrogen atmosphere at a kneading temperature of 260 °C and an extrusion rate of 16 kg/hour, with an added amount of maleic anhydride of 1.0% by weight, an added amount of styrene of 1.9% by weight, Mooney viscosity at 121°C (ML1+4
A modified ethylene-propylene copolymer rubber having a temperature of 121°C>37 was produced. Hereinafter, this modified ethylene-propylene copolymer rubber will be abbreviated as C-1.

(ii) In a stainless steel autoclave equipped with a stirrer, 100 parts by weight of the above C-1 (shredded material), 350 parts by weight of pure water, 4.0 parts by weight of tribasic calcium phosphate, 5 Pluronic F-68 (trade name, Asahi Manufactured by Denka Kogyo ■) 4.
0 parts by weight was added, and sufficient nitrogen substitution was performed while stirring.

Thereafter, 32 parts by weight of styrene and 0.75 parts by weight of Sanperox TO (trade name, manufactured by Sansei Kako@) as a radical initiator were added. After raising the temperature to 100'C over 70 minutes, the reaction was continued for 1 hour.

After cooling, the styrene-grafted copolymer rubber was taken out by filtration, thoroughly washed with pure water, and then vacuum-dried. Hereinafter, this modified ethylene-propylene rubber will be used as C-2
It is abbreviated as

(iii) Sumitomo Nisprene E-606 (trade name, ethylene-propylene-diene copolymer rubber (EPDM)) as a raw material rubber in a stainless steel autoclave equipped with a stirrer.
, manufactured by Sumitomo Chemical ■, Mshi1+4121℃=75>1
Add 00 parts by weight (shredded material), 350 parts by weight of pure water, 4.0 parts by weight of tertiary calcium phosphate, and 4.0 parts by weight of Pluronic F-68 (trade name, manufactured by Asahi Denka Kogyo ■) and stir thoroughly. Nitrogen replacement was performed.

6 Thereafter, 8 parts by weight of styrene, 3 parts by weight of methyl methacrylate, 13 parts by weight of glycidyl methacrylate, and Sanperox TO (trade name, Sansoku Kakoi) as a radical initiator were added.
t1. 0.8 parts by weight (manufactured by L.L.) was added. 1 over 70 minutes
After raising the temperature to 10'C, the reaction was continued for 1 hour. After cooling, the rubber was taken out, thoroughly washed with pure water, and then vacuum dried. Hereinafter, this modified ethylene-propylene-diene rubber will be abbreviated as C-3.

(iv) The following commercial products were used as other rubber-like substances.

Ethylene-propylene rubber; Sumitomo Nisprene E201
[Product name, manufactured by Sumitomo Chemical ■, M L 1,4100'
C=45] (hereinafter abbreviated as C-4), styrene-isoprene block copolymer; Kraton D1320
X [Product name, manufactured by Shell Chemical ■] (hereinafter abbreviated as (, -5)), Bond Fast 2B [Product name, manufactured by Sumitomo Chemical ■] (
Hereinafter, (abbreviated as -6), Acrylonitrile-butadiene rubber: N2155L7 [Product name, Japan Goffffm (t! [, ML1+410
0'G=48] (hereinafter abbreviated as C-7), Sumitomo 5BR1507 [trade name, manufactured by Sumitomo Chemical Co., Ltd., ML1
+4100'C=35] (hereinafter abbreviated as C-8) Styrene-butadiene-styrene block copolymer; Force 1 Noflex TR1186 [trade name, manufactured by Shell Chemical ■] (hereinafter abbreviated as C-9) 〉, ethylene-ethyl acrylate-maleic anhydride copolymer; Pontine-X8200 [trade name, manufactured by Sumitomo Chemical Co., Ltd. (hereinafter referred to as C
It is abbreviated as -10. 〉, Styrene-ethylene-butylene block copolymer; Kraton G1652 [trade name, manufactured by Shell Chemical Co., Ltd.] (hereinafter abbreviated as C-11), Styrene-■ styrene-propylene block copolymer; Kraton G1701X [product Made by Shell Chemical
(hereinafter abbreviated as C-12), fluororubber: G-2
01 [Product name, manufactured by Daikin ■] (hereinafter abbreviated as C-13). 〉.

Examples 1 to 13 and Comparative Examples 1 to 9 8 Each of the above fractions was blended in the proportions (parts by weight) shown in Tables 1 and 2,
Each compound was kneaded using a TEX44 twin-screw extruder manufactured by Nippon Steel Corporation at a cylinder temperature of 260° C. and a screw rotation speed of 25 Orpm.

The resulting resin composition was injection molded using Is150E manufactured by Toshiba Machine Corporation under conditions of a cylinder temperature of 260°C and a mold wetness of 60'C to prepare test pieces according to ASTM standards, and their physical properties were measured. . The results are shown in Tables 1 and 2.

As is clear from Tables 1 and 2, η8. /C is 0.20~
0.45 polyphenylene ether, MI 10-10
It can be seen that the composition containing the modified propylene polymer of No. 0 and/or the mixture of the modified propylene polymer and the propylene polymer has excellent heat resistance and the appearance of the Tsurugi molded product.

It is also understood that a composition with excellent impact resistance can be obtained by blending a rubber-like substance with the grains.

9 [Effects of the Invention] As explained above, the thermoplastic resin composition of the present invention is remarkable in that not only the heat resistance and mechanical properties of the molded article are excellent, but also the molding processability is excellent. It has a great effect.

The novel resin composition provided by the present invention can be easily processed into molded products by molding methods used for ordinary polyphenylene ether thermoplastic resin compositions, such as injection molding and extrusion molding, and has excellent impact resistance and heat resistance. It provides a product with an extremely good balance of physical properties such as hardness and hardness, and excellent uniformity and smoothness in appearance.

Claims (1)

[Claims] 1) (a) Reduced viscosity (ηsp/C) is 0.20 to 0.4
5 polyphenylene ether or a composition containing the polyphenylene ether, (b) 230°C based on JIS K6758, load 2.1
Melt index at 6kg is 10-100g/
(i) Graft copolymerization of a modified propylene polymer obtained by graft copolymerizing a styrenic monomer and/or a mixture of a styrenic monomer and a monomer that can be copolymerized with the styrenic monomer. modified propylene polymer,
or (ii) a mixture of the modified propylene polymer and the propylene polymer, and (c) a rubber-like substance, wherein the ratio of component (a) to component (b) is
) is 1 to 98% by weight, component (b) is 99 to 2% by weight, and component (c) is 0 to 50 parts by weight relative to 100 parts by weight of the total amount of component (a) and component (b). A thermoplastic resin composition characterized in that: 2) Component (a) polyphenylene ether has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1, R_2, R_3, R_4 and R_5
are the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, a hydrocarbonoxy group or a substituted hydrocarbonoxy group. However, one of R_1 to R_5 is always hydrogen. 2. The thermoplastic resin composition according to claim 1, which is a polyphenylene ether obtained by oxidative coupling polymerization of one or more phenolic compounds represented by the following formulas.