JPH05287193A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject resin composition comprising an acid-modified polyphenylene ether resin, a polyamide resin. a specific impact resistance- improver and a specified aromatic vinyl copolymer, excellent in impact resistance, heat resistance and rigidity, and useful for automotive exterior materials, etc. CONSTITUTION:The objective thermoplastic resin composition excellent in mechanical strength, impact resistance and heat resistance comprises (A) 20-80 pts.wt. of an acid-modified polyphenylene ether resin, (B) 80-20 pts.wt. of a polyamide, (C) 5-40 pts.wt. of an impact resistance-improver comprising at least one kind of an acid-modified styrenic aromatic hydrocarbon/conjugated diene block copolymer, its hydrogenated product, an acid-modified olefinic copolymer, etc., and, if necessary, a non-modified styrenic aromatic hydrocarbon/non- conjugated dienic block copolymer or its hydrogenated product, and (D) 0.5-30 pts.wt. of at least one of an oxazolinyl group-containing aromatic vinyl polymer, an epoxy group-containing aromatic vinyl polymer, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has an excellent balance of basic characteristics represented by impact resistance, heat resistance, rigidity, etc., and excellent characteristics such as thermal stability and moisture resistance of molded products. The present invention relates to a thermoplastic resin composition.

[0002]

2. Description of the Related Art A polymer blend composed mainly of polyphenylene ether and polyamide is a material which has excellent molding processability and chemical resistance of polyamide and excellent heat resistance, dimensional stability and water resistance of polyphenylene ether. As a result, in recent years, it is expected to be applied to automobile parts. Among them, the development of applications for automobile exterior panel exterior materials has begun to attract attention.

Generally, it is required to have heat resistance to withstand a coating temperature of up to about 150 ° C. and high impact resistance as important and required properties as an exterior material for automobile exteriors.

However, since the heat resistance and the impact resistance of the resin material are inherently contradictory to each other, many studies have been reported to solve this problem.

That is, a polyphenylene ether resin and a polyamide resin are simply melt mixed (Japanese Patent Publication No. 45-99).
No. 7 and Japanese Patent Publication No. 59-41663), but both resins are incompatible and phase-separated largely, and a molded product excellent in mechanical strength cannot be obtained. Therefore, as a means for improving the compatibility between the polyphenylene ether resin and the polyamide resin, for example, a compound having a carbon-carbon double bond and a carboxyl group, an acid anhydride group, an acid amide group, a functional group such as an imide group. A method of blending as a third component (JP-A-56-26913), a method of blending a copolymer of a styrene compound and an α, β-unsaturated dicarboxylic acid (JP-B-59-33614), and the like. is there. However, even these compositions have insufficient impact strength.

In order to improve the impact strength of multi-component polymer blend materials such as polyamide resin and polyphenylene ether resin, it has been proposed to further mix and disperse an elastomer which is an impact strength improver.

Among them, a particularly well-balanced blend system is one in which a polyamide and a specific modified polyphenylene ether are used and a rubber component is further added as a third component, and typical examples thereof include polyamide and acid-modified polyphenylene. A combination of ether and styrene-butadiene-styrene block copolymers (Japanese Patent Laid-Open Publication No. 6-58242)
1-146433), polyamide, acid-modified polyphenylene ether, hydrogenated styrene-butadiene-styrene copolymer (JP-A-62-13855).
3), polyamide, acid-modified polyphenylene ether,
A combination of acid-modified hydrogenated styrene-conjugated diene block copolymer (JP-A-62-68850, JP-A-63-130658), polyamide, acid-modified polyphenylene ether, acid-modified and unmodified hydrogenated styrene-
Examples thereof include those in which butadiene-styrene block copolymers are used in combination (Japanese Patent Laid-Open No. 149853/1989) and the like, and those in which polyphenylene ether and rubber-like components are improved.

Further, a polyphenylene ether resin is added in the presence of a hydrogenated product of a block copolymer represented by (vinyl aromatic hydrocarbon polymer block)-(conjugated diene hydrocarbon polymer block)-(vinyl aromatic hydrocarbon polymer block). The modified polyphenylene ether resin obtained by reacting with a 1,2-substituted olefin compound exemplified by maleic anhydride in a molten state, a polyamide resin, a styrene resin, and an organic compound having at least two oxazoline rings in one molecular chain. There is also a proposal of a resin composition which is compounded and is excellent in mechanical strength, impact resistance, heat resistance and fluidity (JP-A-2-75655).

A resin composition composed of polyphenylene ether and polyamide is excellent in mechanical strength, but on the other hand, it is a technique of blending a polyolefin resin in order to complement the drawback that polyamide itself has high hygroscopicity (Japanese Patent Application Laid-Open No. Sho. 63-146948, JP-A-63-33471, and JP-A-2-115263).

[0010]

However, in the resin composition disclosed in the above-mentioned prior art, a composition in which polyphenylene ether or an elastomer component, which is a component of the resin composition, is improved has impact resistance and heat resistance. Although it provides appropriate improvement in terms of basic properties such as properties, impact resistance is deteriorated in a high temperature atmosphere, or thermal stability during molding is insufficient and there is room for improvement. Further, the resin composition composed of polyphenylene ether and polyamide has a considerably improved high hygroscopicity as compared with the polyamide itself, however, physical property variation and dimensional change due to moisture absorption are large, and further improvement in practical physical properties is achieved. There is room for it.

Further, if a polyolefin resin is added for the purpose of improving the high hygroscopicity, the hygroscopicity is reduced, but the basic characteristics are deteriorated, which is not preferable.

That is, the present invention uses polyphenylene resin and polyamide as the main resin components and is excellent in mechanical strength, impact resistance and heat resistance in basic physical properties, and further, the hygroscopicity and the impact strength in a high temperature atmosphere are improved. Another object of the present invention is to provide a thermoplastic resin composition.

[0013]

Means for Solving the Problems As a result of research to achieve the above object, the inventors selected a specific modified polyphenylene ether resin, a polyamide resin, and a specific impact modifier, and further selected By combining an oxazolinyl group- or epoxy group-containing aromatic vinyl polymer, the basic properties such as impact resistance, heat resistance, and rigidity are highly balanced, and the impact properties are further reduced in a high temperature atmosphere. The inventors have found that a material having improved hygroscopic properties can be obtained and arrived at the present invention.

That is, according to the present invention, (A) an acid-modified polyphenylene ether resin, (B) a polyamide resin,
(C) Unmodified styrene-based aromatic hydrocarbon optionally blended with at least one selected from acid-modified styrene-based aromatic hydrocarbon / conjugated diene block copolymer, hydrogenated product thereof and acid-modified olefin copolymer -Impact resistance improver comprising a non-conjugated diene block copolymer or a hydrogenated product thereof, and (D) an oxazolinine group-containing aromatic vinyl polymer (D-1) and an epoxy group-containing aromatic vinyl polymer ( A thermoplastic resin composition comprising at least one copolymer selected from D-2) is provided.

The constitution of the present invention will be described in detail below, but more preferable embodiments of the present invention and advantages based on them will become apparent. (A) Acid-Modified Polyphenylene Ether Resin The acid-modified polyphenylene ether resin of the present invention is an unmodified polyphenylene ether-based resin having a structural unit represented by the following general formula (I) in the main chain and a carboxyl group or /
And an acid anhydride group is introduced.

[0016]

[Chemical 1] (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ ,
R ₃ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. )

Such polyphenylene ether may be a homopolymer or a copolymer, and specifically, for example,
Poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly ( 2-methyl-6-ethyl-1,4
-Phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, and the like, but especially poly (2,6-dimethyl-1,4-phenylene) ether, 2,6- Dimethylphenol / 2,3,
6-trimethylphenol copolymer is preferred. These polyphenylene ether resins have an intrinsic viscosity [η] measured in toluene at 25 ° C. of usually 0.20 to 0.80.
dl / g.

The method of introducing the carboxyl group and the acid anhydride group into the polyphenylene ether resin can be carried out by a method known per se. For example, the following (1)
The methods (3) to (3) can be exemplified.

(1) As disclosed in JP-B-52-30991 and JP-B-52-19864, a carboxyl group and an acid anhydride group are added to a solution containing a polyphenylene ether resin in the presence of a radical generator. Add a radically polymerizable compound that has, at a temperature of 50 ~ 200 ℃ dozens of minutes ~
Stir for several hours.

(2) As disclosed in Japanese Patent Publication No. 59-11605, a method of bringing the above components into contact with each other under melt-kneading in a system containing substantially no solvent or a system containing a small amount of solvent.

Specific examples of the radical polymerizable compound having a carboxyl group and an acid anhydride group, which are reacted with the polyphenylene ether resin by the above methods (1) and (2), include maleic anhydride, maleic acid and itacone anhydride. Examples thereof include acids, fumaric acid, methyl nadic acid anhydride, dichloromaleic anhydride, acrylic acid and methacrylic acid, with maleic anhydride or acrylic acid and methacrylic acid being particularly preferred.

The radical generator is, for example, an organic peroxide or a diazo compound, and specific examples thereof are benzoyl peroxide, dicumyl peroxide and di-
Examples thereof include t-butyl peroxide, cumene hydroperoxide and azobisisobutyronitrile. These radical generators can be used in combination of two or more.

(3) A method of reacting an acid chloride having a carboxyl group or an acid anhydride group, for example, trimellitic anhydride chloride with polyphenylene ether, which is described in JP-A-62-500456.

The modified product of the component (A) and the following component (C) of the present invention can be simultaneously produced by using the above method (1) or (2). That is, the unmodified polyphenylene ether resin and the corresponding unmodified copolymer are melt-mixed, and the radical-polymerizable monomer is allowed to be present so that they can be produced and used as a mixture at the same time.

The amount of carboxyl groups and / or acid anhydride groups contained in the modified polyphenylene ether resin (A) is usually 0.1 to 3.0 wt%, preferably 0.2 to 1.
It is about 5 wt%, and within this range, a resin composition excellent in both mechanical strength and impact resistance can be obtained.

(B) Polyamide Resin The polyamide resin used as the component (B) in the present invention may be a polyamide resin that can be used in ordinary injection molding, and is a polymer having a —CONH— bond in the main chain. Yes, it can be heated and melted. Typical examples are 4-nylon, 6-nylon, 6,6-
Nylon, 4,6-nylon, 12-nylon, 6,1
0-nylon, polyamide from terephthalic acid and / or isophthalic acid and hexamethylenediamine, polyamide from terephthalic acid and trimethylhexamethylenediamine, polyamide from adipic acid and metaxylylenediamine, terephthalic acid and 4,4′-diamino Examples include polyamides from dicyclohexylmethane. Among these, 6-nylon and 6,6-nylon are particularly preferable.

(C) Impact modifier The impact modifier of the present invention is selected from acid-modified styrenic aromatic hydrocarbon / conjugated diene block copolymers, hydrogenated products thereof and acid-modified olefin copolymers. An unmodified styrenic aromatic hydrocarbon / non-conjugated diene block copolymer or a hydrogenated product thereof is optionally blended with at least one of the above.

When the styrene aromatic hydrocarbon polymer block is A and the conjugated diene polymer block is B, the styrene aromatic hydrocarbon / conjugated diene block copolymer is, for example, AB type or AB type. -Type A is typical. Such a block copolymer can be easily obtained by a method known per se, for example, anion living polymerization method, and a part thereof is commercially available.

Examples of the styrenic aromatic hydrocarbon include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene and a mixture thereof. Further, as an example of the conjugated diene, butadiene,
Mention may be made of isoprene, 1,3-pentadiene and mixtures thereof.

Preferred styrenic aromatic hydrocarbon / conjugated diene block copolymers are styrene / butadiene block copolymers and styrene / isoprene block copolymers.

The hydrogenated product of such a block copolymer is one obtained by hydrogenating all or part of the double bond of the polymer block (B) of the conjugated diene, and is, for example, US Pat. No. 3,431. , 323, the manufacturing method is disclosed. And a part of it is used as a hydrogenated product of styrene-butadiene block copolymer (SEBS) and also as a hydrogenated product of styrene-isoprene block copolymer (SE).
It is sold as P) and can be preferably used.

In the above block copolymer or hydrogenated product thereof, the proportion of styrene aromatic hydrocarbon is 10 to 50.
About wt% is preferable. The average molecular weight is 1 × 1.
It is preferably about 0 ^{4 to} 20 × 10 ⁴ .

The above block copolymer and its hydrogenated product can be acid-modified by reacting a radical polymerizable compound having a carboxyl group or an acid anhydride group in the presence of a radical generator. The method and the radically polymerizable compound that can be used are the same as in the case of preparing the (A) acid-modified polyphenylene ether resin.

The acid-modified olefin copolymer can be obtained by introducing a carboxyl group or an acid anhydride group into the olefin copolymer by the above method. As the olefin copolymer, ethylene, propylene, 1-butene, 1-
A typical example is one obtained by copolymerizing any two or more kinds of olefins such as pentene, 1-hexene, and 4-methyl-1-pentene. In the copolymerization, a small amount of a non-conjugated diene such as 1,4-hexadiene, dicyclopentadiene and ethylidene norbornene may be copolymerized.

Specific examples of preferable olefin copolymers include ethylene / propylene copolymer and ethylene / 1-
A butene copolymer, an ethylene / propylene / 1,4-hexadiene copolymer, an ethylene / propylene / dicyclopentanediene copolymer, or an ethylene / propylene / ethylidene norbornene copolymer, which is substantially amorphous Are preferred.

The amount of the carboxyl group and / or the acid anhydride group contained in the acid-modified styrene aromatic hydrocarbon / conjugated diene block copolymer, its hydrogenated product, and the acid-modified olefin copolymer is usually 0. 01 to 5 wt%, preferably 0.1 to 3 wt%, and in this range, favorable results in strength and impact resistance can be obtained.

Some of such acid-modified products can be easily obtained on the market. For example, "Clayton and Califlex series" manufactured by Shell Chemical Co., Ltd., "Tuftec and Tuffprene manufactured by Asahi Kasei Kogyo Co., Ltd.""Series", N-Tuffmer series manufactured by Mitsui Petrochemical Co., Ltd., and the like, and are easily available.

In the present invention, as an impact resistance improver, the above-mentioned unmodified styrene aromatic hydrocarbon / non-conjugated diene block copolymer or hydrogenated product thereof is optionally compounded with an acid-modified product. be able to. In this case, it is preferable that the compounding amount is such that the amount of the carboxyl group and / or the acid anhydride group is within the above range based on the total amount of the acid-modified product and the unmodified product. Further, the compounding amount of the unmodified product is about 200 parts by weight at maximum per 100 parts by weight of the acid-modified product.

(D) Aromatic vinyl containing oxazolinyl group
-Based copolymer (D-1) and epoxy group-containing aromatic vinyl
Copolymer (D-2)

(D-1) Oxazolinyl Group-Containing Aromatic Bi
Nyl Copolymer The oxazolinyl group-containing aromatic vinyl copolymer of the present invention has the general formula (II) in the aromatic vinyl polymer.

[Chemical 2] Is a copolymer having a polymerized unit derived from vinyl oxaline (formula (III)).

[0041]

[Chemical 3] (In the formulas (II) and (III), R ¹ is hydrogen or an alkyl group, preferably hydrogen or a methyl group)

Such a polymer (D-1) is obtained by random copolymerization or block copolymerization with an aromatic vinyl compound and vinyloxazoline (III), or by graftcopolymerizing vinyloxazoline with an aromatic vinyl polymer. Is obtained by

As the aromatic vinyl compound, styrene,
Examples include α-methylstyrene, p-methylstyrene, pt-butylstyrene, chlorinated styrene,
Preferred are styrene and α-methylstyrene. Of course, these can be used alone or in combination.

As a method for producing an aromatic vinyl polymer having an oxazolinyl group by graft-copolymerizing vinyl oxazoline with an aromatic vinyl polymer, the aromatic vinyl polymer and vinyl oxazoline are added in the presence of a radical initiator or It is also possible to employ a method of melt-kneading under the condition of heating in the absence of an aromatic vinyl polymer and vinyl oxazoline under the condition of heating in a solvent in the presence or absence of a radical initiator. A method of reacting can also be adopted. The temperature during the grafting reaction is 50 to 330 ° C, preferably 60 to 300 ° C.
Is.

Further, as a method for producing an oxazolinyl group-containing aromatic vinyl polymer, including the above graft reaction,
Generally known polymerization methods such as bulk polymerization, solution polymerization, bulk / suspension polymerization, suspension polymerization and emulsion polymerization can be used.

In the oxazolinyl group-containing aromatic vinyl copolymer (D-1), the proportion of the oxazolinyl group-containing unsaturated monomer is preferably 0.1 to 30% by weight,
The range is more preferably 0.5 to 20% by weight. When the amount of copolymerization is too small, the effect of improving the hygroscopic property and thermal stability of the composition (impact strength) is low, and when it is excessive, the copolymer tends to gel and the basic physical properties deteriorate and It is difficult to obtain a molded product in good condition.

Further, a total of 10 of the above-mentioned copolymerization components is added.
It is also possible to copolymerize 0 to 70 parts by weight of another copolymerizable monomer with 0 parts by weight. Examples of other copolymerizable monomers include α, β-unsaturated carboxylic acid esters such as methyl methacrylate, ethyl methacrylate, -t-butyl methacrylate and cyclohexyl methacrylate.

Further, as an oxazolinyl group-containing aromatic vinyl polymer, an oxazolinyl group-containing ABS obtained by graft-copolymerizing vinyloxazoline with an oxazolinyl group-containing acrylonitrile / styrene copolymer or a styrene / butadiene / acrytronitrile copolymer rubber. It may include a resin or the like. Also in this case, the proportion of the oxazolinyl group-containing unsaturated monomer is the same as above.

(D-2) Epoxy group-containing aromatic vinyl polymer
Combined (D-2) The component (D-2) is one in which an epoxy group is introduced into an aromatic vinyl polymer, for example, a random copolymer of an aromatic vinyl compound and an epoxy group-containing unsaturated monomer. Examples thereof include those obtained by graft-copolymerizing an aromatic vinyl polymer with an epoxy group-containing unsaturated monomer, and those obtained by graft-copolymerizing an epoxy group-containing ethylene copolymer with an aromatic vinyl compound.

Regarding the kind of the aromatic vinyl compound, the contents described in the section of the component (D-1) can be applied as they are.

Examples of the unsaturated monomer having an epoxy group include glycidyl methacrylate, butyl glycidyl acrylate, butyl glycidyl fumarate, propyl glycidyl fumarate and glycidyl acrylate. These may be used alone or in combination of two or more. You can also

Examples of the aromatic vinyl polymer serving as a trunk polymer in the graft copolymerization of the above-mentioned epoxy group-containing unsaturated monomer include homopolymers of polystyrene, polychlorostyrene, poly α-methylstyrene, and the like. Examples thereof include styrene-acrylonitrile copolymers and styrene-divinylbenzene copolymers.

In either case, the aromatic vinyl compound is randomly copolymerized with the epoxy group-containing unsaturated monomer or the aromatic vinyl polymer is graft-copolymerized with the epoxy group-containing unsaturated monomer. Monomers such as methyl acrylate, methyl methacrylate, vinyl acetate and the like may be copolymerized.

When an aromatic vinyl compound is graft-copolymerized with an epoxy group-containing ethylene copolymer, a copolymer of ethylene and an epoxy group-containing unsaturated monomer, for example, an ethylene / glycidyl acrylate copolymer, is used as a trunk polymer. , Ethylene / glycidyl methacrylate copolymer and the like can be used. Of course, other monomers such as methyl acrylate, methyl methacrylate and vinyl acetate may be contained. The content of the epoxy group-containing unsaturated monomer contained in this trunk polymer is 0.1 to 20.
It is preferably in the weight%.

As another embodiment of the component (D-2), the carbon-carbon unsaturated bond present in the aromatic vinyl polymer is oxidized by a known method, for example, hydrogen peroxide or an organic peracid. As a result, one having an epoxy group introduced into the molecule can be mentioned.

Whatever type of epoxy group-containing aromatic vinyl polymer (D-2) is used, it is preferable that the aromatic vinyl unit accounts for 20% by weight or more, particularly 30% by weight or more, of the whole. The proportion of the epoxy group-containing unsaturated monomer is 0.1 to 30% by weight, especially 0.1 to 30% by weight.
It is preferably 20% by weight.

When the content is within this range, the composition of the present invention finally obtained is excellent in the effect of improving the hygroscopic property and the thermal stability, and the basic physical properties are hardly impaired.

The random copolymerization method and the graft copolymerization method used for obtaining the component (D-2) are known per se and can be easily produced by those skilled in the art.

The preferable blending amount of the components (A), (B), (C), and (D) in the proportion of the blending amount or more is 20 to 80 parts by weight, and particularly 30 to 70 parts by weight of the (A) modified polyphenylene ether. 80 parts by weight of the polyamide resin (B), especially 70 parts by weight.
-30 parts by weight (C) Impact modifier is 5-40 parts by weight, especially 10-
30 parts by weight (wherein the total amount of (A), (B) and (C) is 100 parts by weight) and (D) the oxazolinyl group- or epoxy group-containing aromatic vinyl polymer is (A). ), (B) and (C) based on 100 parts by weight in total, the amount is preferably 0.5 to 30 parts by weight, particularly 1 to 25 parts by weight.

When the compounding ratio of the acid-modified polyphenylene ether resin (A) and the polyamide resin (B) is within the above range, the excellent water resistance, dimensional stability and heat resistance of the polyphenylene ether resin are not impaired and the oil resistance is improved. And the moldability are excellent, and favorable results are obtained.

When the amount of the impact resistance improver (C) is within the above range, the molded article has high impact resistance, excellent mechanical strength and heat resistance, and a good balance of basic characteristics of the molded article. ..

The blending of the oxazolinyl group- or epoxy group-containing aromatic vinyl polymer (D) is carried out for the purpose of improving the hygroscopicity and thermal stability of the molded article. Since there is a concern that the fluidity will deteriorate and the molding processability will decrease, if it is within the above range, the intended purpose can be achieved without deteriorating the processability.

The reason why the incorporation of the oxazolinyl group- or epoxy group-containing aromatic vinyl copolymer (D) improves both the hygroscopicity and the thermal stability while balancing the basic properties of the molded article. (D) has a low hygroscopic property because it contains polystyrene chains in the molecule, and at the same time, it is not merely physically dispersed in the molded product, but an acid-modified polyphenylene ether resin, polyamide resin and impact resistance. It is presumed that it intervenes with a strong interaction among the three improvers to stabilize the microstructure of the molded product.

Method for Preparing Composition The method for mixing the respective components constituting the resin composition of the present invention is not particularly limited. For example, a method for mixing the respective components at once and melt-kneading; modified polyphenylene ether (A) and polyamide Method of blending (B), impact modifier (C), oxazolinyl group- or epoxy group-containing aromatic vinyl polymer (D) and melt-kneading; after melt-kneading components (A) and (D) (B) ) And component (C) and melt kneading;
Any method such as a method of melt-kneading the components (B) and (D) and then melt-kneading the components (A) and (C) is added.

The temperature of melt mixing is 230 to 330 ° C, preferably 250 to 300 ° C. As the melt mixing method, an extruder, a kneader, a Banbury mixer, a roll, or other device can be used.

The resin composition of the present invention may optionally contain
Other resins, elastomers, flame retardants, flame retardant aids, stabilizers,
Various additives such as UV absorbers, plasticizers, lubricants; pigments,
Fillers and other components can be appropriately mixed.

As examples of the above-mentioned various additives, examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, phosphate obtained from a mixture of isopropylphenol and phenol, and bifunctional such as benzohydroquinone or bisphenol A. Phosphates such as phosphate obtained from soluble phenol and other alcohols or phenols; decabromobiphenyl, pentabromotoluene, decabromobiphenyl, pentabromotoluene, decabromobiphenyl ether, hexabromobenzene, brominated polystyrene, etc. And a nitrogen-containing compound such as a melamine derivative. Further, a flame retardant aid can be blended, and specific examples thereof include antimony, boron, zinc or iron compounds and the like.

Further, as other additives, stabilizers such as sterically hindered phenols and phosphite compounds; UV absorbers exemplified by oxalic acid diamide compounds and sterically hindered amine compounds; polyethylene wax, polypropylene wax, paraffin. Examples thereof include lubricants. Furthermore, pigments exemplified by titanium oxide, zinc sulfide, zinc oxide; glass fiber, glass beads, asbestos, wollastonite, mica, talc, clay, calcium carbonate, magnesium hydroxide, silica, potassium titanate fiber, diatomaceous earth. , Rock wool, mineral fillers; aluminum and zinc flakes, or brass,
Inorganic fillers represented by metal fibers such as aluminum zinc; organic fillers represented by carbon fibers can be mentioned.

[0069]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to these. The properties described in Examples and Comparative Examples were evaluated by the following methods. (1) Izod impact strength: ASTM D256 (2) Bending property: ASTM D790 (3) Heat distortion temperature: ASTM D648 (4) Thermal stability: ASTM standard (1/8 ")
After heat-treating a size test piece in a nitrogen stream at 150 ° C. for 60 minutes, measure the Izod impact strength of the test piece,
The ratio to the untreated product was calculated. (4) Hygroscopicity: ASTM standard size (1 /
8 ″) test piece using a constant temperature and humidity machine (Toyo Seiki)
Treated at 0 ° C, 80% (RH: relative humidity) for 200 hours,
During this time, the water absorption amount and the dimensional change of the test piece were measured. The injection molding conditions for each ASTM standard size test piece are as follows. Nozzle temperature: 275 ° C Mold temperature: 100 ° C Injection pressure: 40-60kg / cm ² Injection speed: 20-70%

Example 1 (a) Production of Maleic Anhydride Modified Polyphenylene Ether Resin (MPPE) Poly (2,6-dimethylphenylene-1) having an intrinsic viscosity of 0.45 dl / g measured in toluene at 25 ° C. , 4-ether) (hereinafter PPE) 100 parts by weight, 1 part by weight of di-t-butyl peroxide and 3 parts by weight of maleic anhydride were dry blended at room temperature, and then the diameter was 37 mm.
Using a twin-screw extruder with co-rotating vents (Toshiba Machinery) of φ, L / D = 31.5 (Toshiba Machine), melt at a cylinder temperature of 300 ° C, a screw rotation speed of 200 rpm, extrude with a residence time of 1 minute, and after water cooling Then, the mixture was pelletized to obtain maleic anhydride-modified poly (2,6-dimethylphenylene-1,4-ether) (hereinafter MPPE). The obtained MPPE pellet was dissolved in chloroform and then reprecipitated in about 10-fold amount of acetone for purification. After drying the purified MPPE, 50 mg was collected and dissolved in chloroform to prepare a cast film having a thickness of about 20 μm. Then
The film was dried and subjected to FT-infrared spectroscopy. Derived from reaction with maleic anhydride in this sample-
The presence of the structure of (CO) ₂ O-
It was confirmed by an absorption peak near 780 cm ⁻¹ , and the addition amount of maleic anhydride (titration value by sodium methylate method) was 0.6% by weight.

(B) Production of oxazolinyl group-containing aromatic vinyl polymer (OX-PS) Polystyrene (Topolex 5 manufactured by Mitsui Toatsu Chemicals, Inc.)
25) 100 parts by weight, 2-vinyloxazoline, 1.2
A twin-screw extruder (manufactured by Toshiba Machine, 37 mmφ, L / D, set to 230 ° C. after mixing 0.05 part by weight of t-butyl peroxide and 0.05 part by weight of t-butyl peroxide.
= 31.5) for melt kneading / pelletizing to obtain a graft copolymer. After the pellets thus obtained were purified with a toluene / methanol system, the graft amount of the oxazoline ring was examined by infrared absorption spectrum and nitrogen analysis. As a result, the graft amount was 1.
It was 2 parts by weight.

(C) Preparation of Composition 45 parts by weight of MPPE obtained in (a), acid-modified hydrogenated styrene-butadiene block copolymer elastic body (manufactured by Asahi Kasei, Tuftec M1953, styrene content 40%, acid value 10 mg N
aOCH ₃ / g) 15 parts by weight, polyamide resin (Toray CM
1007) 20 parts by weight of the oxazolinyl group-containing polystyrene obtained in (b) was added to 100 parts by weight of the mixture, which was composed of 40 parts by weight, and dry-dried using a Henschel mixer, and then the cylinder temperature was set to 280 ° C. Co-rotating twin-screw extruder (Toshiba Machine, caliber 37mm, L
/P=31.5), melted and kneaded, cooled and pelletized to obtain a pelletized resin composition. This resin composition was dried at 80 ° C. for 4 hours at 4 mmHg or less for 6 hours and then injection-molded, and the obtained ASTM standard test pieces were used as test pieces for measuring predetermined physical properties. The results are shown in Table 1. The resin composition had basic properties such as Izod impact strength, heat distortion temperature, and bending rigidity balanced at a high level, low hygroscopicity, little dimensional change, and good thermal stability.

Comparative Examples 1 to 4 In Comparative Example 1, Example 1
When the oxazolinyl group-containing polystyrene obtained in (b) is not added, Comparative Examples 2 and 3 are unmodified polyphenylene ether and an impact modifier (hydrogenated styrene-butadiene block copolymer elastomer manufactured by Shell Chemical Co., Ltd., In the case of using each of the styrene contents of 29% by weight, in Comparative Example 4, polystyrene (manufactured by Mitsui Toatsu Chemicals, Inc., Topolex 5) was used.
25) is used alone, except for the above, Example 1
However, the basic properties such as impact resistance, heat distortion temperature, and rigidity were generally low, and the hygroscopicity and the dimensional change were large, and the impact strength in the high temperature atmosphere was significantly reduced.

Example 2 As an impact resistance improver, FG1901X (styrene content 28% by weight, maleic anhydride addition amount 2.0% by weight) manufactured by Shell Chemical Co., Ltd., and oxazolinyl manufactured by Nippon Shokubai Co., Ltd. Group-containing polystyrene (RP
Example 1 was repeated, except that S1001 and vinyl oxazoline content: 1% by weight) were used. The results are almost the same as in Example 1, as shown in Table 1.

Example 3 Example 3 was repeated except that the contents of MPPE and impact resistance improver (FG1901X) in Example 2 were changed. When the content of PPE is relatively increased (the content of the impact resistance improver is relatively decreased), the rigidity and the heat distortion temperature are increased, but the impact resistance is slightly decreased, The basic properties were still balanced at a high level, low humidity, little dimensional change, and good thermal stability.

Example 4 CM1021 (having a higher molecular weight than CM1007) manufactured by Toray Industries, Inc. was used as a polyamide resin, and oxazolinyl group-containing polystyrene (RPS1005, vinyl oxazoline content 5 manufactured by Nippon Shokubai Co., Ltd.) was used. %) And the amount added was reduced, and the same procedure as in Example 1 was performed. The same results as in Example 1 were obtained except that the impact resistance as a basic physical property was increased.

Example 5 As an impact resistance improver, an acid-modified hydrogenated styrene-butadiene block copolymer elastic body (M1953) manufactured by Asahi Kasei Corporation and an acid-modified ethylene-propylene copolymer (JSR manufactured by Japan Synthetic Rubber Co., Ltd.) were used. T7741P) and a 1: 1 mixture with MPPE with a relatively low MPPE content, with the same results as in Example 4.

Example 6 Instead of the oxazolinyl group-containing polystyrene (RPS1005) used in Example 4, an oxazolinyl group-containing polystyrene-acrylonitrile copolymer (RAS1005, vinyloxazoline content 5% by weight, styrene, manufactured by Nippon Shokubai Co., Ltd.) was used. The content was 70%, the acrylonitrile content was 25% by weight), and the same procedure as in Example 4 was performed except that FG1901X manufactured by Shell Chemical Co. was used as the impact resistance improver. As a result, as shown in Table 1, almost the same results as in Example 4 were obtained.

[Examples 7 to 9] In Example 7, the content of impact modifier was increased, in Example 8 the content of MPPE was increased, and in Example 9 the content of polyamide was increased.
I went the same way. Although basic properties such as impact strength, heat distortion temperature, and rigidity change with changes in the content of each component, they remain at a high level, and there is almost no drop in hygroscopicity and impact strength in a high temperature atmosphere.

Example 10, Comparative Example 5 In Example 10, as an impact resistance improver, an acid-modified ethylene-propylene copolymer (JSR T7741 manufactured by Japan Synthetic Rubber Co., Ltd.) was used.
Example 2 was repeated except that P) was used. The results are almost the same as in Example 2 as shown in Table 1. Further, Comparative Example 5 is a case where oxazolinyl group-containing polystyrene is not added, and as a result of being carried out in the same manner as in Example 10 except for the above, although hygroscopicity and dimensional change are reduced, impact resistance, heat distortion temperature, Basic characteristics such as rigidity were generally low.

Examples 11 to 12 and Comparative Example 6 Example 1
In No. 1, as an impact resistance improver, an acid-modified hydrogenated styrene-butadiene block copolymer elastic body (M1953) manufactured by Asahi Chemical Industry Co., Ltd. and an unmodified hydrogenated styrene-butadiene block copolymer elastic body manufactured by Shell Chemical Co., Ltd. 1: 1 mixture with (G1650), in Example 12, the unmodified hydrogenated styrene-butadiene copolymer elastomer (G1650) and an acid-modified ethylene-propylene copolymer (JS manufactured by Japan Synthetic Rubber Co., Ltd.).
R T7741P) but using a 1: 1 mixture with
The same procedure as in Example 4 was performed, and the same results as in Example 4 were obtained.
On the other hand, in Comparative Example 6, the acid-modified hydrogenated styrene-butadiene copolymer elastic body (M1953) and unmodified ethylene-
Propylene copolymer (Esplen EP20 manufactured by Sumitomo Chemical Co., Ltd.
Example 1 was repeated except that a 1: 1 mixture with 1) was used, but the basic properties such as impact resistance, heat distortion temperature, and rigidity were generally low, and the hygroscopicity was not improved.

Example 13 (a) Epoxy Group-Containing Aromatic Vinyl Polymer (EPO-P)
Preparation of SI and EPO-PS2) (a-1) 100 parts by weight of polystyrene (Topolex 525, manufactured by Mitsui Toatsu Chemicals, Inc.), 5 parts by weight of glycidyl methacrylate, and 1 part by weight of di-t-butyl peroxide were placed in a Henschel mixer. Twin screw extruder (Toshiba Machine, 37 mmφ, L / D = 3)
1.5) and melt-kneading / pelletizing while removing unreacted glycidyl methacrylate by suction from the ventro, the graft copolymer (EPO-PS).
1) was obtained. The pellets thus obtained were purified and dried in a toluene / methanol system and titrated for epoxy value. As a result, the graft copolymerization amount of glycidyl methacrylate was 0.9% by weight.

(A-2) 500 g of styrene and 27 g of glycidyl methacrylate (GMA) were subjected to a copolymerization reaction at 80 ° C. for 5 hours using ethylbenzene as a solvent and benzoyl peroxide as a polymerization initiator to give styrene-GM.
A copolymer (EPO-PS2) was obtained. After the obtained polymer was purified and dried with a toluene / methanol system, the epoxy value was titrated and analyzed to find that the copolymerization amount of glycidyl methacrylate was 5.0% by weight.

(B) Preparation of Composition 45 parts by weight of MPPE, an acid-modified hydrogenated styrene-butadiene block copolymer elastic body (Kreton FG manufactured by Shell Chemical Co., Ltd.)
Mixture 1 consisting of 1901X, styrene content 28% by weight, maleic anhydride addition amount 2.0% by weight) 15 parts by weight, polyamide resin (CM1007 manufactured by Toray Industries, Inc.) 40 parts by weight
To 100 parts by weight, 5 parts by weight of the epoxy group-containing polystyrene (EPO-PS2) obtained in (a-2) was added, and the same procedure as in Example 1 was performed. The results are almost the same as in Example 1, as shown in Table 1.

Example 14 Using epoxy group-containing polystyrene (EPO-PS1) prepared in (a-1) and increasing the addition amount, the same procedure as in Example 13 was carried out, and substantially the same results were obtained. It was

[Comparative Example 7] An unmodified styrene block copolymer elastic material (G1650) was used as an impact resistance improver.
The same procedure as in Example 14 was carried out except that was used, but the basic physical properties were generally low, the water absorption rate was high, and the dimensional stability was low.

Example 15 The procedure of Example 13 was repeated, except that a 1: 1 mixture of oxazolinyl group-containing polystyrene (RPS1005) and epoxy group-containing polystyrene (EPO-PS2) was used, and substantially the same results were obtained. Obtained.

Example 16 Polystyrene graft ethylene-glycidyl methacrylate copolymer (polystyrene content 30 wt%, glycidyl methacrylate content 10.5 wt%) manufactured by NOF CORPORATION as an epoxy group-containing aromatic vinyl copolymer (EPO) Example 4 was carried out in the same manner except that -PS3) was used, and substantially the same basic characteristics as well as excellent moisture absorption characteristics and thermal stability were obtained.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

EFFECTS OF THE INVENTION The resin composition of the present invention balances basic properties such as impact resistance, heat resistance and rigidity at a high level, and further has improved thermal stability and hygroscopic property in a high temperature atmosphere. It is a thing. Therefore, a molded product obtained by molding the resin composition of the present invention by a method such as injection molding, blow molding, and extrusion molding has excellent heat resistance, water resistance, dimensional stability, impact resistance, rigidity, and thermal stability. Yes, these are especially car fenders, door panels, quarter panels,
It is extremely useful as exterior parts such as bumpers, spoilers, wheel caps, FEEL lids, side shields, and other general mechanical parts.

Front page continuation (72) Inventor Kazuya Takemura, 1 Kawasaki-cho, Chuo-ku, Chiba, Chiba Prefecture Technical Research Division, Kawasaki Steel Co., Ltd. (72) Masahiro Wakui 1, Kawasaki-cho, Chuo-ku, Chiba Address: Kawasaki Steel Corporation, Technical Research Division

Claims (2)

[Claims] 1. (A) Acid-modified polyphenylene ether resin, (B) Polyamide resin, (C) Acid-modified styrene aromatic hydrocarbon / conjugated diene block copolymer, hydrogenated product thereof and acid-modified olefin copolymer An impact resistance improver comprising an unmodified styrenic aromatic hydrocarbon / non-conjugated diene block copolymer or a hydrogenated product thereof, which is optionally blended with at least one selected from the group, and (D) an oxazolinyl group-containing fragrance Group vinyl polymer (D
-1) and an epoxy group-containing aromatic vinyl polymer (D
-2) A thermoplastic resin composition comprising at least one copolymer selected from the above. 2. The thermoplastic resin composition according to claim 1, wherein the blending ratio of each component is as follows. (A) 20 to 80 parts by weight, (B) 80 to 20 parts by weight, (C) 5 to 40 parts by weight (where (A) + (B) +
(C) should be 100 parts by weight), (D) 0.5 to 30 parts by weight per 100 parts by weight of the total amount of (A), (B), and (C).