JP3504342B2 - Heat resistant resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent mechanical properties and molding processability, and particularly excellent heat aging resistance.

[0002]

2. Description of the Related Art Polyphenylene ether resin is a resin having excellent dimensional stability, electrical characteristics, heat resistance, water resistance and the like, and is industrially widely used in a form blended with polystyrene resin. It has a major drawback of being inferior in oil resistance and moldability. On the other hand, polyamide resin has excellent mechanical strength, oil resistance, heat resistance, etc.
Widely used as the most representative engineering resin, dimensional stability, hygroscopicity, heat resistance under high load,
It has the drawback of poor impact resistance when dried. Therefore, it has been attempted to formulate both resins into compositions for the purpose of complementing the drawbacks of the two resins by making use of the respective advantages of the above resins, and various compositions have been proposed and put to practical use so far. .

Compositions of this polyphenylene ether resin and polyamide resin are widely used because they exhibit the impact strength and ductility required for automobile parts, and have heat resistance to withstand on-line baking coating. Further, it is expected to develop into a field that makes the best use of this heat resistance, but in the present situation, it is the actual situation that it does not reach a satisfactory level in terms of heat aging resistance. As a technique for improving the heat aging resistance, a technique of adding a highly sterically hindered phenol compound (Japanese Patent Laid-Open No. 62-273256) and a technique of adding a copper stabilizer generally used in polyamide ( JP-A-1-163262) has been proposed.
However, these techniques use stabilizers generally used in polyphenylene ether resins and polyamide resins in compositions of polyphenylene ether resins and polyamide resins, and are not novel at all.

[0004]

The object of the present invention is to provide a composition consisting of a polyphenylene ether resin and a polyamide resin with a long-term heat resistance aiming at practical application in the field where heat resistance, particularly heat aging resistance is required. This is aimed at improving the aging property.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a composition comprising a polyphenylene ether resin, a polyamide resin and the like can be used as a stabilizer for a polyamide resin and a polyphenylene ether. It has been found that the heat aging resistance can be remarkably improved by effectively using a resin phase stabilizer composed of a resin and a rubbery polymer, and the present invention has been completed based on this finding.

That is, the present invention relates to the following:
is there. 1. (A) polyamide resin 5 to 95% by weight , (B) polyphenylene ether resin 95 to 5% by weight , (C) rubber-like polymer 0.1 to 50% by weight , and as a modifier ,
Note that the total amount of components (A), (B) and (C) is 100 parts by weight.
On the other hand, in a resin composition comprising 0.05 to 5 parts by weight of (D) a compound having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule, (E): stability of a polyamide resin Agent contained in component (A) resin phase,
(F): Poly stabilizer polyphenylene ether resin and rubber-like polymer (B) and (C) Ri Na contained in the resin phase made of components, the stabilizer (E) Polyamide resin copper compound
And at least one of alkali metal halides
The amount of copper compound used is 100 parts by weight of polyamide resin.
On the other hand, 0.0005 to 0.2 parts by weight of copper, alkali
The amount of the remetal halide is 0.005 to 1.0 part by weight.
And (F) polyphenylene ether resin and
The rubbery polymer stabilizer is a combination of metal sulfide and metal oxide.
Combination, metal deactivator, amines, hindered pheno
Selected from alcohols, phosphites and thioethers
Stabilizer or a combination thereof.
Liphenylene ether resin and rubber-like polymer 100
Range der Ru resin composition of 0.01 to 5 parts by weight per part by weight. 2. (E): Polyamide resin stabilizer and (F): Polyphenylene ether resin and rubber-like polymer stabilizer are contained in each resin, so that each resin is blended in a high concentration. The method for producing a resin composition according to the above item 1, characterized in that these are added in the form of a masterbatch.

The present invention will be described in detail below. The polyamide resin used as the component (A) in the present invention is
Amide bond to the polymer main chain {-NH-C (= O)-
}, And any material that can be melted by heating can be used. Typical examples are 4-nylon, 6-nylon, 6,6-nylon,
12-nylon, 6,10-nylon, polyamide from terephthalic acid and hexamethylenediamine, polyamide from isophthalic acid and hexamethylenediamine, polyamide from adipic acid and metaxylylenediamine , adipic acid and azelaic acid and 2,2 '- bis (p- aminocyclohexyl) - polyamide from propane, or terephthalic acid and 4,4'-diaminodicyclohexylmethane
Et polyamides and these copolymerized nylon and the like. Of these, 6-nylon, 6,6-nylon and 6-6,6 copolymer nylon are preferably used alone or in combination.

In the present invention, the polyphenylene ether resin used as the component (B) is represented by the following general formula (1),

[0009]

[Chemical 1]

(Wherein R1, R2, R3, R4, R5,
R6 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen and hydrogen, and R5 and R6 are not hydrogen at the same time) and the constitutional unit is represented by the formula [1]. Homopolymers of a] and [b], or copolymers and mixtures of these with styrene polymers can be used.

A typical example of a homopolymer of a polyphenylene ether resin is poly (2,6-dimethyl-1,4).
-Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl) -1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-)
1,4-phenylene) ether, poly (2-ethyl-6)
-Isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly ( Homopolymers such as 2-methyl-6-chloroethyl-1,4-phenylene) ether are mentioned.

The polyphenylene ether copolymer is 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure such as a copolymer with cresol.

Further, in the polyphenylene ether resin of the present invention, various other phenylene ether units which have been conventionally proposed to be allowed to exist in the polyphenylene ether resin are included as long as they do not violate the gist of the present invention. It may be included as a structure. As an example of what is proposed to coexist in a small amount, Japanese Patent Application No. 63-12
698 and JP-A-63-301222, 2- (dialkylaminomethyl) -6-methylphenylene ether units and 2- (N-alkyl-N-phenylaminomethyl) -6-methyl. Examples include a phenylene ether unit.

Further, a polyphenylene ether resin in which a small amount of diphenoquinone or the like is bound in the main chain is also included.
The polyphenylene ether resin used in the present invention has an intrinsic viscosity (chloroform solution, 30 ° C.) of 0.30 to 1.5, preferably 0.35 to 1.0.

In the present invention, the styrene resin used in combination with the polyphenylene ether resin is obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. Is a polymer. The styrene compound is represented by the general formula [2],

[0016]

[Chemical 2]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5). Means a compound. Specific examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like. The compounds copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile;
Examples thereof include acid anhydrides such as maleic anhydride, which are used together with styrene compounds. Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, hydrogenated products thereof, and ethylene-propylene copolymer rubbers.

The method for producing the styrene resin of the present invention is not limited, and any of bulk polymerization, solution polymerization, emulsion polymerization and suspension polymerization well known to those skilled in the art may be used. In the present invention, the rubber-like polymer used as the component (C) includes a styrene-butadiene block copolymer, a hydrogenated styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a hydrogenated styrene-isoprene block. Copolymer, ethylene-propylene elastomer, ethylene-based ionomer resin, core consisting of rubber-like core and non-rubber-like polymer shell.
Shell polymers and the like are preferable, and styrene-butadiene block copolymers and styrene-butadiene block copolymers in which some or all of the butadiene moieties are hydrogenated are particularly preferable. Further, it is also possible to use those obtained by modifying these rubber-like polymers with an epoxy compound, an unsaturated carboxylic acid and its derivative, or the like.

The blending ratio of the resin component of the present invention is as follows: (A) polyamide resin 5 to 95% by weight, (B) polyphenylene ether resin 95 to 5% by weight, and (C) rubbery polymer 0.1 to 50%. Used in the range of wt%. In the present invention, the compound having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group at the same time, which is used as the component (D), is an unsaturated dicarboxylic acid and its derivative, and a hydroxycarboxylic acid. . Maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and their acid anhydrides,
Examples include esters, half-alkyl esters, amides, imides, citric acid, lactic acid, malic acid, and the like.
α, β-Unsaturated dicarboxylic acids and their derivatives, specifically citric acid, fumaric acid, maleic acid and maleic anhydride are preferred, with maleic anhydride being most preferred. The unsaturated dicarboxylic acid and its derivative and the hydroxycarboxylic acid may be used alone or in combination of two or more kinds. The amount of the component (D) added is 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the total amount of the components (A), (B) and (C). It is desirable to select within the range. If the addition amount is less than 0.05 parts by weight, the particle size of the dispersed phase becomes large, which is not preferable in terms of physical properties. If the addition amount exceeds 5 parts by weight, there is a problem that the resin is colored or the physical properties are deteriorated, which is not preferable.

As a stabilizer for the polyamide resin used in the component (E) of the present invention, a metal compound such as copper, nickel or tin, a halide of an alkali metal, and a combination of both are known. Examples of the metal compound include cupric chloride, cupric chloride, copper iodide, copper sulfate, copper nitrate, metal salts of inorganic acids such as copper phosphate, copper acetate, copper salicylate, copper stearate, and copper benzoate. Examples thereof include copper salts of organic acids such as copper lactate and copper sebacate, or copper chelate compounds, with copper acetate and copper iodide being preferred.

Examples of alkali metal halides include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium bromide and sodium chloride, with potassium iodide being preferred. This polyamide compound stabilized with a copper compound or an alkali metal halide is easily available on the market, and it is preferable to use an effective amount of these commercially available polyamides in order to obtain the composition of the present invention. .

In the present invention, it is important to disperse the copper-based stabilizer in the polyamide resin so that it is preliminarily used as a masterbatch with a high-concentration of the stabilizer or in an amount required for the final composition. It is preferable to use a polyamide containing copper. The amount of the stabilizer for the polyamide resin used in the present invention is 0.0005 to 0.2 part by weight, preferably 0.001 to 0.1 part by weight, as copper, relative to 100 parts by weight of the polyamide resin used. The amount of alkali metal halide is 0.005 to 1.0 part by weight, preferably 0.02 to 0.5 part by weight.

As the stabilizer for the polyphenylene ether resin and the rubber component used in the component (F) of the present invention, the following stabilizers and combinations thereof are used. 1. Combination of metal sulfide and metal oxide 2. Metal deactivator 3. Amines 4. Hindered phenols 5. Phosphorous acid esters 6. Thioethers These are specifically explained as follows. As a combination of a metal sulfide and a metal oxide, a combination of zinc sulfide and zinc oxide or magnesium oxide may be used. As the metal deactivator, hydrazine derivatives such as adipic acid dihydrazide and isophthalic acid dihydrazide,
Irganox (trademark) MD1024 (manufactured by Ciba Geigy), melamine and its derivatives or similar compounds (JP-A-4-239547, JP-A-4-239).
556, JP-A-4-239557 and JP-A-4-239557.
239558, compounds described in each publication) and ADEKA STAB (trademark) mark CDA-1, mark CDA-6, mark ZS-27, mark ZS-81 (all manufactured by Asahi Denka Co., Ltd.), Stabinol (trademark) CS-. 42 (manufactured by Sumitomo Chemical Co., Ltd.), etc. Amines, 4. Hindered phenols, 5. Phosphorous acid esters and 6. As the thioethers, the compounds described in JP-A-4-239556 are used.

The amount of the stabilizer for the resin composed of the polyphenylene ether resin and the rubber-like polymer used in the present invention is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin, and more preferably 0. 05 to 2 parts by weight is more preferable. If it is less than 0.01 parts by weight, the improvement effect is not sufficient, and 5
Even if added in excess of parts by weight, the improvement effect is small, but the heat resistance and impact resistance are decreased, which is not preferable.

It is preferable that the polyphenylene ether resin and the stabilizer for the resin composed of the rubber-like polymer are blended so as to be selectively distributed to the resin. For that purpose, it is preferable to knead in advance. The composition of the polyamide resin and the polyphenylene ether resin requires a step of modifying with a modifier, and even if a stabilizer is added in this step, the effect is remarkably reduced, which is not preferable. Therefore, a method of adding a stabilizer after denaturation is conceivable, but there is a problem that the effect cannot be obtained by simply adding the stabilizer and the effect is small. Therefore, as a countermeasure, polyphenylene ether resin, polystyrene resin, rubber-like polymer, etc.
As a result of examining the method of adding the stabilizer in the form of a so-called masterbatch in which the stabilizer was kneaded at a high concentration, it was found that this method was effective and most practical.

The temperature and time for melting and kneading the components constituting the present invention may be set according to the type and blending ratio of the resin components used, but normally 240 to 360 ° C.,
Preferably a temperature of 260-340 ° C. is also 0.1-1
A kneading time of 0 minutes, preferably about 0.3 to 3 minutes, is suitable. As the melt-kneading device, a single-screw extruder, a twin-screw extruder, a heating roll, a Banbury mixer, a kneader or the like can be used, but an extruder is preferable, and a twin-screw extruder is most preferable.

If desired, the composition of the present invention may contain other additives such as reinforcing agents such as glass fibers, carbon fibers and various whiskers, or particulate or fibrous fillers, flame retardants and plasticizers. An ultraviolet absorber, a colorant, a release agent, etc. can be added.

[0028]

EXAMPLES Next, the present invention will be specifically described with reference to Examples. The following examples are all exemplary,
It does not limit the content of the present invention. The components used in the examples and comparative examples are as follows. (A) Polyamide resin A-1: ηr = 2.45 (95.5% sulfuric acid, 25 ° C.) polyamide 6 (B) Polyphenylene ether resin B-1: Intrinsic viscosity 0.50 (30 ° C. in chloroform) Poly-2,6-dimethyl-1,4- phenylene which is
Ether B-2: Reduced viscosity ηsp / c is 1.00 dl / g (3
Polystyrene at 0 ° C. in toluene). (C) Rubber-like polymer C-1: Hydrogenated styrene-butadiene block copolymer (manufactured by Asahi Kasei Corporation, Tuftec (trademark) H127
1) C-2: partially hydrogenated styrene-butadiene block copolymer having a hydrogenation rate of 30% (styrene content 35%, molecular weight 12
(D) Compound D-1 having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule D-1: a stabilizer of maleic anhydride (E) polyamide, which is stabilized by the stabilizer Polyamide E-1: Polyamide 6 represented by (A-1)
Polyamide 6 containing 0.1% by weight of copper and melt-kneaded.

E-2: Copper acetate and potassium iodide were added at the polymerization stage to carry out polymerization, and ηr = 2.45 (9 after polymerization).
5.5% sulfuric acid at 25 ° C.), and copper is 0.1% by weight in terms of copper,
Polyamide 6 which also contains iodine in an amount of 0.5% by weight in terms of iodine. (F) Polyphenylene ether resin and rubber-like polymer stabilizer F-1: pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] F-2: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate F-3: NN′-hexamethylenebis (3,5-di-t-butyl-) 4-Hydroxyhydrocinmanamide) F-4: 2,4-bis- (n-octylthio) -6-
(4-hydroxy-3,5-di-t-butylanilino)
-1,3,5 Triazine F-5: 2-t-butyl-6- (3-t-butyl-2)
-Hydroxy-5-methylbenzyl) -4-methylphenyl acrylate F-6: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate F-7: Di-stearyl-3,3 '-Thio-di-propionate F-8: tris (2,4-di-t-butylphenyl)
Phosphite F-9: triethanolamine F-10: zinc sulfide / zinc oxide = 1/1 weight ratio mixture F-11: isophthalic acid dihydrazide F-12: ADEKA STAB (trademark) CDA-1
(Asahi Denka Kogyo KK) F-13: Irganox (trademark) MD1024 (Ciba-Geigy Co., Ltd.) F-14: Stabinol (trademark) CS-42 (Sumitomo Chemical Co., Ltd.) F-15: Succinoguanamine F-16:

[0030]

[Chemical 3]

The physical property evaluation conditions and methods are as follows. A test piece was prepared with an injection molding machine (IS80C manufactured by Toshiba Machine Co., Ltd., cylinder temperature 280 ° C., molding cycle 1 minute), and the following physical property measurements and tests were carried out. (1) Thermal aging test A 1/8 inch Izod test piece was subjected to an aging test in an oven at 120 ° C, taken out at 500 hours and 1000 hours, and measured at 23 ° C and -30 ° C to obtain a retention rate before and after aging. It was

Izod impact strength: ASTM D256
Measured according to.

[0033]

Example 1 In advance, polyphenylene ether (B-1)
2.5 parts by weight of rubber-like polymer (C-1) and 0.5 parts by weight of stabilizer (F-1) in a ratio of 0.5 parts by weight of stabilizer (F-1) at 280 ° C. and a screw diameter of 25 mm. Was pre-kneaded to prepare a masterbatch of (F-1). Next, the screw diameter was set at a ratio of 32.5 parts by weight of the polyphenylene ether resin (B-1), 12.5 parts by weight of the rubber-like polymer (C-1) and 0.3 part by weight of the modifier (D-1). 25 mm
Supplied from the top (previous stage) of the co-rotating twin-screw extruder of
45 parts by weight of polyamide 6 (A-1), 5 parts by weight of stabilized polyamide 6 (E-1) and 5.5 parts by weight of a masterbatch of (F-1) produced in advance were used in the extruder ( (Middle stage), and extruded and kneaded at 300 ° C., 300 rpm and a discharge rate of 20 Kg / Hr to obtain composition pellets. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1. (The resin compositions shown in Tables 1 to 4 are shown with the stabilizer masterbatch portion corrected for each component.)

[0034]

Examples 2 to 9 The same procedure as in Example 1 was carried out except that the component (F) was changed to the type shown in Table 1. The results are shown in Table 1.

[0035]

[Comparative Example 1] Polyphenylene ether resin (B-1)
35 parts by weight, 15 parts by weight of the rubber-like polymer (C-1) and 0.3 parts by weight of the modifier (D-1), and the screw diameter 25.
mm from a co-rotating twin-screw extruder at the top (previous stage), and 50 parts by weight of polyamide 6 (A-1) from the middle of the extruder (middle stage) at 300 ° C., 300 rpm and a discharge rate of 20 kg / The composition was pelletized by extrusion kneading with Hr. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0036]

Comparative Example 2 Polyphenylene ether resin (B-1)
35 parts by weight, 15 parts by weight of the rubber-like polymer (C-1) and 0.3 parts by weight of the modifier (D-1), and the screw diameter 25.
mm from the top of the twin-screw co-rotating extruder (the first stage), 45 parts by weight of polyamide 6 (A-1) and 5 parts by weight of stabilized polyamide 6 (E-1) are in the middle of the extruder (middle stage). Supply from 300 ℃, 300rpm, discharge amount 20Kg
The mixture was extruded and kneaded with / Hr to obtain composition pellets. Then, various tests were conducted by the above-mentioned method. (Stabilized Polyamide 6 (E-1): Kneaded in advance to form a masterbatch) Evaluation results are shown in Table 1.

[0037]

[Comparative Example 3] Polyphenylene ether resin (B-1)
35 parts by weight, 15 parts by weight of the rubber-like polymer (C-1) and 0.3 parts by weight of the modifier (D-1), and the screw diameter 25.
mm from the top of the twin-screw co-rotating extruder (previous stage), 50 parts by weight of polyamide 6 (A-1) and 0.5 parts by weight of stabilizer (F-1) from the middle of the extruder (middle stage). Supply, 300 ℃, 300rpm, discharge rate 20Kg / Hr
Was extruded and kneaded to obtain a composition pellet. ("F-1"
In order to contain the component (F) in the component (B) and the component (C), it was kneaded in advance and did not become a master batch.) Then, various tests were carried out by the method described above. The evaluation results are shown in Table 1.

[0038]

[Comparative Example 4] Polyphenylene ether resin (B-1)
35 parts by weight, 15 parts by weight of the rubber-like polymer (C-1) and 0.3 parts by weight of the modifier (D-1), and the screw diameter 25.
supplied from the top (previous stage) of a co-rotating twin-screw extruder of mm, 45 parts by weight of polyamide 6 (A-1), 5 parts by weight of stabilized polyamide 6 (E-1) and a stabilizer (F-1). )
30 parts by feeding 0.5 parts by weight from the middle of the extruder
The composition was pelletized by extrusion kneading at 0 ° C., 300 rpm and a discharge rate of 20 Kg / Hr. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0039]

[Comparative Example 5] Polyphenylene ether resin (B-1)
35 parts by weight, 15 parts by weight of the rubber-like polymer (C-1) and 0.3 parts by weight of the modifier (D-1), and the screw diameter 25.
supplied from the top (previous stage) of a co-rotating twin-screw extruder of mm, 50 parts by weight of polyamide 6 (A-1), 1st iodide
Copper (0.015 parts by weight) and stabilizer (F-1) (0.5 parts by weight) were supplied from the middle of the extruder to obtain 300 ° C., 30
The composition was pelletized by extrusion kneading at 0 rpm and a discharge rate of 20 kg / hr. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 1.

[0040]

Examples 10 to 13 The same procedure as in Example 1 was carried out except that the component (F) was changed to that shown in Table 2. In addition, as for the combined use system of the stabilizers, the increase in the combined use was dealt with by increasing the master batch. The results are shown in Table 2.

[0041]

Examples 14 to 28 The procedure of Example 1 was repeated, except that the component (F) was changed to that shown in Table 3. In addition, as for the combined use system of the stabilizers, the increase in the combined use was dealt with by increasing the master batch. The results are shown in Table 3.

[0042]

Example 29 5 parts by weight of polystyrene (B-2) and 0.5 part by weight of stabilizer (F-4) were preliminarily kneaded at 200 ° C. in a co-rotating twin screw extruder having a screw diameter of 25 mm,
A masterbatch of stabilizer was prepared. Next, screw system 25 mm with a ratio of 30 parts by weight of polyphenylene ether resin (B-1) and 0.3 parts by weight of modifier (D-1).
Supplied from the top (previous stage) of the co-rotating twin-screw extruder of
45 parts by weight of polyamide 6 (A-1), 5 parts by weight of stabilized polyamide 6 (E-2), and rubber-like polymer (C-2) 1
5 parts by weight and 5.5 parts by weight of a masterbatch of a pre-produced stabilizer were supplied from the middle of the extruder, and extruded and kneaded at 300 ° C., 300 rpm and a discharge rate of 20 Kg / Hr to form a composition pellet. Got Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 4.

[0043]

Examples 30 to 35 The same procedure as in Example 29 was carried out except that the component (F) was changed to those shown in Table 4.
In addition, as for the combined use system of the stabilizers, the increase in the combined use was dealt with by increasing the master batch. The results are shown in Table 4.

[0044]

Comparative Example 6 Polyphenylene ether resin (B-1)
30 parts by weight and 0.3 part by weight of the modifier (D-1) were supplied from the top (previous stage) of a co-rotating twin-screw extruder having a screw diameter of 25 mm, and polyamide 6 (A-1) was added at 50 parts.
Parts by weight, 5 parts by weight of polystyrene (B-2) and 15 parts by weight of the rubber-like polymer (C-2) are supplied from the middle of the extruder (middle stage), 300 ° C., 300 rpm, discharge rate 20 Kg /
The composition was pelletized by extrusion kneading with Hr. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 4.

[0045]

Comparative Example 7 Polyphenylene ether resin (B-1)
30 parts by weight and 0.3 parts by weight of the modifier (D-1) were supplied from the top (previous stage) of a co-rotating twin-screw extruder having a screw diameter of 25 mm, and polyamide 6 (A-1) was added to 4 parts.
5 parts by weight and 5 parts by weight of stabilized polyamide 6 (E-1),
5 parts by weight of polystyrene (B-2) and 15 parts by weight of a rubber-like polymer (C-1) were supplied from the middle of the extruder (middle stage), and extruded and kneaded at 300 ° C., 300 rpm and a discharge rate of 20 Kg / Hr. A product pellet was obtained. Then, various tests were conducted by the above-mentioned method. The evaluation results are shown in Table 4.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

INDUSTRIAL APPLICABILITY The resin composition of the present invention contains a stabilizer for polyamide and a stabilizer for polyphenylene ether resin so as to be distributed to the respective resins, whereby the heat aging resistance is greatly improved. . In addition to the above characteristics,
It is useful for various applications such as automobiles, electric / electronic parts, etc. as a material excellent in chemical resistance, which is a characteristic of the polyphenylene ether / polyamide composition, in which there is little dimensional change upon water absorption and rigidity reduction.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-157894 (JP, A) JP-A-5-295129 (JP, A) JP-A-7-41657 (JP, A) JP-A-6- 166812 (JP, A) JP 7-102168 (JP, A) JP 7-41658 (JP, A) JP 6-157895 (JP, A) JP 7-48504 (JP, A) Japanese Patent Publication No. 40-1647 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 71/12 C08K 3/00-5/59 C08L 21/00-21/02 C08L 77 / 00-77/12

Claims (2)

(57) [Claims] 1. (A) Polyamide resin 5 to 95% by weight ,
(B) Polyphenylene ether resin 95 to 5% by weight ,
(C) 0.1 to 50% by weight of a rubbery polymer, and 10 parts by weight of the above components (A), (B) and (C) as a modifier.
A resin composition comprising 0.05 to 5 parts by weight relative to 0 parts by weight of (D) a compound having a carboxylic acid group, an acid anhydride group, an epoxy group, an amino group or a hydroxyl group in the molecule,
(E): containing stabilizers of the polyamide resin component (A) resin phase, (F): containing stabilizers of the polyphenylene ether resin and rubber-like polymer consisting of (B) and component (C) resin phase Ri greens and, the stabilizer (E) polyamide resin
At least one of copper compounds and alkali metal halides
The amount of copper compound used is 100 weight of polyamide resin.
0.0005 to 0.2 part by weight of copper, based on the amount of
0.005 to 1.0 weight of alkali metal halide
(F) Polyphenylene ether resin
And the stabilizer of the rubber-like polymer is the stabilizer of the following 1 to 6 or
It is a combination and the amount used is polyphenylene
Based on 100 parts by weight of ether resin and rubber-like polymer
Range der Ru resin composition of 0.01 to 5 parts by weight. 1. Combination of metal sulfide and metal oxide 2. Metal deactivator 3. Amines 4. Hindered phenols 5. Phosphorous acid esters 6. Thioethers 2. A stabilizer for each of the resins such that (E): a stabilizer for a polyamide resin and (F): a stabilizer for a polyphenylene ether resin and a rubber-like polymer are contained in each resin. Is blended in a high concentration, and these are added in the form of a masterbatch, the method for producing a resin composition according to claim 1 .