JP2546344B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a thermoplastic resin composition having excellent impact resistance, moldability, chemical resistance, weld strength, and good appearance.

b. Conventional technology Polyamide resins such as nylon-6, nylon-66, nylon-12 and nylon-46, and polyester resins such as polyethylene terephthalate and polybutylene terephthalate have various excellent characteristics. It is utilized in many fields such as plastic products and films. However, the polyamide resin and the polyester resin are not so excellent in impact resistance, and particularly have a defect that the impact resistance is low when a notch is formed.

Due to these drawbacks, the above materials have not always been satisfactory for a wider range of applications.

Therefore, in order to improve impact resistance, many methods of blending rubber or rubber-reinforced resin have been reported, but depending on these methods, it is possible to sufficiently improve the impact resistance of polyamide resin and polyester resin. I can't
Weld strength and molding appearance are also insufficient.

c. Problems to be Solved by the Invention As described above, the conventional methods have not been able to sufficiently improve the impact resistance, weld strength and molding appearance of polyamide resins and polyester resins.

As a result of intensive studies to solve the above-mentioned drawbacks, the present inventors have found that (A) a styrene-based copolymer obtained by copolymerizing a carboxyl group-containing unsaturated compound, (B) a styrene-based polymer,
The composition comprising (C) polyamide resin and / or polyester resin, and (D) organic phosphite compound has impact resistance, moldability, chemical resistance, weld strength,
And, they have found that they are excellent in molding appearance, and have reached the present invention.

d. Means for Solving the Problems The thermoplastic resin composition of the present invention comprises (A) a styrene-based copolymer in which a carboxyl group-containing unsaturated compound is copolymerized, 5 to 80% by weight, and (B) a styrene-based copolymer. Mixture 100 comprising 5 to 85% by weight of polymer and 10 to 90% by weight of (C) polyamide polymer and / or polyester polymer
A composition containing 0.1 to 10 parts by weight of an organic phosphite compound (D) in parts by weight, wherein the content of the carboxyl group-containing unsaturated compound in the whole composition (a) is 0.02 to 4% by weight. (B) The content of the rubber component in the entire composition is 5 to 40% by weight, and the intrinsic viscosity (30 ° C., methyl ethyl ketone) of the matrix component in the components (c) (A) and (B) is
It is characterized by being 0.35 dl / g or more.

The styrene-based copolymer (A) in which the carboxyl group-containing unsaturated compound is copolymerized is a carboxyl group-containing unsaturated compound, an aromatic vinyl compound and, if necessary, in the absence or presence of the rubbery polymer. It is a copolymer obtained by polymerizing another monomer copolymerizable with these.
From the viewpoint of heat resistance, it is preferable to carry out the polymerization in the absence of a rubbery polymer.

Examples of the carboxyl group-containing unsaturated compound in the component (A) include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, and maleic acid, with acrylic acid and methacrylic acid being preferred. These are used alone or in combination of two or more.

As the aromatic vinyl compound as the component (A), styrene,
α-methylstyrene, methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, n-tert-butylstyrene, ethylstyrene, vinylnaphthalene, o-methylstyrene, p-methylstyrene, dimethyl Styrene and the like can be used alone or in combination of two or more. Of these, the preferred aromatic vinyl compound is styrene, and when two or more aromatic vinyl compounds are used in combination, it is preferable to use styrene in a proportion of 50% by weight or more.

Examples of the monomer copolymerizable with the carboxyl group-containing unsaturated compound and the aromatic vinyl compound include a maleimide compound, a vinyl cyan compound and another vinyl compound.

Examples of the maleimide compound include maleimide and N.
-Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-o-chlorophenylmaleimide,
Examples thereof include N-cyclohexylmaleimide and the like. Particularly preferred are N-phenylmaleimide, N-o-chlorophenylmaleimide, N-cyclohexylmaleimide and the like, and these can be used alone or in combination of two or more.

Examples of the vinyl cyan compound include acrylonitrile and methacrylonitrile, and of these, acrylonitrile is preferable.

Other copolymerizable vinyl compounds include alkyl esters of acrylic acid such as methyl acrylate, ethyl acrylate and propylene acrylate; methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and propylene methacrylate. Can be used alone or in combination of two or more.

Further, the rubbery polymer is not always necessary, but when used, the following rubbery polymers are preferable.

Ethylene-α-olefin copolymers such as ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers; ethylene-methacrylate, ethylene-
Copolymer of ethylene and unsaturated carboxylic acid ester such as butyl acrylate; Copolymer of ethylene and fatty acid vinyl such as ethylene-vinyl acetate; Ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer Ethylene-propylene-non-conjugated diene terpolymers such as coalesce; polybutadiene,
Random copolymers and block copolymers of isoprene, styrene-butadiene, diene rubbers such as hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers; butylene-isoprene copolymers There are polymers and the like, and these can be used alone or in combination of two or more.

Of these, preferred rubbery polymers in terms of impact resistance are diene rubber, ethylene-propylene rubber, and ethylene-propylene-non-conjugated diene terpolymer.
Polybutadiene and styrene-butadiene copolymer are more preferred, and the styrene content in this styrene-butadiene copolymer is preferably 50% by weight or less from the viewpoint of impact resistance.

Specific examples of the component (A) include the following types.

1) A copolymer in which a carboxyl group-containing unsaturated compound and aromatic vinyl are essential, 2) A monomer in which aromatic vinyl and a carboxyl group-containing unsaturated compound are essential components in the presence of a rubbery polymer. A graft copolymer obtained by copolymerizing 3), 3) a mixture of 1) and 2).

In the above 1) to 3), styrene is preferable as the aromatic vinyl, and acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl.

The unsaturated compound containing a carboxyl group is 0.1 in the component (A).
Is preferably 8 to 8% by weight, more preferably 0.2 to 7% by weight, and particularly preferably 0.3 to 7% by weight. If it is less than 0.1% by weight, impact resistance and weld strength are low, and if it exceeds 8% by weight, impact resistance, moldability, weld strength and molding appearance are poor. The content of the carboxyl group-containing unsaturated compound in the entire composition is 0.02 to 4% by weight, preferably 0.05 to 3.5% by weight, more preferably 0.1 to 3% by weight.
Is. If it is less than 0.02% by weight, impact resistance and weld strength are low, and if it exceeds 4% by weight, impact resistance, molding processability,
Weld strength and molded appearance deteriorate.

In the composition of the present invention, the compounding ratio of the styrene-based copolymer (A) obtained by copolymerizing a carboxyl group-containing unsaturated compound is
5 to 80% by weight, preferably 5 to 70% by weight,
More preferably, it is 5 to 65% by weight. If it is less than 5% by weight, impact resistance is poor, and if it exceeds 80% by weight, moldability and appearance are deteriorated.

The styrene polymer (B) contains an aromatic vinyl compound as an essential component in the presence or absence of a rubbery polymer,
It is a polymer obtained by polymerizing a resin component containing at least one monomer selected from a maleimide compound, a vinyl cyan compound and another copolymerizable vinyl monomer, if necessary.

The rubbery polymer, the aromatic vinyl compound, the maleimide compound, and the other vinyl monomer copolymerizable therewith are the same as those shown in the component (A).

The styrene-based polymer (B) is a polymer obtained by polymerizing a monomer of a resin component in the presence of a rubbery polymer, and a polymer of a monomer of the resin component in the absence of a rubbery polymer. It may be a composition with a resin.

Specific examples of the styrene polymer (B) include acrylonitrile-butadiene rubber-styrene resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene resin (AES resin), acrylonitrile-butadiene rubber-methyl methacrylate-styrene resin. (ABSM resin), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-styrene copolymer (MS resin), high impact polystyrene (HIPS), acrylonitrile-n-butyl acrylate rubber-styrene resin (AAS resin) And so on.

The compounding ratio of the styrene polymer (B) in the composition is 5 to 85% by weight, preferably 7 to 80% by weight, more preferably 10 to 75% by weight. If the amount of component (B) exceeds 85% by weight, the weld strength will be poor. If it is less than 5% by weight, impact resistance is poor. When polyamide is selected as the component (C), the preferable blending ratio of the component (B) is 10 to 80% by weight, whereby a thermoplastic resin composition having excellent impact resistance and molding appearance can be obtained.

The content of the rubber component in the total composition is 5 to 40% by weight, preferably 6 to 38% by weight, more preferably 7 to 35% by weight. If it is less than 5% by weight, the impact resistance is low, and if it is 40% by weight or more, the fluidity and gloss are poor.

The average graft ratio of the monomer to the rubber component in the entire composition of the present invention is preferably 30% by weight or more, more preferably
It is 40% by weight or more, particularly preferably 50 to 150% by weight. 3
If it is less than 0% by weight, the molding appearance of the molded article is affected by the molding temperature, and the gloss decreases.

 Here, the graft ratio was measured by the following method.

Accurately sample 1 g of material, add 20 cc of acetone to this,
The mixture was shaken for a period of time and then separated into a soluble component and an insoluble component by using a centrifugal separator having a rotation speed of 20,000 rpm, and the insoluble component was dried by a vacuum dryer to obtain an insoluble component (C). On the other hand, the amount of rubber (R) in the insoluble matter (C) was calculated from the polymerization composition and the polymerization conversion, and the graft ratio was determined from the following equation.

Further, the matrix component in the components (A) and (B) is an acetone-soluble component in the components (A) and (B). The intrinsic viscosity (solvent methyl ethyl ketone at 30 ° C.) of the matrix is 0.35 dl / g or more, preferably 0.4 dl / g
~ 1 dl / g. If it is less than 0.35 dl / g, impact resistance and weld strength will be low.

The polyamide polymer (C) of the present invention is not particularly limited, but ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4 and 2,4,4- Trimethylhexamethylenediamine, 1,3 and 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexyl) methane, m-xylylenediamine, p-
Derived from aliphatic, alicyclic and aromatic diamines such as xylylenediamine and aliphatic, alicyclic and aromatic dicarboxylic acids such as adipic acid, speric acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid and isophthalic acid. Polyamide obtained: polyamide obtained by ring-opening polymerization of lactams such as ε-caprolactam, ω-dodecaractam; 6-aminocaproic acid, 1,1-aminoundecanoic acid,
Polyamides derived from 1,2-aminododecanoic acid and the like, copolyamides thereof, and mixed polyamides, which are industrially inexpensive and produced in large quantities, nylon-6 (polycaproamide), nylon-66 (polyamide). Hexamethylene adipamide), nylon-12 (polydodecamide), nylon-610 (polyhexamethylene sebacamide), nylon-46 and copolymers and mixtures thereof are useful.

The degree of polymerization of the polyamide polymer (C) used here is not particularly limited, and usually the relative viscosity (polymer 1 g is 98
% Polyamide which is dissolved in 100 ml of H ₂ SO ₄ and measured at 25 ° C.) is in the range of 1.8 to 6.0. However, if it is in the range of 2 to 5, impact resistance and A product with an excellent balance of molding processability can be obtained. The molecular structure of polyamide is also not limited, and either linear polyamide or branched polyamide may be used.

The polyester polymer (C) used in the present invention is not particularly limited, but is obtained by a polycondensation product of a dicarboxylic acid or a derivative such as an alkyl ester of dicarboxylic acid and a diol. Of the constituent components of polyester, 70 to 100 mol% of the part constituted by dicarboxylic acid is introduced by terephthalic acid.
.About.0 mol% is introduced by isophthalic acid, terephthalenedicarboxylic acid, adipic acid, sebacic acid and the like. The part composed of glycol is introduced by ethanediol, propanediol, butanediol, pentanediol, and hexanediol, and may be composed of two or more of these. There may be a portion introduced with oxybenzoic acid or bisphenol A, and a mixed polyester obtained by mixing one or more of these polyesters is also included in the scope of the present invention. Such polyesters include polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate and copolymers and mixtures thereof.

When the component (C) in the composition is a polyamide polymer,
The blending ratio is 10 to 90% by weight, preferably 10 to 80
% By weight. If it is less than 10% by weight, moldability and chemical resistance are poor, and if it exceeds 90% by weight, impact resistance, weld strength and molded appearance are poor. When the component (C) is a polyester polymer alone or a mixture of a polyester polymer and a polyamide polymer, the mixing ratio is 10 to 90.
%, Preferably 10 to 80% by weight. If it is less than 10% by weight, moldability and chemical resistance will be poor, and if it exceeds 90% by weight, impact resistance, weld strength and molded appearance will be poor.

The mixing ratio of the polyamide-based polymer and the polyester-based polymer is not particularly limited, and they can be mixed and used in any ratio.

As the organic phosphoric acid compound and / or the organic phosphorous acid compound (D), various compounds can be used, and the phosphoric acid ester or phosphorous acid ester of an organic group is an aliphatic group or aromatic group as the organic group. Various substances such as groups can be used. Among them, the most preferable organic phosphoric acid compound (D)
Is represented by the general formula (I).

Specifically, distearyl pentaerythritol diphosphite in which R ₁ and R ₂ are C ₁₈ H ₃₇ , Di (2,4-ditertiarybutylphenylpentaerythritol diphosphite, or And bis (2,6 ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite is preferred.

The blending ratio of the organic phosphite compound (D) in the composition of the present invention is (A) + (B) + (C) = 100 resin mixture 1
0.1 to 10 parts by weight with respect to 00 parts by weight, preferably 0.1
-8 parts by weight, more preferably 0.1-5 parts by weight.
If less than 0.1 part by weight, impact resistance cannot be expected. Again 1
If it is 0 parts by weight or more, the heat resistance is extremely lowered.

The addition of the component (D) is effective in improving the impact resistance, and the impact resistance at a low temperature is remarkably improved. This is an unexpected effect from the prior art.

A usual method is used for mixing the components (A) to (D) of the composition of the present invention. For example, after mixing the respective components with a mixer, the mixture may be melt-kneaded with a pressing machine at 200 to 320 ° C. for granulation. More simply, each component can be directly melt-kneaded in a molding machine and molded.

However, in order to further improve the impact resistance,
This can be achieved by first melt-kneading the components (A) and (C) at 200 to 320 ° C., then adding the components (B) and (D) and kneading again. The kneading temperature at this time is 200 to 320 ° C., and the kneading time may be 30 minutes or more and is not particularly limited.

The compositions of the present invention include antioxidants such as 2,6-di-t.
-Butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,2-methylene-bis- (4-ethyl-6-t-butylphenol), tris (di-nonylphenyl) ) Phosphite; UV absorbers such as p-t-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-m-octoxyphenyl) benzotriazole; lubricants For example, paraffin wax, stearic acid, hydrogenated oil, stearamide, methylenebis stearamide, n-butyl stearate, ketone wax, octyl alcohol, hydroxystearic acid triglyceride; flame retardant such as antimony oxide.
Aluminum hydroxide, zinc borate, tricresyl phosphate, tris (dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A; antistatic agent such as stearoamidopropyldimethyl-β-hydroxyethyl , Ammonium trates; colorants such as titanium oxide, carbon black; fillers such as calcium carbonate,
Clay, silica, glass fibers, glass spheres, carbon fibers; pigments and the like can be added as necessary. These additives may be added to the composition at any point.

e. Examples Next, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.

A styrene copolymer resin obtained by copolymerizing the carboxyl group-containing unsaturated compound as the component (A) was produced as follows.

(1) Production of a styrene-based copolymer in which a carboxyl group-containing unsaturated compound is copolymerized (A-1 to A-3, A-5
A-8): Ion-exchanged water 300 in a 7 glass flask equipped with a stirrer
Parts, sodium dodecylbenzenesulfonate (2.0 parts) and t-dodecyl mercaptan (0.3 parts) were added, and batch polymerization components composed of various monomers were added in the proportions shown in Table 1, and the temperature was raised with stirring. When the temperature reached 40 ° C, 0.1 part of potassium persulfate was added and the reaction was continued for 2 hours. The resulting resin latex was coagulated with 2 parts by weight of potassium chloride to coagulate the product, dehydrated, washed with water and dried to recover a powdered resin.

(2) Production of Styrene Copolymer Copolymerized with Carboxyl Group-Containing Unsaturated Compound (A-4): Ion-exchanged water was placed in a 7-glass flask equipped with a stirrer.
100 parts, sodium todecylbenzene sulfonate 0.5 parts,
0.01 parts potassium hydroxide, 0.1 t-dodecyl mercaptan
Parts and batch polymerization components consisting of various monomers of A-4 shown in Table 1 were added, and the temperature was raised with stirring. Temperature is 45 ℃
Ethylenediaminetetraacetic acid sodium salt
0.1 part, ferrous sulfate 0.003 part, formaldehyde sodium sulfoxylate dihydrate 0.2 part, and an activator aqueous solution consisting of 15 parts ion-exchanged water and 0.1 part diisopropylbenzene hydroperoxy are added, and the reaction is carried out for 1 hour. Continued.

Next, 50 parts of ion-exchanged water, 1 part of sodium dodecylbenzene sulfonate, 0.02 part of potassium hydroxide, 0.1 part of t-dodecyl mercaptan, 0.2 part of diisopropylbenzene hydroperoxide, and various monomers in the proportions shown in Table 2 are included. The mixture of increment polymerization components was continuously added over 3 hours to continue the reaction. After the addition was completed, the reaction was continued for 1 hour with further stirring, and then 2,2
0.2 part by weight of methylene-bis- (4-ethyl-6-t-butylphenol) was added, and the reaction product was taken out from the flask. The product was coagulated with 2 parts by weight of potassium chloride, dehydrated, washed with water and dried to recover a powdered graft resin.

Table 1 shows the monomer polymerization conversion rate, the graft rate measured by the method described above, and the intrinsic viscosity [η].

The rubber-like polymer of A-4 shown in Table 1 was polymerized as follows.

Using a stainless steel polymerization reactor with an internal volume of 100 equipped with a 4-stage paddle blade, the polymerization reaction was carried out under the formulation and conditions shown in Table-2. The temperature of the paddle blade is increased with stirring at 90 rpm, potassium persulfate is added when the temperature reaches 50 ° C, and then the polymerization reaction is performed while controlling the reaction temperature to be constant at 50 ° C. When the polymerization rate reached 90%, 0.1 part by weight of diethylhydroxyamine was added to stop the reaction, and unreacted monomers were substantially distilled off by steam distillation to obtain a latex of a rubber-like substance.

Table-2 [R-1 formulation and conditions] 1,3-Butadiene (parts by weight) 100 Sodium dodecylbenzenesulfonate 1.5 Potassium chloride 1.0 Potassium hydroxide 0.12 Potassium persulfate 0.25 Ion-exchanged water 100 Polymerization temperature (° C) 50 Polymerization Time (hrs) 50 Weight ratio (%) 88 Average particle size (Å) ^(*) 1500 (*) Measured using Nanosizer (Nippon Kagaku Kikai Co., Ltd.).

Table 3 shows the components (B) (B-1 to B-5).

The following was used as the component (C).

C-1: Nylon 6: Toray's Alamine CM1017 C-2: PBT (polybutylene terephthalate): Polyplastic Duranex XD499 Examples 1-12, Comparative Examples 1-7 Table 4 (A) component and (C) ) Components were melt-kneaded at a temperature of 250 ° C. with a 40 m / m extruder to prepare pellets. The pellets and the components (B) and (D) were melt-kneaded again at a temperature of 250 ° C. with a 40 m / m extruder to prepare pellets.

Example 13, Comparative Example 8 Components (A) to (D) in Table 4 were heated at a temperature of 250 m in a 40 m / m extruder.
Melt kneading was performed at 0 ° C. to prepare pellets.

The pellets prepared as described above and the pellets of Comparative Example 9 were molded using a 50Z injection molding machine (Toshiba IS-80A) at a molding temperature of 260 ° C. to prepare test pieces.

 The physical properties of the obtained test pieces were evaluated by the following methods.

 The results are shown in Table-4.

Liquidity Melt flow index (MFR:
The measurement conditions were 260 ° C and 10 kg).

Impact resistance Izod impact strength (ASTM D256 14 ″ with notch 23 °)
(Hereinafter referred to as Izod Imp) was measured.

Appearance of molded product The glossiness (ASTM D523 23 ° C, 45 °) of the test piece was measured.

Chemical resistance A constant strain with a strain rate of 1% was applied to a test piece (1/8 "x 1/2" x 5 "), and dioctyl phthalate (hereinafter DOP) was added to the flexure.
Say. ) And brake fluid were applied and left at 23 ° C., and the time until breakage was measured.

(○ indicates the case where breakage or crack did not occur for 100 hours or more.) Weld strength retention rate Molded using a mold with a weld line in the center of ASTM No. 1 dumbbell, and measure the tensile strength (Tw). Next, the tensile strength (To) of the test piece by the mold without the weld line was measured.

The weld strength retention rate was calculated as (Tw / To) × 100%.

Heat resistance A test piece (1/2 ″ × 1/2 ″ × 5 ″) was heated under a load of 4.6 kg / cm ² to determine the heat strain temperature (HDT) (ASTM D648).

As is clear from the results shown in Table 4, Examples 1 to 13
According to the above, the thermoplastic resin composition intended by the present invention is obtained. On the other hand, in Comparative Examples 1-9, the composition aimed at by the present invention cannot be obtained.

That is, in the compositions of Comparative Examples 1 and 2, the blending ratio of the component (D) was outside the range of the present invention, and Comparative Example 1 had a low impact resistance (Imp). In Comparative Example 2, the heat resistance is low. Comparative Example 3
The composition (A) is a component in which the component (A) does not contain carboxyl group-containing unsaturation, and has low impact resistance. The composition of Comparative Example 4 has a low impact resistance because the component (A) and the component (B) do not contain a rubber substance. Since the composition of Comparative Example 5 contained a large amount of the unsaturated compound containing a carboxyl group, it had low impact resistance, weld strength retention, MFR and gloss.

The composition of Comparative Example 6 has a low intrinsic viscosity [η] of the matrix component in the component (A) and a low graft ratio of the component (B), and thus has low impact resistance, glossiness, and retention of weld strength.

Since the composition of Comparative Example 7 has a low [η] of the matrix in the components (A) and (B), it has low impact resistance, glossiness and weld strength retention rate.

Since the composition of Comparative Example 8 does not contain the component (C) (nylon 6), it has low impact resistance, MFR, chemical resistance, glossiness and heat resistance.

The composition of Comparative Example 9 is an example of using nylon-6 alone, and has low impact resistance.

f. Effects of the Invention At present, in the molding processing industry using thermoplastic resins, the characteristics required for molded articles tend to become complicated as the uses of the molded articles are diversified. To obtain such a molded product,
It is required that the impact resistance, molding processability, chemical resistance, and weld strength are far superior to those of conventional products.

However, conventional polyamide resins, polyester resins and their compositions have not been able to sufficiently meet this demand.

The composition of the present invention has a high balance of impact resistance, moldability, chemical resistance and weld strength, and can sufficiently meet the above requirements.

Further, the composition of the present invention is a molding material that improves the drawbacks of conventional polyamide resins, polyester resins and the like and satisfies the requirements of the molding processing industry, and its industrial value is great.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical location C08L 77/00 LQS C08L 77/00 LQS (72) Inventor Shinichi Kimura 2-11 Tsukiji, Chuo-ku, Tokyo No. 24 in Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A 63-179957 (JP, A) JP-A 1-141940 (JP, A) JP-A 54-25951 (JP, A) JP-A 61-165397 (JP, A)

Claims (2)

(57) [Claims] 1. A styrene-based copolymer in which (A) a carboxyl group-containing unsaturated compound is copolymerized 5 to 80% by weight (B) a styrene-based polymer 5 to 85% by weight (C) a polyamide-based polymer and A composition containing (D) an organic phosphoric acid compound and / or an organic phosphorous acid compound in an amount of 0.1 to 10 parts by weight in 100 parts by weight of a mixture consisting of 10 to 90% by weight of a polyester polymer. ) (A) The content of the carboxyl group-containing unsaturated compound in the whole composition is 0.02 to 4% by weight, and (B) the content of the rubber component in the whole composition is 5 to 40% by weight, (C) A thermoplastic resin composition, wherein the matrix component in the components (A) and (B) has an intrinsic viscosity (30 ° C., methyl ethyl ketone) of 0.35 dl / g or more. 2. The content of the carboxyl group-containing unsaturated compound in the component (A) is 0.1 to 8% by weight, and the average graft ratio to the rubber component in the entire composition is 30% by weight or more. The thermoplastic resin composition according to claim 1, which is characterized.