JPH09249792A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which can give moldings having excellent impact resistance and good surface gloss. SOLUTION: This composition comprises a graft copolymer obtained by polymerizing a monomer mixture comprising an aromatic vinyl compound and/or an alkyl unsaturated carboxylate and a vinyl cyanide compound in the presence of a latex of a diene polymer (a) having a particle diameter distribution in which the mean particle diameter is 0.05-0.25μm, and at least 80wt.% of the particles have particle diameters in the range represented by the formula and a latex of a diene polymer (b) having a particle diameter distribution in which the mean particle diameter is 0.40-0.80μm, and at least 80wt.% of the particles have diameters in the range represented by the formula and a copolymer obtained by polymerizing a monomer mixture comprising an aromatic vinyl compound and/or an alkyl unsaturated carboxylate and a vinyl cyanide compound. 0.9×M<=X<=1.1×M (wherein M is the mean particle diameter (m), and X is the diameter (μm) of an individual rubber particle).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent impact resistance and good gloss.

[0002]

2. Description of the Related Art Rubber-reinforced styrene resins represented by ABS resins have excellent impact resistance, mechanical properties, moldability and luster, and are quasi-engineering plastics having intermediate properties between general-purpose resins and engineering resins. Used in a wide range of applications.

In recent years, demands for products having higher impact strength and higher gloss than conventional products for the purpose of further increasing the commercial value in general equipment applications and home electric appliance applications have been increasing.

In general, when the particle size of the rubbery polymer contained in the resin composition is reduced, the surface gloss is improved, but the impact resistance is reduced. Conversely, when the particle size is increased, the impact resistance is improved, but the gloss is reduced.

Therefore, in order to improve these drawbacks,
A method of combining a small particle size rubber and a medium to large particle size rubber (Japanese Patent Laid-Open Nos. 50-144747, 52-141859, and 53-57293) has been proposed.

Further, a method for producing an ABS resin using a medium to large particle size rubber by bulk-suspension polymerization (JP-A-51-6).
Nos. 248 and 53-29353) and a method of enlarging and using a small particle size rubber without using a medium to large particle size rubber (Japanese Patent Laid-Open No. 59-129215).

Further, a method for defining the particle size distribution of rubber (Japanese Patent Laid-Open No. 62-11714), a method for defining the composition of matrix resin (Japanese Patent Laid-Open No. 60-11514) and the like have been proposed.

[0008]

However, a resin composition satisfying both surface gloss and impact resistance cannot be obtained by a method of simply combining a small particle diameter rubber and a medium to large particle diameter rubber.

Further, in the method of controlling the dispersed particle size of rubber by the block or block-suspension method, it is difficult to obtain a desired rubber particle size because it depends on the phase transition timing of the rubber.

Therefore, an object of the present invention is to provide excellent impact resistance,
At the same time, it is to provide a thermoplastic resin composition having a good gloss on the surface of a molded article.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.

That is, in the present invention, the average particle size is 0.0
The latex of the diene polymer (a) having an average particle size of 0.5 to 0.25 μm and 80% by weight or more of which has a particle size distribution in a range satisfying the following formula (1).
In the presence of a latex of a diene polymer (b) having a particle size distribution of 40 to 0.80 μm and 80% by weight or more of which is in a range satisfying the following formula (1), an aromatic vinyl compound and / or Graft copolymer (A) obtained by polymerizing a monomer mixture comprising an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound, and an aromatic vinyl compound and / or unsaturated carboxylic acid alkyl ester compound and cyanation The present invention provides a thermoplastic resin composition obtained by mixing a copolymer (B) obtained by polymerizing a monomer mixture containing a vinyl compound.

0.9 × M ≦ X ≦ 1.1 × M (1) where M: average particle diameter (μm) X: individual rubber particle diameter (μm)

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The diene polymer (a) which is a constituent of the graft copolymer (A) used in the present invention is preferably a polymer or copolymer containing a conjugated diene as a main component. is there. The content of the conjugated diene is preferably 75% by weight or more, more preferably 85% by weight or more. Specifically, polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer and the like can be used.

The average particle diameter of these diene polymers (a) is 0.05 to 0.25 μm, preferably 0.10 to
It must be in the range of 0.22 μm. here,
The average particle size of the diene polymer latex is 0.05 μm
If it is less than 0.25 μm, impact resistance is insufficient even when used in combination with a rubber latex having a large particle size described below, and conversely, if it exceeds 0.25 μm, the surface gloss is lowered, which is a satisfactory resin composition. Can't get

The diene polymer (a) used here is 80% by weight or more, preferably 8% by weight of the polymer particles.
It is a necessary condition that 5% by weight or more has a particle size distribution in a range satisfying the following formula (1).

0.9 × M ≦ X ≦ 1.1 × M (1) where M: average particle diameter (μm) X: individual rubber particle diameter (μm) Particle diameter satisfying the above formula (1) The diene polymer (a) having a distribution is excellent in impact resistance when used together with the diene polymer (b), and at the same time, a resin composition having good surface gloss can be obtained, and the object of the present invention is achieved. To be done.

Further, the gel content of the diene polymer (a) is 70% by weight or more, preferably 75% by weight or more, from the viewpoint of difficulty in generating aggregates and lower manufacturing cost.
More preferably, it is 80% by weight or more.

As a method for producing the diene polymer (a) latex, a usual emulsion polymerization method can be adopted. To set the average particle size and particle size distribution to the desired range,
It is possible by precisely controlling the amount of polymerization initiator, the amount of water for polymerization, the amount of emulsifier, the amount of chain transfer agent, the amount of electrolysis, the polymerization temperature, the stirring speed and the polymerization time during the polymerization.

The diene polymer (b), which is another constituent of the graft copolymer (A) used in the present invention, is the same as that described for the diene copolymer (a). Used.

However, the average particle size of the diene polymer (b) is 0.40 to 0.80 μm, preferably 0.42.
0.75 μm, particularly preferably 0.45 to 0.65 μm
The requirement is that Here, when the average particle diameter of the diene polymer latex is less than 0.40 μm, the impact resistance of the resulting thermoplastic resin composition is poor even when it is used in combination with the diene polymer (a), and conversely, it is 0. If it exceeds 80 μm, the surface gloss tends to be significantly reduced depending on the amount used.

The diene polymer (b) used here is 80% by weight or more, preferably 8% by weight of the polymer particles.
It is a necessary condition that 5% by weight or more has a particle size distribution in a range satisfying the following formula (1).

0.9 × M ≦ X ≦ 1.1 × M (1) where M: average particle diameter (μm) X: individual rubber particle diameter (μm) Particle diameter satisfying the above formula (1) The diene polymer (b) having a distribution is excellent in impact resistance when used together with the diene polymer (a), and at the same time, a resin composition having good surface gloss can be obtained, and the object of the present invention is achieved. To be done.

As the method for producing the diene polymer (b) latex, an ordinary emulsion polymerization method can be adopted, and the adjustment of the average particle size and the particle size distribution will be described in the diene polymer (a). It can be performed in the same manner as described above.

The proportion of the diene polymers (a) and (b) is 30 to 30 (a) with respect to the sum of (a) and (b).
80% by weight, (b) is 70 to 20% by weight, preferably (a) is 40 to 80% by weight, and (b) is 60 to 20%.
%, Particularly preferably (a) is 50 to 75% by weight, and (b) is 50 to 25% by weight. If the proportion of the diene polymer (b) is 70% by weight or more, the gloss of the molded article tends to decrease, and if it is 20% by weight or less, the impact resistance tends to decrease.

In the present invention, the monomer which is graft-polymerized in the presence of the diene polymer latex is a monomer mixture containing an aromatic vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound. Is.

Aromatic vinyl compounds include styrene and α
-Methylstyrene, vinyltoluene, o-ethylstyrene, o-chlorostyrene and o, p-dichlorostyrene, among which styrene and α-methylstyrene are particularly preferred, and one or more of these may be used. Can be.

As the unsaturated carboxylic acid alkyl ester compound, an acrylic acid ester and / or a methacrylic acid ester having an alkyl or substituted alkyl group having 1 to 6 carbon atoms is preferable, and one kind or two or more kinds may be used. it can. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n
-Propyl, n-butyl (meth) acrylate, (meth)
Examples thereof include n-hexyl acrylate, cyclohexyl (meth) acrylate, 2-chloromethyl (meth) acrylate, and chloroethyl (meth) acrylate. Among them, methyl (meth) acrylate can be preferably used.

Examples of vinyl cyanide compounds include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being particularly preferred.

The graft copolymer (A) is used in an amount of 10 to 80 parts by weight (in terms of solid content) of the diene polymer latex, preferably 15 to 80 parts by weight, 90 to 20 parts by weight of the monomer mixture, It can be obtained by the emulsion polymerization method, preferably using 85 to 20 parts by weight.

Further, the ratio of each component in the monomer mixture is
Aromatic vinyl compound and / or unsaturated carboxylic acid alkyl ester compound is 40 to 95% by weight, preferably 45 to 90% by weight, more preferably 45 to 85% by weight, and vinyl cyanide compound is 60 to 5% by weight. %, Preferably 55 to 10% by weight, more preferably 55 to 15% by weight. When the ratio of each component in the monomer mixture is out of the above range, the impact resistance of the resin tends to be poor and the thermal stability tends to be remarkably lowered.

Various methods can be adopted as the method for adding the components such as the monomer mixture, the emulsifier, the polymerization initiator and the chain transfer agent in the graft polymerization. That is, (1) a method in which the whole amount is added at the beginning of polymerization, (2) a method in which a part is added at the initial stage, and the rest is continuously added at a constant rate, and (3) a method in which the addition is performed in two or more portions. It is.

There are no particular restrictions on the types of emulsifier, polymerization initiator and chain transfer agent used, and reagents used in ordinary emulsion polymerization can be used. Typical emulsifiers include potassium rosinate, potassium stearate, potassium oleate, etc., polymerization initiators such as organic hydroperoxide and persulfate, and chain transfer agents include alkylthiol compounds.

The graft ratio of the graft copolymer (A) thus obtained is preferably 10 to 60%, and preferably 15 to 55%, in order to obtain a thermoplastic resin composition excellent in impact resistance and gloss. Is more preferable. The graft ratio can be controlled by adjusting the ratio of the rubbery polymer to the monomer mixture, the type and amount of the polymerization initiator, and the type and amount of the chain transfer agent.

The intrinsic viscosity [η] (measured at 30 ° C.) of the methyl ethyl ketone soluble component of the graft copolymer (A)
Is preferably 0.15 to 0.60 dl / g, and 0.18
-0.55 dl / g is more preferred. When in these ranges, the object of the present invention can be achieved.

As a method for producing the graft copolymer (A), the graft copolymer (A1) obtained from the diene polymer (a) alone and the diene polymer (b) obtained from the latex alone are used. It is also possible to use the graft copolymer (A2) as the graft copolymer (A) after mixing it in the state of the graft copolymer latex or in the solid state obtained by coagulating this latex.

The content of the graft copolymer (A) in the thermoplastic resin composition of the present invention is such that the total amount of the diene polymers (a) and (b) in the thermoplastic resin composition is 5 to 5. 30% by weight, further 5 to 25% by weight, especially 7 to
It is preferable to adjust the content to be 20% by weight. If the total amount of the diene polymers (a) and (b) is less than 5% by weight, the impact improving effect of the diene polymer is insufficient and 3
If it exceeds 0% by weight, rigidity and fluidity at the time of molding tend to decrease.

The copolymer (B) in the present invention is a copolymer obtained by polymerizing a monomer mixture containing an aromatic vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound.

As the aromatic vinyl compound, styrene, α
-Methylstyrene, vinyltoluene, o-ethylstyrene, o-chlorostyrene, o, p-dichlorostyrene 7 and the like can be mentioned, but styrene and α-methylstyrene are particularly preferable, and these are used alone or in combination of two or more. be able to.

As the unsaturated carboxylic acid alkyl ester compound, acrylic acid ester and / or methacrylic acid ester having an alkyl or substituted alkyl group having 1 to 6 carbon atoms is preferable, and one kind or two or more kinds are used. be able to. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n
-Propyl, n-butyl (meth) acrylate, (meth)
Examples thereof include n-hexyl acrylate, cyclohexyl (meth) acrylate, 2-chloromethyl (meth) acrylate, and chloroethyl (meth) acrylate. Among them, methyl (meth) acrylate can be preferably used.

Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being particularly preferred.

The ratio of each component in the monomer mixture of the copolymer (B) is as follows: aromatic vinyl compound and / or unsaturated carboxylic acid alkyl ester compound 40 to 95% by weight, vinyl cyanide compound 60 to 5% by weight. % And 0 to 60% by weight of a vinyl monomer copolymerizable therewith.

Here, as the other copolymerizable vinyl-based monomer, α, β such as maleic anhydride and itaconic anhydride are used.
Examples thereof include imide compounds of α, β-unsaturated carboxylic acids such as unsaturated dicarboxylic acid anhydrides, N-phenylmaleimide, N-methylmaleimide and Nt-butylmaleimide.

The intrinsic viscosity [η] of the solution of the copolymer (B) in methyl ethyl ketone is preferably in the range of 0.30 to 0.80 dl / g, more preferably 0.32 to 0.70 dl / g, and especially 0.35. 0.70 dl / g is preferred. When the intrinsic viscosity [η] is less than 0.30 dl / g, the impact resistance is poor,
If it exceeds 0.80 dl / g, the fluidity tends to decrease.

There is no particular limitation on the method for producing the resin composition of the present invention. For example, powders, pellets or flakes of the graft copolymer (A) and the copolymer (B) can be placed in a high speed stirrer or the like. It is possible to employ various methods such as a method of performing uniform mixing and then melt-kneading with a single-screw or multi-screw extruder having a sufficient kneading ability.

The resin composition of the present invention contains other thermoplastic polymers such as polymethyl methacrylate, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66). ), Polyphenylene oxide, MBS resin, AES resin, AAS resin and other thermoplastic resins are appropriately mixed, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / propylene / dicyclo Pentadiene copolymer, ethylene / propylene / 5-
It is also possible to adjust to more desirable physical properties and characteristics by appropriately mixing olefin rubber such as ethylidene-2-norbornene copolymer, ethylene / vinyl acetate copolymer and ethylene / butyl acrylate copolymer. .

Further, according to purposes, reinforcing materials and fillers such as pigments and dyes, metal flakes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, antistatic agents and flame retardants. Etc. can also be added.

The thermoplastic resin composition obtained by the present invention is further molded by heating and melting to obtain a resin molded product made of the thermoplastic resin composition of the present invention. The molding method is not particularly limited, and molding methods such as injection molding, extrusion molding, blow molding, vacuum molding and compression molding are possible, but the effects of the present invention are most exhibited in injection molding. The obtained molded article can be used for various parts and products including general equipment use and home electric appliance use.

[0049]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but these examples do not limit the present invention.

Unless otherwise specified here,
“Parts” means parts by weight, and “%” means% by weight.

The method for analyzing the polymer properties of the present invention is shown below.

Particle size distribution of rubber latex: Measured by the sodium alginate method.

Gel content: 100 g of diene polymer
It is the percentage of the dry weight of the precipitate obtained by centrifugation after addition to g of toluene and vigorous stirring at room temperature with respect to the weight of diene polymer.

Graft ratio: Acetone was added to a predetermined amount (m) of the graft copolymer and refluxed for 4 hours. The solution was centrifuged at 8,800 rpm for 30 minutes, and the insoluble matter was filtered. This insoluble matter was dried under reduced pressure at 60 ° C. for 5 hours, and the weight (n) was measured.

The graft ratio was calculated by the following formula.

Graft ratio = [(n)-(m) × L] / ((m) × L) × 100 where L is the rubber content of the graft polymer.

The finally obtained thermoplastic resin composition was molded by the injection molding method, and then the physical properties were measured by the following test methods. Izod impact strength: ASTM D-256 1/2 inch Notched 23 ° C Surface gloss: Using a UGV-5D digital variable-angle gloss meter manufactured by Suga Test Instruments Co., Ltd., the surface reflected light of a molded article at an incident angle of 60 degrees. A measurement was made. Test piece: length 120mm x width 80m
mx 3mm thick

Reference Example (1) Production of Graft Copolymer (A) The latexes of the diene polymers (a) and (b) having the rubber properties shown in Table 1 were placed in a glass reactor and charged with nitrogen. After replacing the inside, the temperature in the reactor was raised to 65 ° C. Ferrous sulfate, sodium pyrophosphate, and glucose dissolved in water were added, and the internal temperature was maintained at 65 ° C. To this mixed solution, a predetermined amount of the monomer mixture shown in Table 1 and an aqueous solution of cumene hydroperoxide of potassium oleate were separately added continuously for 5 hours. Raise the internal temperature to 75
After the temperature was set to 0 ° C. and stirring was further continued for 1 hour to complete the reaction, 2,6-di-tert-butylparacresol was added as an antioxidant. The polymerization rate was 98.4%.

The obtained graft copolymer latex is coagulated with sulfuric acid, neutralized with sodium hydroxide, washed with water, dehydrated,
After drying, a graft copolymer A-1 was obtained. The graft ratio of this graft copolymer was 36%, and the intrinsic viscosity of the methyl ethyl ketone soluble component was 0.31 dl / g.

With the same formulation, the graft copolymer A-2 to
A-10 was obtained. The graft ratio and the intrinsic viscosity of the methyl ethyl ketone soluble component are shown in Table 1.

[0061]

[Table 1]

(2) Production of Copolymer (B) Copolymer B was produced by suspension polymerization of a monomer mixture consisting of 76% styrene and 24% acrylonitrile. The intrinsic viscosity [η] of the methyl ethyl ketone soluble component is 0.58 dl /
g.

Examples 1 to 5 and Comparative Examples 1 to 5 The graft copolymers (A) and copolymers (B) prepared in the above reference examples were mixed in a Henschel mixer at the compounding ratios shown in Table 2. Next, after extruding with a 40 mmφ extruder at a kneading temperature of 220 ° C. and pelletizing each, each pellet was subjected to injection molding under the conditions of a molding temperature of 230 ° C. and a mold temperature of 60 ° C. to prepare each test piece, and An evaluation was made. Table 2 shows the results.

[0064]

[Table 2]

The following is clear from the examples and comparative examples.

That is, the resin composition of the present invention (Example 1)
All of items (5) to (5) have high impact strength, and at the same time, the gloss of the surface of the molded product is good.

On the other hand, the diene polymer (a) alone (b)
Those which do not contain are inferior in impact strength (Comparative Example 1). On the contrary, when (b) alone does not contain (a), the surface gloss is inferior (Comparative Example 2).

The diene polymer (a) or (b)
If the average particle size of 1 is out of the specified value or the particle size distribution is out of the specified value, the surface gloss is lowered (Comparative Examples 3 to 5).

[0069]

EFFECTS OF THE INVENTION The composition of the present invention has been found to have a significantly improved impact strength without impairing the mechanical properties of molded articles.
At the same time, the gloss of the surface of the molded product is also good, and it is suitable as a molding material for general equipment and home appliances. This effect is a combination of two types of diene polymer particles with a specific average particle size and particle size distribution. It is only exhibited by using a graft copolymer containing the above.

Claims (20)

[Claims] 1. A latex of a diene polymer (a) having an average particle size of 0.05 to 0.25 μm, and 80% by weight or more of which has a particle size distribution in a range satisfying the following formula (1). And in the presence of a latex of a diene polymer (b) having an average particle size of 0.40 to 0.80 μm and 80% by weight or more of which has a particle size distribution in a range satisfying the following formula (1): Graft copolymer (A) obtained by polymerizing a monomer mixture of an aromatic vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound, and an aromatic vinyl compound and / or an unsaturated carboxylic acid A thermoplastic resin composition comprising a copolymer (B) obtained by polymerizing a monomer mixture containing an alkyl ester compound and a vinyl cyanide compound. 0.9 × M ≦ X ≦ 1.1 × M (1) where M: average particle diameter (μm) X: individual rubber particle diameter (μm) 2. The ratio of each component in the monomer mixture is 40 to 95% by weight of aromatic vinyl compound and / or unsaturated carboxylic acid alkyl ester compound and 60 to 5% by weight of vinyl cyanide compound. The thermoplastic resin composition according to claim 1, which is a graft copolymer (A) in the range of. 3. The graft ratio of the graft copolymer (A) is
The thermoplastic resin composition according to claim 1 or 2, which is in the range of 10 to 60%. 4. The intrinsic viscosity [η] of the graft copolymer (A) soluble in methyl ethyl ketone is 0.15 to 0.60 d.
The thermoplastic resin composition according to any one of claims 1 to 3, which has a ratio of 1 / g. 5. The ratio of the diene polymer is (a) and (b).
(A) 30 to 80% by weight, and (b) 70 to
It is 20 weight%, The thermoplastic resin composition in any one of Claims 1-4. 6. The gel content of the diene polymer (a) is 70.
The thermoplastic resin composition according to any one of claims 1 to 5, which is at least wt%. 7. The thermoplastic resin composition according to claim 1, wherein the total amount of the diene polymers (a) and (b) is 5 to 30% by weight in the thermoplastic resin composition. 8. The ratio of the respective components in the monomer mixture of the copolymer (B) is such that the aromatic vinyl compound and / or the unsaturated carboxylic acid alkyl ester compound is 40 to 95% by weight, and the vinyl cyanide compound is 60 to 5% by weight and 0 to 60% by weight of a vinyl monomer copolymerizable therewith.
7. The thermoplastic resin composition according to any one of 7. 9. The thermoplastic resin composition according to claim 1, wherein the solution of the copolymer (B) in methyl ethyl ketone has an intrinsic viscosity [η] in the range of 0.30 to 0.80 dl / g. . 10. A molded product obtained by molding the thermoplastic resin composition according to claim 1. 11. A latex of a diene polymer (a) having an average particle size of 0.05 to 0.25 μm, and 80% by weight or more of which has a particle size distribution in a range satisfying the following formula (1). And in the presence of a latex of a diene polymer (b) having an average particle size of 0.40 to 0.80 μm and 80% by weight or more of which has a particle size distribution in a range satisfying the following formula (1): A step of polymerizing a monomer mixture comprising an aromatic vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound to obtain a graft copolymer (A), and the graft copolymer (A) (B) Mixing with a copolymer obtained by polymerizing a monomer mixture containing an aromatic vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound and a vinyl cyanide compound A thermoplastic resin composition comprising steps. 0.9 × M ≦ X ≦ 1.1 × M (1) where M: average particle diameter (μm) X: individual rubber particle diameter (μm) 12. The ratio of each component in the monomer mixture is 40 to 95% by weight of aromatic vinyl compound and / or unsaturated carboxylic acid alkyl ester compound and 60 to 5% by weight of vinyl cyanide compound. The method for producing a thermoplastic resin composition according to claim 11, which is the graft copolymer (A) in the range of. 13. The method for producing a thermoplastic resin composition according to claim 11, wherein the graft ratio of the graft copolymer (A) is in the range of 10 to 60%. 14. The graft copolymer (A) having a methyl ethyl ketone-soluble component has an intrinsic viscosity [η] of 0.15 to 0.60.
The method for producing a thermoplastic resin composition according to any one of claims 11 to 13, which is in a range of dl / g. 15. The proportion of the diene polymer is (a) 30 to 80% by weight, (b) based on the sum of (a) and (b).
70 to 20% by weight is the method for producing a thermoplastic resin composition according to any one of claims 11 to 14. 16. The gel content of the diene polymer (a) is 7
It is 0 weight% or more, The manufacturing method of the thermoplastic resin composition in any one of Claims 11-15. 17. The thermoplastic resin composition according to claim 1, wherein the total amount of the diene polymers (a) and (b) is 5 to 30% by weight in the thermoplastic resin composition. Production method. 18. A ratio of each component in the monomer mixture of the copolymer (B) is 40 to 95% by weight of an aromatic vinyl compound and / or an unsaturated carboxylic acid alkyl ester compound, and a vinyl cyanide compound of 60 to 60% by weight. 5% by weight and 0 to 60% by weight of a vinyl-based monomer copolymerizable therewith.
A method for producing the thermoplastic resin composition according to any one of 1 to 17. 19. The thermoplastic resin composition according to claim 11, wherein the methyl ethyl ketone solution of the copolymer (B) has an intrinsic viscosity [η] in the range of 0.30 to 0.80 dl / g. Manufacturing method. 20. The method for producing a thermoplastic resin composition according to claim 11, wherein the step of producing the graft copolymer (A) is an emulsion polymerization method.