JPH09302173A - Thermoplastic resin composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition, having good gloss, excellent in shock resistance and chemical resistance and useful as an industrial material, etc., by compounding a specific resin composition, a fatty acid glycerin ester and a weather-resting agent, at specific ratios. SOLUTION: This thermoplastic resin composition is obtained by compounding 100 pts.wt. of a resin composition with (C) 0.2-5 pts.wt. of a fatty acid glycerin ester and (D) 0.01-5 pts.wt. of a weather-resisting agent. This resin composition consists of (A) 60-95 pts.wt. of (i) a copolymer composed of an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and an epoxy group-containing vinyl monomer unit or (ii) a composition composed of the component (i) and a copolymer composed of an aromatic vinyl monomer unit and a vinyl cyanide monomer unit and (B) 5-40 pts.wt. of a modified polyolefin polymer obtained by treating with 0.1-10wt.% of an unsaturated dicarobxylic acid anhydride monomer unit or an unsaturated carboxylic acid monomer unit. The content of the vinyl monomer unit containing an epoxy group in the component (i) is 0.1-10wt.% based on 100wt.% of the component A.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a copolymer containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, which has improved impact resistance and good weather resistance and chemical resistance. Further, the present invention relates to a thermoplastic resin composition having good gloss and balance of other physical properties, and a method for producing the same.

[0002]

2. Description of the Related Art Copolymers composed of aromatic vinyl monomer units and vinyl cyanide monomer units are widely used, but they have the drawback of low impact resistance. Heretofore, as a method for improving such a defect, graft polymerization of these monomers onto a diene rubber has been carried out (Japanese Patent Publication No. 34-3341 and Japanese Patent Publication No. 42-13).
616, Japanese Patent Publication No. 42-19330, Japanese Patent Publication No. 46-26865). However, the copolymer resin improved by this method has poor weather resistance because it has a double bond. Thus, a copolymer resin obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer onto a diene rubber has been achieved to improve impact resistance, but to reduce weather resistance. Met.

[0003]

The present invention has solved these drawbacks, and an object of the present invention is to provide a copolymer containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit. Impact resistance by adding a fatty acid glycerin ester and a weathering agent into a resin composition of a copolymer obtained by introducing a specific vinyl monomer unit and improving it, and a specific modified polyolefin-based polymer. Another object of the present invention is to provide a thermoplastic resin composition which is excellent in weather resistance and chemical resistance, and has good gloss and a good balance of other physical properties.

[0004]

The present invention is summarized as follows. The present invention relates to a resin composition, which comprises (I) an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and an epoxy group. A copolymer (A) containing a vinyl monomer unit having, or a copolymer (B) containing the aromatic vinyl monomer unit and a vinyl cyanide monomer unit with the copolymer (A). 60-95, wherein the amount of the vinyl monomer unit having an epoxy group in the copolymer (A) is 0.1 to 10% by weight in 100% by weight of (I). A resin comprising 5 parts by weight and (II) 5 to 40 parts by weight of a modified polyolefin-based polymer modified with 0.1 to 10% by weight of an unsaturated dicarboxylic acid anhydride monomer unit or an unsaturated carboxylic acid monomer unit. (III) fatty acid glycerin ester 0 based on 100 parts by weight of the composition 2-5 parts by weight, a thermoplastic resin composition characterized by containing 0.01 to 5 parts by weight (IV) weatherability agent.

That is, the thermoplastic resin composition of the present invention is
(I) A copolymer (A) containing an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group (hereinafter referred to as a copolymer (A)), or A composition of the copolymer (A), a copolymer (B) containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit (hereinafter referred to as the copolymer (B)), and (II) Containing (III) fatty acid glycerin ester and (IV) weathering agent for a resin composition comprising a modified polyolefin polymer modified with a saturated dicarboxylic acid anhydride monomer unit or an unsaturated carboxylic acid monomer unit It was made.

Specific examples of the aromatic vinyl monomer used in the copolymer (A) and the copolymer (B) of the present invention include styrene, α-methylstyrene, vinyltoluene and t-butylstyrene. Specific examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile.

Specific examples of the vinyl monomer having an epoxy group include glycidyl methacrylate, glycidyl methyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether and methallyl glycidyl ether.

Further, the copolymer (A) and the copolymer (B) of the present invention may use other copolymerizable monomers, if necessary.

The proportion of each component of the copolymer (A) of the present invention is not particularly limited as long as it is within a copolymerizable range, but preferably an aromatic vinyl monomer unit and a vinyl cyanide monomer. The total amount of the body units is 99.9 to 70% by weight, more preferably 99.9 to 90% by weight.

The ratio of the aromatic vinyl monomer unit in the total 100% by weight of the aromatic vinyl monomer unit and the vinyl cyanide monomer unit is preferably 50 to 90% by weight, more preferably 65 to 90% by weight. It is 85% by weight. When the ratio of the aromatic vinyl monomer unit is outside this range, the chemical resistance and fluidity are deteriorated, which is not preferable.

Next, the ratio of the aromatic vinyl monomer unit to the vinyl cyanide monomer unit of the copolymer (B) of the present invention is
Although not particularly limited, preferably the sum of both is 1
Aromatic vinyl monomer units account for 50 to 90% by weight, more preferably 65 to 85% by weight, based on 00% by weight. When the ratio of the aromatic vinyl monomer unit is outside this range, the chemical resistance and fluidity are deteriorated, which is not preferable.

The amount of the vinyl monomer unit having an epoxy group copolymerized in the copolymer (A) of the present invention is 100% by weight of the copolymer (A) when the copolymer (B) is not contained. 0.1 to 10% by weight in parts, and when the copolymer (B) is included, it is 0.1 in 100 parts by weight of the total amount of the copolymer (A) and the copolymer (B). If the amount of the vinyl monomer unit having an epoxy group is within the above range, the mixing ratio of the copolymer (A) and the copolymer (B) is limited. Not a thing.

When the amount of the vinyl monomer unit having an epoxy group is less than 0.1% by weight, the impact resistance of the resin composition is poor, and when it exceeds 10% by weight, the impact resistance of the resin composition is poor. Liquidity is extremely low.

The modified polyolefin-based polymer used in the present invention refers to a polymer obtained by polymerizing an olefin monomer or a modified product of a copolymer, and specific examples of the olefin monomer used include ethylene and propylene. , 1-butene, isobutylene, 2-butene, cyclobutene, 3-methyl-
1-butene, 4-methyl-1-butene, 4-methyl-1
-Pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene and 1-dodecene.

To exemplify a preferable composition range of a polymer or a copolymer obtained by polymerizing an olefin monomer as a base of a modified polyolefin-based polymer, ethylene monomer unit 2
0-90 mol%, α-olefin monomer unit 10-80
Mol% and other monomer units 0 to 10 mol%,
The ethylene monomer unit content is preferably 50 to 85 mol%, particularly preferably 50 to 80 mol%.

Further, the glass transition temperature of these modified polyolefin polymers is -10 ° C or lower, particularly preferably -30 ° C or lower.

Specific examples of the unsaturated dicarboxylic acid anhydride monomer for modifying the polyolefin-based polymer or copolymer include maleic anhydride, methylmaleic anhydride, and anhydrous 1,
Examples thereof include 2-dimethylmaleic acid, ethylmaleic anhydride and phenylmaleic anhydride, with maleic anhydride being particularly preferred.

Specific examples of the unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid.

The modified polyolefin-based polymer of the present invention is
An unsaturated dicarboxylic acid anhydride monomer unit or an unsaturated carboxylic acid monomer unit is modified with 0.1 to 10% by weight, and when the modified amount is less than 0.1% by weight, the thermoplasticity is The impact resistance of the resin composition is inferior, and if it exceeds 10% by weight, the impact resistance of the thermoplastic resin composition is inferior and the fluidity is also low.

The term "modified" as used in the present invention means that a monomer unit used for modification, for example, a maleic anhydride group is present in the main chain or side chain of a polyolefin-based polymer, and random copolymerization. The modification can be carried out by a known technique such as graft polymerization. The denaturing method is not particularly limited,
For example, Japanese Patent Publication No. 39-6810 and Japanese Patent Publication No. 52-4
Modification can be carried out according to the methods disclosed in Japanese Patent No. 3677, Japanese Patent Publication No. 53-5716, Japanese Patent Publication No. 56-9925 and Japanese Patent Publication No. 58-445.

The modification is preferably such that the grafted product is modified rather than introduced into the main chain from the viewpoint of low temperature impact value and the like, and the unreacted monomer residual amount is 0.5% by weight or less. Are preferred in terms of physical properties.

The weight average molecular weight of the modified polyolefin-based polymer is not particularly limited, but from the balance of impact resistance and moldability, it is preferably 50,000 to 500,000, particularly preferably 100,000 to 300,000. Examples of these modified polyolefin-based polymers include commercially available Tuffmer MP-0620 (trade name, manufactured by Mitsui Petrochemical Co., Ltd.).

In the thermoplastic resin composition of the present invention, the content of the modified polyolefin polymer (II) in the total 100 parts by weight of (I) and (II) is 5 to 40 parts by weight. When the amount of the system polymer is less than 5 parts by weight,
The impact resistance strength of the thermoplastic resin composition is poor, and when it exceeds 40 parts by weight, heat resistance and rigidity are deteriorated, which is not preferable.

The fatty acid glycerin ester used in the present invention is, for example, a widely used fatty acid monoglyceride, fatty acid diglyceride, fatty acid triglyceride, or a combination thereof. Among them, fatty acid triglyceride is particularly preferred, and 12-hydroxystearic acid triglyceride is more preferred.

When the thermoplastic resin composition of the present invention contains 0.2 to 5 parts by weight of fatty acid glycerin ester, the appearance, particularly gloss and impact resistance are improved.
If it is less than 2 parts by weight, the effect is small, and if it exceeds 5 parts by weight, impact strength, heat resistance and gloss are lowered, which is not preferable.

The weathering agent used in the present invention may be a widely used one, for example, a combination of an ultraviolet absorber, a light stabilizer and an antioxidant.

Specific examples of the ultraviolet absorber include 2- (5
-Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2-
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2-
(3,5-di-t-amyl-2-hydroxyphenyl)
Benzotriazole, 2-ethoxy-2'-ethyl oxac acid bisanilide, 2-ethoxy-5-t-
Butyl-2′-ethyl oxac acid bisanilide, 2-hydroxy-4-n-octoxybenzophenone and the like can be mentioned.

Specific examples of the light stabilizer include bis (2,2
2,6,6-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, dimethyl succinate.1- (2-
(Hydroxyethyl) -4-hydroxy-2,2,6,6
-Tetramethylpiperidine polycondensate, poly [[6,
(1,1,3,3-tetramethylbutyl) amino-1,
3,5-triazine-2,4-diyl] [(2,2,2
6,6-Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and 1- [2- [3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy]
-2,2,6,6-tetramethylpiperidine and the like can be mentioned.

Specific examples of the antioxidant include triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,
4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl tetrakis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,
2-thiobis (4-methyl-6-t-butylphenol) and 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
There is benzene etc.

The thermoplastic resin composition of the present invention has a weather resistance of 0.01 to 5 relative to 100 parts by weight of (I) and (II) in total.
If the content is less than 0.01 parts by weight, the weather resistance is insufficient, and if it exceeds 5 parts by weight, the impact strength is lowered, which is not preferable.

The thermoplastic resin composition of the present invention may contain other additives or modifiers depending on the application,
Specific examples include reinforcing fibers such as glass fiber, carbon fiber and aramid fiber, talc, silica, clay,
Examples thereof include fillers such as mica and calcium carbonate, and flame retardants and colorants.

Next, the mixing for obtaining the thermoplastic resin composition of the present invention can be carried out by using an ordinary melt-kneading device, and the melt-kneading device which can be suitably used includes a screw extruder and a Banbury. There are mixers, co-kneaders and mixing rolls.

In the case where the thermoplastic resin composition of the present invention is produced by melt mixing, when the copolymer (B) is used, (B) may be added in a lump even if all of them are added at once. It may be added in portions. Further, in the case of divided addition, copolymers having different compositions may be used for (B) within the scope of the present invention.

A specific method for melt-mixing the weatherproofing agent and the other components is, for example, the copolymer (A) or the copolymer (A) and the copolymer (B), the modified polyolefin polymer and the fatty acid. A two-step melt mixing method in which a weathering agent, or a weathering agent and a copolymer (B) are added to a pellet obtained by melt-extruding glycerin ester to form a composition, and melt-extruded and mixed, a copolymer (A) or a copolymer A method in which a weathering agent and a copolymer (B) are added and melt-mixed during melt extrusion of the polymer (A) and the copolymer (B) with the modified polyolefin-based polymer and the fatty acid glycerin ester, and a mixing roll is used. A copolymer (A) or a copolymer (A) and a copolymer (B), and a weathering agent and a copolymer (B) are added during the melt-mixing of the modified polyolefin-based polymer and the fatty acid glycerin ester. How to mix Various methods can be used. As described above, the mixing method is particularly limited except that the weatherproofing agent is not added and mixed before melt-mixing (A) and (II) or (A), (B) and (II). is not.

The thermoplastic resin composition of the present invention is useful for applications such as an automobile front grill, an air spoiler, an air conditioner outdoor unit, and a satellite broadcasting antenna.

[0036]

The present invention will be described in more detail with reference to the following examples. These are merely examples and do not limit the content of the present invention.

The measuring methods of various properties are as follows. Heat resistance: According to ASTM D-648, a heat distortion temperature (HDT) was measured with a load of 18.6 kg / cm ² using an injection molded product having a thickness of 1/4 inch. Impact strength: 1/4 thickness according to ASTM D-256
Notched Izod impact values were measured by inch injection molded parts. Flowability: according to JIS K-6874, temperature 220 ° C,
The melt flow rate (MFR) was measured with a load of 10 kg. Elongation: Measured according to ASTM D-638 using an injection molded article having a thickness of 1/8 inch. Rigidity: According to ASTM D-790, a bending elastic modulus was measured using an injection molded product having a thickness of 1/4 inch. Gloss: According to JIS K-7105, a 60-degree specular gloss was measured using an injection-molded plate. Weather resistance: Using a fade meter, the elongation after irradiation with ultraviolet rays for 1200 hours at a temperature of 63 ° C. was measured by ASTM D
According to -638, measurement was performed using an injection molded product having a thickness of 1/8 inch, and the retention rate from before irradiation was determined.

The respective copolymers, polymers, lubricants and weatherproofing agents used are as follows. (1) Copolymer (A) consisting of an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group (A): a styrene monomer unit, an acrylonitrile monomer unit and glycidyl Using a copolymer in which the weight ratio of methacrylate monomer units is 74/25/1 (a-1)
And

(2) Copolymer (B) consisting of aromatic vinyl monomer unit and vinyl cyanide monomer unit: The weight ratio of the styrene monomer unit and the acrylonitrile monomer unit is 75.
/ 25 standard commercially available styrene-
It was designated as (b-1) using an acrylonitrile copolymer resin.

(3) Modified polyolefin copolymer (C): An ethylene-propylene copolymer having an ethylene monomer unit content of 80 mol% is used, and the ethylene-propylene copolymer and the maleic anhydride monomer unit are used. Weight ratio is 100 /
Polymers of 0, 99.1 / 0.9 and 98.7 / 1.3 were obtained to obtain (c-1), (c-2) and (c-3), respectively.
And

For example, (c-2) includes 8.0 kg of the above ethylene-propylene copolymer pellets, 96 g of powdered maleic anhydride and 2,5-dimethyl-2,5-di (t-butylperoxy). ) Hexane-3 (8.0 g) was weighed out, charged into a 20-liter Henschel mixer in which nitrogen was passed, and stirred for 5 minutes to uniformly blend,
This was extruded into a 40 mmφ extruder (flowing nitrogen, L / T = 28,
Dalmage type) and pelletized. The cylinder temperature was adjusted so that the polymer temperature was 240 ° C. to obtain a graft reaction product.

(4) Fatty acid glycerin ester (D):
Commercially available K-3 wax (Kawaken Fine Chemicals Co., Ltd.)
Manufactured, trade name) was used as (d-1).

(5) Weathering agent (E): 2- (5-methyl-)
2-hydroxyphenyl) benzotriazole, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. The mixture of the weight ratio of 40/40/20 was used as (e-1).

Example 1 1.95 kg of a copolymer (A) comprising an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group, in the composition shown in Table 1. And 1.05 kg of the modified polyolefin copolymer (C) and 60 g of the fatty acid triglyceride (D) were charged into a 20 liter Henschel mixer and blended, and then at a temperature of 210 ° C. in a TEM35B extruder (Toshiba, twin-axial same direction). Extruded and pelletized. Next, 2.06 kg of the above pellets, 1.94 kg of a copolymer of an aromatic vinyl monomer unit and a vinyl cyanide monomer unit (B) and 40 g of a weatherproofing agent (E) were added.
Add to a 0 liter Henschel mixer and blend,
Pellets were obtained by extrusion at a temperature of 210 ° C. with a TEM35B extruder. Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1.

[0045]

[Table 1]

Examples 2 to 6 Examples except that the copolymer (A), the copolymer (B), the modified polyolefin polymer (C) and the fatty acid glycerin ester (D) were blended as shown in Table 1 The same operation as in 1 was performed. Table 1 shows the measurement results of various physical properties.

Example 7 3.28 kg of a copolymer (A) of an aromatic vinyl monomer unit, a vinyl cyanide monomer unit and a vinyl monomer unit having an epoxy group and a modified polyolefin copolymer ( C) 0.72 kg and fatty acid triglyceride (D)
40 g was added to a 20 liter Henschel mixer and blended, and then extruded with a TEM35B extruder (Toshiba, biaxial same direction) at a temperature of 210 ° C. to form pellets. Then
3 kg of the above pellets and 30 g of weathering agent (E) were put into a 20 liter Henschel mixer, blended, and then TEM.
Extruders were extruded at a temperature of 210 ° C. to obtain pellets.
Using these pellets, test pieces for measuring physical properties were prepared by an injection molding machine, and various physical properties were measured. The results are shown in Table 1.

Comparative Examples 1 to 5 As shown in Table 2, the copolymer (A), the copolymer (B), the modified polyolefin polymer (C), the fatty acid glycerin ester (D) and the weather resistant agent (E) are shown. In Comparative Example 1, the amount of the vinyl monomer containing an epoxy group was out of the range, in Comparative Example 2, the modified amount of the modified polyolefin-based copolymer was out of the range, and in Comparative Examples 3 and 4, fatty acid glycerin was used. The same operation as in Example 1 was performed except that the amount of the ester was out of the range and that of Comparative Example 5 was out of the range. Table 2 shows the measurement results of various physical properties.

Comparative Example 6 1.34 kg of copolymer (A), 1.94 of copolymer (B)
kg, modified polyolefin-based copolymer (C) 0.72k
g, fatty acid triglyceride (D) 40 g and weather resistance agent (E) 40 g were charged into a 20 liter Henschel mixer and blended, and then extruded at a temperature of 210 ° C. by a TEM35B extruder (Toshiba, biaxial same direction) to pelletize. .

Comparative Example 7 The weight ratio of styrene monomer unit / acrylonitrile monomer unit / butadiene monomer unit of ABS resin was 61/21.
Various physical properties were measured by using the composition of / 18 and the composition of the lubricant (D) and the weather resistance (E) added in the same manner as in Example 1. The measurement results are shown in Table 2.

[0051]

[Table 2]

The molding temperature was 240 ° C. as a standard, and some corrections were made depending on the condition of the molded product.

From the results of Examples and Comparative Examples, the following is clear. From Example 1 and Comparative Example 1, the impact value is low unless the vinyl monomer having an epoxy group is included. From Example 1 and Comparative Example 2, the impact value is low when the unmodified polyolefin-based polymer is used. From Example 1 and Comparative Example 3, the impact strength is low unless the fatty acid glycerin ester is added. From Example 1 and Comparative Example 4, when the amount of fatty acid glycerin ester is too much, impact resistance and glossiness are low. From Example 1 and Comparative Example 5, the weather resistance is extremely poor unless the weather resistance agent is added. From Example 1 and Comparative Example 6, the impact strength is low when all the components are mixed together. From Example 1 and Comparative Example 7, the weather resistance is extremely poor when the diene rubber is used.

As described above, the copolymer having an epoxy group contains an appropriate amount of an epoxy group, and the modified polyolefin polymer further contains an unsaturated dicarboxylic acid anhydride monomer unit or an unsaturated carboxylic acid monomer unit. It can be seen that the weather resistance and the impact strength are excellent, and the gloss and the balance of other physical properties are good only when the fatty acid glycerin ester and the weather resistance are added in an appropriate amount.

[0055]

The thermoplastic resin composition of the present invention is excellent in weather resistance, impact resistance and chemical resistance, has a good balance of physical properties such as heat resistance, elongation and rigidity, has good moldability, and is obtained. The appearance of the molded product, especially the gloss is excellent and beautiful,
It has extremely high practical value as an industrial material.

Claims (3)

[Claims] 1. A copolymer (A) containing (I) an aromatic vinyl monomer unit, a vinyl cyanide monomer unit, and a vinyl monomer unit having an epoxy group, or the copolymer (A). )
And a copolymer (B) containing an aromatic vinyl monomer unit and a vinyl cyanide monomer unit, the vinyl monomer unit having an epoxy group in the copolymer (A) The amount of (I) is 0.1 to 10% by weight in 100% by weight, 60 to 95 parts by weight of the composition, and (II) unsaturated dicarboxylic acid anhydride monomer unit or unsaturated carboxylic acid unit 0.2 parts by weight of (III) fatty acid glycerin ester to 100 parts by weight of a resin composition consisting of 5 to 40 parts by weight of a modified polyolefin-based polymer modified by 0.1 to 10% by weight of a body unit.
A thermoplastic resin composition comprising 5 parts by weight and 0.01 to 5 parts by weight of (IV) weathering agent. 2. (I), (II) and (II) according to claim 1.
A method for producing a thermoplastic resin composition, which comprises melt-mixing a composition comprising I), and further adding (IV) according to claim 1 and performing melt-mixing. 3. (A) and (II) of (I) according to claim 1.
And (III) are melt-mixed, and (IV) and (I) (B) according to claim 1 are further added and melt-mixed, which is a method for producing a thermoplastic resin composition. .