JPH07138448A - Thermoplastic resin composition excellent in matte effect - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition composed of a graft copolymer, a polyamide resin and a modified styrene-based resin, excellent in matte effect, mold transfer properties and impact resistance, capable of ready fabrication and useful, e.g. for interior of an automobile. CONSTITUTION:This resin composition is prepared by blending (B) 0.1 to 40 pts.wt. styrene-based copolymer synthesized by using a carboxylic acid-containing unsaturated compound, preferably (C) 0.1 to 40 pts.wt. rubber-reinforced styrene- based copolymer with (A) a resin composition composed of (i) 10 to 90wt.% graft copolymer synthesized by polymerizing 30 to 90 pts.wt. monomer mixture composed of (a) 15 to 45wt.% vinyl cyanide compound, (b) 55 to 85wt.% aromatic vinyl compound and (c) O to 30wt.% another copolymerizable vinyl compound in the presence of 10 to 70 pts.wt. conjugated diene-based rubber, (ii) 0 to 70wt.% copolymer synthesized by copolymerizing a monomer mixture composed of 15 to 45wt.% component (a), 55 to 85wt.% component (b) and 0 to 30wt.% component (c) and (iii) 10 to 90wt.% polyamide resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a matte appearance and is excellent in the transferability of the embossed die surface, so that the surface glossiness of the embossed surface is extremely low, and the impact resistance, heat resistance and molding processability are excellent. , And a thermoplastic resin composition suitable for applications requiring these properties, for example, automobile interior parts, home electric appliance parts, etc., due to their excellent chemical resistance.

[0002]

2. Description of the Related Art Rubber-reinforced styrene resins represented by ABS resins have excellent impact resistance, heat distortion resistance, molding processability, and good surface gloss, and are therefore suitable for automobiles and home appliances. Used as various resin materials for various purposes. On the other hand, in recent years, in the fields of automobile interior parts, home electric appliances, etc., there is a need for resin materials with matte properties that suppress the gloss (light reflectance) of the product surface, with the intention of seeking high quality. It is rising.

[0003] As a method for obtaining a matte part with suppressed gloss, conventionally, a mold surface is textured, a matte coating method is used, a fine particle inorganic filler such as talc or a rubber component is blended. Came. However, these methods are not preferable in terms of cost because they do not exhibit a high degree of mattness and increase the number of manufacturing steps in coating. That is, in the improvement of the mold surface, it is difficult to repair and manage the mold, and the gloss condition depends on the molding conditions, and it is difficult to obtain a molded product having a certain gloss. Further, the rubber-reinforced styrene-based resin described above has poor transferability on the mold surface even if the mold surface is subjected to graining, so that it is difficult to obtain a surface of a molded product with suppressed gloss. Furthermore, the impact resistance is significantly reduced when the inorganic fine particle filler is blended, and the heat distortion resistance is reduced when the rubber-like substance is added, and flow marks and weld lines are easily generated, so that a molded article having an excellent appearance can be obtained. was difficult.

Further, in JP-A-4-55455 and JP-A-4-55458, glycidyl ester compounds of α, β-unsaturated acids and ethylenically unsaturated compounds are referred to as A
An ABS resin which has been graft-copolymerized with an S-based resin has been proposed, but it is difficult to obtain a satisfactory appearance with this method because uneven gloss and flow marks are observed.

[0005]

As a result of intensive studies aimed at solving these drawbacks, the present inventor has found that a graft copolymer, a polyamide resin, a modified styrene resin, and a rubber-reinforced modified styrene resin are used as components. The resin composition has a matte low gloss (light reflectance) and is excellent in the transferability of the textured die surface, so that the glossiness of the molded article having the textured surface is extremely low. The present invention has been completed and the present invention has been completed by discovering that it is excellent in impact resistance, heat resistance, molding processability, and chemical resistance.

That is, the present invention provides a conjugated gen rubber 1
Vinyl cyanide compound 15 in the presence of 0 to 70 parts by weight
~ 45 wt%, aromatic vinyl compound 55-85 wt%,
And 10 to 90% by weight of a graft copolymer (a) obtained by polymerizing 30 to 90 parts by weight of a monomer mixture consisting of 0 to 30% by weight of another copolymerizable vinyl compound, and a vinyl cyanide compound. Copolymer (b) obtained by polymerizing a monomer mixture consisting of 15 to 45% by weight, an aromatic vinyl compound 55 to 85% by weight, and another copolymerizable vinyl compound 0 to 30% by weight. A styrene-based copolymer in which a carboxylic acid-containing unsaturated compound is copolymerized with 100 parts by weight of a resin composition (A) consisting of 0 to 70% by weight and a polyamide resin (c) from 10 to 80% by weight ( d) 0.
1 to 40 parts by weight and, if necessary, 0.1 to 40 parts by weight of a rubber-reinforced styrenic copolymer (e) in which a carboxylic acid-containing unsaturated compound is copolymerized are blended to provide excellent matting properties The present invention relates to a thermoplastic resin composition, which is excellent in matteness and has a low gloss on the surface of a molded product having a textured surface due to its high mold transferability, and also has strength, impact resistance, and chemical resistance. It is characterized by being excellent in.

The present invention will be specifically described below.

Graft copolymer (a) used in the present invention
(Hereinafter, referred to as ABS) means the following.
Aromatic vinyl compounds in the presence of 10 to 70 parts by weight of gen-based rubber, 55 to 85% by weight, vinyl cyanide compounds, 1
Monomer mixture 30 to 9 consisting of 5 to 45% by weight and other vinyl compound copolymerizable therewith and 0 to 30% by weight
It means a graft copolymer obtained by copolymerizing 0 part by weight.

The term "gen-based rubber" as used herein means polybutadiene (PBD), styrene-butadiene rubber (S
BR) and the like.

As the aromatic vinyl compound in the above ABS, styrene (ST), α-methylstyrene, ρ
-Methylstyrene and the like are exemplified, and these may be used in combination.

Examples of vinyl cyanide compounds include acrylonitrile (AN) and methacrylonitrile, with AN being more preferred.

Examples of the vinyl compound which can be copolymerized with the aromatic vinyl compound and the vinyl cyanide compound include methyl (meth) acrylate and butyl acrylate. In order to obtain the resin composition of the present invention having excellent matting properties and physical properties, it is preferable that the composition ratio of each component in ABS is within the above range. If the amount of gen-based rubber in ABS exceeds 50 parts by weight, the moldability of the final composition will deteriorate. On the other hand, if the amount of rubber in the ABS component is less than 10 parts by weight, the mechanical properties of the final composition, especially the impact resistance, will be low.
Further, if the amount of the aromatic vinyl compound in the monomer mixture forming the matrix resin in ABS exceeds 85% by weight, the physical properties of ABS deteriorate, while the amount of the vinyl cyanide compound exceeds 45% by weight. When the resin composition becomes non-uniform, the resin is likely to be colored. It is necessary that the content of other vinyl monomers copolymerizable with the aromatic vinyl compound and the vinyl cyanide compound is 30% by weight or less. AB over 30% by weight
The physical properties of S, especially impact resistance and fluidity, deteriorate.

As a method for producing ABS, known emulsion polymerization method, bulk suspension polymerization method or solution polymerization method can be mentioned. In particular, since emulsion polymerization ABS using rubber latex has good blending workability afterwards. More preferable.

The copolymer (b) used in the present invention (hereinafter referred to as AS
Is described) means the following. That is, a monomer mixture of 55 to 85% by weight of an aromatic vinyl compound, 15 to 45% by weight of a vinyl cyanide compound and 0 to 30% by weight of another vinyl compound copolymerizable therewith is copolymerized. It is a thing.

As the aromatic vinyl compound in the above AS, styrene (ST), α-methylstyrene (AM
S), β-methylstyrene and the like are exemplified, and these can be used in combination.

Examples of vinyl cyanide compounds include acrylonitrile (AN) and methacrylonitrile, with AN being more preferred.

Examples of the vinyl compound that can be copolymerized with the aromatic vinyl compound and the vinyl cyanide compound include methyl (meth) acrylate and butyl acrylate.

55% by weight of aromatic vinyl compound in AS
If it is less than 85%, AS becomes brittle, and if it exceeds 85% by weight, the thermal stability of the resin is deteriorated. On the other hand, if the amount of the vinyl cyanide compound is less than 15% by weight, the chemical resistance of AS is low, and if it exceeds 45% by weight, the moldability is deteriorated.
Further, the amount of the fifth component monomer should be at most 30% by weight or less, and if it is copolymerized more than that, fluidity and the like deteriorate.

Further, as a method for producing AS, there are an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like, but there is no problem even if they are produced by any polymerization method.

When a mixture of ABS and AS is used in the present invention, the mixing ratio on a weight basis is ABS.
/ AS = 100/0 to 12.5 / 87.5 should be selected. As long as it is within this mixing ratio range, there are no particular restrictions on the mixing method. ABS / AS ratio is 10
When it is out of the range of 0/0 to 12.5 / 87.5, the physical properties of the final composition, particularly the impact resistance are lowered, and it is not suitable as the material resin which is the object of the present invention.

The polyamide resin used in the present invention is not limited in its kind, but is a polycondensate of diamine and dibasic acid, a self-condensate of ω-aminocarboxylic acid, a ring-opening polymer of cyclic lactam, and the like. There are, for example, poly ε-caprolactam (polyamide-6), polyhexamethylene adipamide (polyamide-6,6), polyamide-4,6, polyamide-MXD6 and the like, and their use alone or in combination is preferred. These polyamide resins have an amino terminal group of 0.
010 to 0.100 mmol / g is preferable. When the terminal amino group content is 0.010 mmol / g or less, the reactivity with the modified styrene resin described in the next section is poor and the physical properties of the final composition, especially the impact resistance, are low. . The amount of amino end groups is 0.100mmo
When it is 1 / g or more, the final composition has poor moldability (melt flowability) and thermal stability. The amount of amino terminal groups can be quantified by ¹ H-NMR or a titration method. In addition, the relative viscosity (ηrel) of the solution dissolved in 96% sulfuric acid at the concentration of 1 g / d ■ was 2.0 at 25 ℃.
Polyamide resins of ˜7.0 are preferred. ηrel is 2.0
Below, the physical properties of the final composition, particularly impact resistance, are low, and conversely, above 7.0, the melt viscosity of the final composition is too high and molding is not easy.

Styrene-based copolymer (d) used in the present invention
Means the following. That is, 0.1 to 8% by weight of the carboxylic acid-containing unsaturated compound and the aromatic vinyl compound 5
5 to 85% by weight, vinyl cyanide compound 15 to 45% by weight, and other vinyl compounds copolymerizable therewith 0
It is a copolymer of a monomer mixture consisting of ˜30% by weight.

As the carboxylic acid-containing unsaturated compound in the styrene-based copolymer (d), acrylic acid (A
A) and methyl (meth) acrylic acid (MAA) are preferred.

Examples of the aromatic vinyl monomer include styrene (ST), α-methylstyrene (AMS), β-methylstyrene and the like, and these can be used in combination.

Examples of vinyl cyanide compounds include acrylonitrile (AN) and methacrylonitrile, with AN being more preferred.

Examples of the vinyl compound which can be copolymerized with the aromatic vinyl compound and the vinyl cyanide compound include methyl (meth) acrylate and butyl acrylate.

The carboxylic acid-containing unsaturated compound is 0.1 to 8% by weight, preferably 0.2 to 5% by weight, more preferably 0.3 to 4% by weight in the component (d). 0.1
If it is less than 8% by weight, the impact resistance is low, and if it exceeds 8% by weight, the impact resistance, molding processability and appearance of the molded product are poor.

If the amount of the aromatic vinyl compound in component d is less than 55% by weight, the resin becomes brittle, and if it exceeds 85% by weight, the thermal stability of the resin becomes poor. On the other hand, when the amount of the vinyl cyanide compound is less than 15% by weight, the heat resistance of the modified styrene resin is low, and when it exceeds 45% by weight, the moldability is deteriorated. Also, the amount of vinyl compound that can be copolymerized is
It should be at most 30% by weight or less, and if it is copolymerized more than that, the fluidity becomes worse.

Further, as a method for producing the styrene-based copolymer (d), there are an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like, but any polymerization method can be used.

Specific examples of the rubber-reinforced styrenic copolymer (e) used in the present invention include: 1) an aromatic vinyl compound or an aromatic vinyl compound in the presence of a rubbery polymer obtained by copolymerizing a carboxylic acid-containing unsaturated compound. A graft copolymer obtained by polymerizing a monomer composed of an aromatic vinyl compound and a carboxylic acid-containing unsaturated compound, 2) an aromatic vinyl compound and a carboxylic acid-containing unsaturated compound in the presence of a rubbery polymer A graft copolymer obtained by copolymerizing a monomer consisting of 3), 3) a rubber-reinforced styrene resin in which a carboxylic acid-containing unsaturated compound is not copolymerized, a carboxylic acid-containing unsaturated compound, and an aromatic vinyl compound A mixture with a copolymer of monomers having as essential components, 4) a mixture of the above 1) or 2) with a copolymer containing a carboxylic acid-containing unsaturated compound and an aromatic vinyl compound 5) There is a mixture of the above 1), 2), 3), or 4) and a copolymer containing an aromatic vinyl compound as an essential component.

In the above 1) to 5), styrene (ST) and α-methylstyrene (AMS) are preferable as the aromatic vinyl compound, and a mixture thereof is also possible. Further, acrylonitrile is preferable as the monomer copolymerized with the aromatic vinyl compound. Moreover, acrylic acid and methyl (meth) acrylic acid are preferable as the carboxylic acid-containing unsaturated compound.

The carboxylic acid-containing unsaturated compound is 0.1 to 8% by weight, preferably 0.2 to 7% by weight, more preferably 0.3 to 7% by weight in the component (e). 0.1
If it is less than 8% by weight, the impact resistance is low, and if it exceeds 8% by weight, the impact resistance, the molding processability and the appearance of the molded product are deteriorated.

In the resin composition (A) of the present invention, the graft copolymer resin (a) is 10 to 90% by weight, preferably 10 to 80% by weight, more preferably 20 to 7%.
It is 0% by weight. If it is less than 10% by weight, impact resistance and molding processability are poor.
Moldability deteriorates.

The copolymer (b) is 0 to 70% by weight,
It is preferably from 0 to 40% by weight, and when it is 90% by weight or more, the impact resistance of the final composition becomes poor.

Next, the amount of polyamide resin (c) used is 10
~ 90 wt% is desirable. If it is less than 10% by weight, the mold transfer property and chemical resistance of the final composition are not sufficient, and if it exceeds 90 parts by weight, physical properties such as impact resistance are deteriorated.

Resin composition (A) 100 comprising the above components
The amount of the styrene-based copolymer (d) added to the weight part is 0.1-
40 parts by weight. More preferably, the addition of 1 to 20 parts by weight is desirable. When the addition amount of the component d is less than 0.1 part by weight,
The matteness of the molded article molded from the final composition is significantly reduced. On the other hand, if it exceeds 40 parts by weight, the fluidity tends to decrease and decomposition during molding tends to occur.

When the rubber-reinforced styrene copolymer (e) is added to the resin composition (A) consisting of the above components for the purpose of imparting impact resistance, the amount used is 100 total amount of the resin consisting of a to d. The amount should be 0.1 to 40 parts by weight per part. More preferably, the addition of 1 to 20 parts by weight is desirable.
If the amount of component e added exceeds 40 parts by weight, the fluidity tends to decrease and decomposition during molding tends to occur. If it is less than 0.1 part by weight, the impact strength is not improved so much.

The content of the carboxylic acid-containing unsaturated compound in the entire composition is 0.04 to 6% by weight, preferably 0.3 to 5% by weight. If it is less than 0.04% by weight, matteness and impact resistance are low, and if it exceeds 6% by weight, impact resistance, molding processability, weld strength and molding appearance are deteriorated.

The rubber content in the total composition is 5 to 40% by weight.
It is desirable to be in the range of, preferably 7 to 35% by weight, and more preferably 7 to 30% by weight. 5% by weight
If it is less than 100, impact resistance and weld strength are low. If it exceeds 40% by weight, moldability becomes poor.

For blending the above components, an extruder and a needle are used.
It is sufficient to melt and knead using a dull, roll or the like. A preferred method is a method in which powdered raw materials are mixed using a Henschel mixer or the like, and this is heated and melted using an extruder to be extruded and pelletized.

In the final composition of the present invention, various kinds of commonly used additives such as plasticizers, antioxidants, stabilizers, inorganic fillers, reinforcing materials such as glass fibers, pigments and dyes, etc. are used. You can do it. Further, a flame retardant may be added to the final composition of the present invention. As the flame retardant, a phosphorus compound such as triphenyl phosphate or a halogen compound such as decabromodiphenyl oxide is used. The filling amount of these additives must be suppressed to 40 parts by weight or less per 100% by weight of the resin composition. If it is added more than this, the physical properties of the final composition deteriorate.

[0042]

EXAMPLES Examples of the present invention will be described below in detail. However, the present invention is not limited to these examples. All parts and% in the examples are based on weight. The types of ABS (a), AS (b), polyamide resin (c), styrene-based copolymer (d) and rubber-reinforced styrene-based copolymer (e) used in the present invention are shown in Tables 1-5.

Further, the performance of the compositions in Examples 1 to 15 and Comparative Examples 1 to 5 was evaluated by the following 5 items.

(1) Izod impact strength It was measured according to ASTM D256.

(2) Flexural Modulus Measured according to ASTM D790.

(3) Heat distortion temperature It was measured according to ASTM D648.

(4) 60 ° reflectance Using black colored pellets, a length of 10 was obtained using an injection molding machine.
It was molded into a flat plate-shaped molded product having a width of 0 mm, a width of 50 mm, and a thickness of 3 mm, and the 60 ° reflectance at a fixed position was measured. As the mold, a mold cavity surface was processed so that the surface of the molded product had a mirror surface and a textured surface. A skin grain (grain C) was used as the grain.

(5) Surface appearance A molded article similar to the above was obtained, and flow marks, uneven gloss, uneven color, and weld lines were visually observed and judged according to the following criteria.

○: good △: somewhat good ×: bad

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5] (Example 1) 50 parts of ABS (a-1) and 5 parts of polyamide resin (c-1; A1030BRL manufactured by Unitika Ltd.)
Based on 100 parts by weight of 0 part, a styrene-based copolymer (d
-1) in an amount of 10 parts by weight, and an antioxidant and a lubricant each in an amount of 0.
After adding 1 part, it was dry blended for 20 minutes using a V-type blender. The resin mixture after blending was kneaded and extruded at 230 ° C. using a 40 mmφ single screw extruder manufactured by Osaka Seiki Co., Ltd.

No bent-up or surging was observed during extrusion. The extruded strand was cooled in a water bath and pelletized. 9 pellets in hot air dryer
After being dried at 0 ° C. for 4 hours, a test piece was obtained by injection molding. Injection molding is injection molding machine TS manufactured by Nissei Plastic Industry Co., Ltd.
A test piece for physical property evaluation was molded with a -100 type. The molding conditions were a cylinder temperature of 230 ° C., a mold temperature of 60 ° C., and a molding cycle of injection for 15 seconds and cooling for 30 seconds.

The test specimens are 1/4 "bars for bending and Izod impact testing.

Table 6 shows the results of the evaluation of the physical properties, matteness and surface appearance of the test pieces thus obtained. It had a high impact resistance, a high degree of mattness, no flow marks, and a good appearance.

(Examples 2, 3, 4) In these examples, the influence of the styrenic copolymer on the matting property was examined. That is, in Example 1, the styrene-based copolymer d
The procedure of Example 1 was repeated, except that the compounding amount of -1 was 2, 5 and 20 parts by weight, respectively. Compared with Example 1, in Example 2 the mattness and impact resistance were slightly reduced. Further, in Example 4, although the heat resistance was improved, the fluidity was slightly lowered.

(Examples 5 and 6) These examples correspond to Example 1
In Example 5, the styrene component in the d-1 component was replaced with styrene /
The one changed to α-methylstyrene was used (d-
2). Furthermore, in Example 6, the acrylic acid in the d-2 component used in Example 5 was changed to methacrylic acid (d-3). At this time, substantially the same results as in Example 1 were obtained in terms of physical properties and matting properties.

(Example 7) In this example, AS is further added to the composition of Example 1. That is, ABS
10 parts by weight of the styrene-based copolymer (d-1) was added to 100 parts by weight of 25 parts of (a-1), 25 parts of AS (b-1) and 50 parts of the polyamide resin (c-1). Except for this, the same procedure as in Example 1 was performed. The impact resistance is slightly reduced, but the rigidity and heat resistance are improved.

Comparative Examples 1 and 2 In Comparative Example 1, the properties of ABS alone were used as a reference example, and in Comparative Example 2, ABS (a-
1) 100 parts by weight of styrene-based copolymer (d-
This is an example in which 10 parts by weight of 1) are blended. In Comparative Example 1, the matteness is completely insufficient, and in Comparative Example 2, the matteness is improved as compared with Comparative Example 1, but the mold transferability is not sufficient.
The surface reflectance of the textured flat plate was high and the matteness was not so high. In addition, flow marks were observed on the surface of the molded product.

(Comparative Example 3) In this example, ABS (a-1)
Example 1 was repeated except that 50 parts by weight and 50 parts by weight of the polyamide resin (c-1) were used. The surface reflection of the textured flat plate was suppressed, but the reflectance of the mirror surface was high, and the matting property of the composition itself was poor.

[0058]

[Table 6] (Examples 8 and 9) These examples are examples in which the type of ABS in the composition was changed. Here, ABS (a-2) with a low rubber content instead of ABS (a-1), or ABS
AB with high acrylonitrile copolymerization ratio in matrix
Example 1 was repeated except that S (a-3) was used. All were good in mattness, strength, and appearance.

(Examples 10 and 11) These examples are examples in which the type of polyamide resin in the composition was changed. In Example 10, instead of the polyamide resin (c-1), (c-
1) using a higher molecular weight nylon (c-2), and in Example 11 using nylon-66 resin (c-3), except for Example 11 in which the molding processing temperature is 260 ° C.
The same procedure as in Example 1 was performed. Since (c-2) was used in Example 10, the melt viscosity was increased, but there was no significant difference in mattness and the like as compared with Example 1. (Example 1
0). In the case of Example 11 using C-3, nylon-
Since the melting point of 66 was high, the molding temperature and the processing temperature were high, but the matteness and strength were good.

(Examples 12 and 13) Here, the amounts of ABS and polyamide resin were examined. That is, Example 1
In Nos. 2 and 13, the amounts of polyamide resin in the resin composition were 30 parts by weight and 70 parts by weight, respectively. Example 12 is Example 1
Compared with the above, the impact resistance was increased, but conversely, the mold transferability was decreased, and therefore the surface reflectance of the textured flat plate was slightly increased. However, the matteness is considered to be at a level that is suitable for use. Further, in Example 13, the matting property was sufficient. However, since the amount of rubber decreased, the impact strength also decreased.

(Comparative Example 4) In this example, a composition having a resin composition ratio out of the claimed range was examined for physical properties and matting properties. That is, the styrene-based copolymer (d-1) was added to 100 parts by weight of the total resin composition consisting of 95 parts by weight of ABS (a-1) and 5 parts by weight of polyamide resin (c-1).
Example 1 was repeated except that 10 parts were used. The matteness was insufficient and the surface appearance was not good.

[0062]

[Table 7] (Examples 14 and 15) In these examples, 100 parts by weight of the resin composition used in Example 1 was compounded with the rubber-reinforced styrene copolymer (e-1, e-2).
The procedure was the same as in Example 1 except that the rubber-reinforced styrene copolymer was blended. Compared to Example 1, the impact resistance was dramatically improved. In addition, the matteness was the same as that of Example 1 and the surface appearance was good.

Comparative Example 5 This example was carried out in the same manner as in Example 14 except that the styrene copolymer (d-1) used in Example 14 or 15 was omitted. It has high strength such as impact resistance, but was not sufficiently matt.

[0064]

[Table 8]

[0065]

EFFECT OF THE INVENTION The molded product of the present invention has excellent matteness, high mold transferability, high impact resistance, and can be easily obtained by molding such as injection molding. It is extremely useful for parts that require matteness such as the exterior of home appliances.

Claims (2)

[Claims] 1. A cyanide vinyl compound in an amount of 15 to 45% by weight, an aromatic vinyl compound in an amount of 55 to 85% by weight, and another copolymerizable vinyl compound in the presence of 10 to 70 parts by weight of a conjugated gen rubber. ~ 30 wt% monomer mixture 3
Graft copolymer (a) 10 to 90% by weight obtained by polymerizing 0 to 90 parts by weight, vinyl cyanide compound 15 to 45% by weight, aromatic vinyl compound 55 to 85% by weight, and other copolymers Resin composition comprising 0 to 70% by weight of a copolymer (b) obtained by polymerizing a monomer mixture comprising 0 to 30% by weight of a possible vinyl compound and 10 to 90% by weight of a polyamide resin (c). Styrene-based copolymer (d) 0.1 in which a carboxylic acid-containing unsaturated compound is copolymerized with 100 parts by weight of the product (A).
A thermoplastic resin composition having an excellent matting property, which is prepared by mixing 40 parts by weight. 2. A rubber-reinforced styrene-based copolymer (e) 0.1 to 100 parts by weight of the resin composition (A) according to claim 1, which is further copolymerized with a carboxylic acid-containing unsaturated compound.
A thermoplastic resin composition containing 40 parts by weight and having excellent matting properties.