KR20090016955A - Low gloss thermoplastic resin composintion - Google Patents

Abstract

A low gloss thermoplastic resin composition is provided to improve impact resistance, strength, weather resistance and flatting effect as compared with conventional thermoplastic resin composition. A low gloss thermoplastic resin composition comprises (A) a graft-copolymer 20-50 parts by weight of an acrylate compound, aromatic vinyl compound and vinyl cyanide compound; (B) a copolymer 40-80 parts by weight of aromatic vinyl compound and vinyl cyanide compound; and (C) a low gloss graft-copolymer 5-40 parts by weight. The low gloss graft-copolymer is formed by graft-polymerizing (i) at least one monomer selected from the group consisting of aromatic vinyl compound, vinyl cyanide compound and alkyl methacrylate compound to (ii) an alkyl acrylate rubber polymer having the average particle diameter of 20-200 nm. The low gloss graft-copolymer forms the aggregate of 1-20 micrometer.

Description

Matte thermoplastic resin composition {LOW GLOSS THERMOPLASTIC RESIN COMPOSINTION}

The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition which is excellent in impact resistance, rigidity, weather resistance, and the like, and which can significantly reduce surface gloss, compared to a conventional thermoplastic resin composition.

High impact thermoplastic resins are prepared by incorporating rubber in the form of particles into a styrene-acrylonitrile copolymer. Such a method is generally a method of graft copolymerization of styrene and acrylonitrile in the presence of rubber, and then mixing the prepared graft product with a matrix resin which is a hard component comprising a styrene-acrylonitrile copolymer. The high impact thermoplastic resin produced in this way varies in the property distribution of the physical properties obtained depending on the rubber used.

The rubber conventionally used in acrylonitrile-butadiene-styrene (ABS) polymers is butadiene rubber polymer. Butadiene polymers have good impact resistance even at very low temperatures, while the weatherability and aging resistance are relatively low. Therefore, in order to obtain a product having not only high impact strength but also excellent weatherability and aging resistance, there should be no ethylenically unsaturated polymer in the graft copolymer.

An acrylate-styrene-acrylonitrile (ASA) polymer using crosslinked alkyl acrylate rubber polymers has proven to be suitable as a representative example where no ethylenically unsaturated polymer is present. ASA polymers using crosslinked alkyl acrylate rubber polymers are commonly used in outdoor applications that require products of various colors, such as garden furniture, boats, signs, street lamp covers, and the like. However, as users' emotional quality level increases in recent years, the demand for matte resins is increasing to create a more elegant atmosphere.In addition, due to environmental problems, the use of matte resins or pads is omitted and the matte resins are used directly. The trend is to try.

In order to achieve such a matte effect, a method of controlling the flatness of the resin surface to be larger than the visible light region to scatter incident light and producing a matte effect is mainly used. The following conventional techniques are widely used.

U. S. Patent No. 5,237, 004 discloses thermoplastic resin compositions of particular core / shell structure in which the surface gloss is reduced by the presence of large diameter polymer particles of 2 to 15 micrometers. The large-diameter polymer particles have a problem in that gloss is reduced but gloss is not uniform, and the hardness and rigidity are greatly reduced.

U. S. Patent 5,965, 665 discloses thermoplastic resin compositions having reduced gloss using certain gel polymers and low molecular weight olefin polymers. However, although the manufacturing method provides a matt effect and impact resistance, it is difficult to obtain an excellent low gloss effect during sheet extrusion, and a serious decrease in the heat deflection temperature.

In addition, US Pat. No. 6,696,165 discloses a weather resistant low gloss styrene copolymer composition incorporating a partially crystalline polymer to express a matt effect. However, such a manufacturing method tends to show impurities on the surface of the molded article due to the partially crystalline polymer, thereby impairing the merchandise value of the molded article and severely reducing weather resistance and impact strength.

In order to solve the problems of the prior art as described above, the present invention is a matt graft copolymer comprising an alkyl acrylate rubber polymer having an average particle diameter of 20 to 200 nm forms an aggregate of 1 to 20 ㎛ in the thermoplastic resin composition An object of the present invention is to provide a matt thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention

A) 20 to 50 parts by weight of a graft copolymer of an acrylate compound, an aromatic vinyl compound and a vinyl cyan compound;

B) 40 to 80 parts by weight of the copolymer of the aromatic vinyl compound and the vinyl cyan compound; And

C) i) at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate compound is formed by graft polymerization in an alkyl acrylate rubber polymer having an average particle diameter of 20 to 200 nm. 5 to 40 parts by weight of the matte graft copolymer,

The matte graft copolymer provides a matte thermoplastic resin composition, characterized in that to form an aggregate of 1 to 20㎛.

At this time, the graft copolymer of the acrylate compound, the aromatic vinyl compound and the vinyl cyan compound of A) is characterized in that the acrylate-styrene-acrylonitrile (ASA) graft copolymer.

Compared with the conventional thermoplastic resin composition, the thermoplastic resin composition according to the present invention has the effect of simultaneously improving both impact resistance, rigidity, weather resistance, and matt effect.

Hereinafter, the present invention will be described in detail.

In the preparation of the matte graft copolymer, the present inventors have prepared i) preparing an alkyl acrylate rubber polymer having an average particle diameter of 20 to 200 nm, and ii) an aromatic vinyl compound, a vinyl cyan compound, and an alkyl methacrylate compound. Graft polymerization of one or more monomers selected from graft, when the graft ratio, the molecular weight and the composition ratio of the monomers are appropriately adjusted, the matte graft copolymers agglomerate with each other in the thermoplastic resin composition to form an aggregate of 1 to 20 μm, Through this, it was confirmed that there is an excellent matt effect due to the excellent gloss reduction while excellent impact resistance, rigidity and heat resistance, and completed the present invention based on this.

That is, in contrast to the prior art in which the matte effect is expressed simply by increasing the size of the particles themselves, the present invention expresses the matte effect by forming small aggregates of aggregates. The problem that the stiffness is greatly reduced can be further improved.

Matte thermoplastic resin composition according to the invention,

A) 20 to 50 parts by weight of a graft copolymer of an acrylate compound, an aromatic vinyl compound and a vinyl cyan compound;

B) 40 to 80 parts by weight of the copolymer of the aromatic vinyl compound and the vinyl cyan compound; And

C) i) at least one monomer selected from the group consisting of i) aromatic vinyl compounds, vinyl cyan compounds and alkyl methacrylate compounds is formed by graft polymerization in alkyl acrylate rubber polymers having an average particle diameter of 20 to 200 nm. 5 to 40 parts by weight of the matte graft copolymer,

The matt graft copolymer is characterized in that it forms an aggregate of 1 to 20 μm.

The graft copolymer of the acrylate compound, the aromatic vinyl compound and the vinyl cyan compound of A) according to the present invention may be prepared by graft polymerization of an aromatic vinyl compound and a vinyl cyan compound on an alkyl acrylate rubber polymer.

The alkyl acrylate rubber polymer monomer preferably has an alkyl group having 2 to 8 carbon atoms, and specifically, butyl acrylate or ethyl hexyl acrylate may be used alone or in combination.

Preferably, the alkyl acrylate rubber polymer has a glass transition temperature of -70 to -20 ° C., and when the glass transition temperature is less than -70 ° C., there is a problem that whitening occurs at a low temperature. In this case, there is a problem that the low temperature impact resistance is lowered.

The alkyl acrylate rubber polymer may be included in an amount of 30 to 70 parts by weight based on 100 parts by weight of the graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound.

As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, or a styrene monomer derivative of vinyl toluene may be used, and the content thereof is a graft copolymer of an acrylate compound, an aromatic vinyl compound, and a vinyl cyan compound. It is preferably included in 15 to 55 parts by weight based on a total of 100 parts by weight.

The vinyl cyan compound may be used alone or mixed with acrylonitrile or methacrylonitrile, the content of which is 5 to about 100 parts by weight of the graft copolymer of the acrylate compound, the aromatic vinyl compound and the vinyl cyan compound in total. It is preferably included in 35 parts by weight.

The graft copolymer of the acrylate compound, the aromatic vinyl compound and the vinyl cyan compound according to the present invention is preferably an acrylate-styrene-acrylonitrile (ASA) graft copolymer.

The graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound may further include an emulsifier, an initiator, a grafting agent, a crosslinking agent, a molecular weight modifier, an electrolyte material, and the like, which are commonly used in the art, depending on the use. Of course it can.

The graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound may be prepared by a conventional emulsion polymerization method.

The graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound prepared above may be recovered in the form of a dry powder by coagulation and spray drying as necessary. Specifically, a coagulant is added to the graft copolymer of the final acrylate compound, the aromatic vinyl compound and the vinyl cyan compound obtained by the emulsion polymerization to agglomerate the polymer particles in the latex, and then washed, dehydrated and dried to form a dry powder. It may also be obtained.

The graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound is preferably included in an amount of 20 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin composition. If the content is less than 20 parts by weight, there is a problem that impact resistance and weather resistance is lowered, and if it exceeds 50 parts by weight, there is a problem that gloss, scratch resistance and rigidity are lowered.

The copolymer of the aromatic vinyl compound of B) and the vinyl cyan compound according to the present invention is included as a hard matrix resin in the thermoplastic resin composition of the present invention.

It is preferable that the aromatic vinyl compound and the vinyl cyan compound are mixed at a weight ratio of 8: 2 to 6: 4. If the mixing ratio is out of the above range, there is a problem that the chemical resistance and workability is lowered.

The aromatic vinyl compound and the vinyl cyan compound may use the same components as those described in the preparation of the graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound of A), in particular the aromatic As the copolymer of the vinyl compound and the vinyl cyan compound, a styrene-acrylonitrile copolymer is preferably used.

The copolymer of the aromatic vinyl compound and the vinyl cyan compound is preferably included in an amount of 40 to 80 parts by weight based on 100 parts by weight of the thermoplastic resin composition. If the content is less than 40 parts by weight, there is a problem that the gloss and scratch resistance is lowered, and if it exceeds 80 parts by weight, there is a problem that the weather resistance and impact resistance is lowered.

The matte graft copolymer of C) according to the present invention is based on a total of 100 parts by weight of the matte graft copolymer i) 30 to 70 parts by weight of an alkyl acrylate rubber polymer having an average particle diameter of 20 to 200 nm ii) aromatic vinyl 30 to 70 parts by weight of one or more monomers selected from the group consisting of compounds, vinyl cyan compounds and alkyl methacrylate compounds may be prepared by graft polymerization.

The alkyl acrylate rubber polymer monomer, the aromatic vinyl compound monomer, and the vinyl cyan compound monomer are each of the components described in preparing a graft copolymer of the acrylate compound, the aromatic vinyl compound, and the vinyl cyan compound of A). The same ingredients can be used.

The alkyl methacrylate compound may be used alone or in combination of methyl methacrylate or ethyl methacrylate.

The matt graft copolymer is preferably included in 5 to 40 parts by weight based on 100 parts by weight of the total thermoplastic resin composition. If the content is less than 5 parts by weight, there is a problem that the matting effect is lowered, if it exceeds 40 parts by weight there is a problem that the impact resistance is lowered.

The matte graft copolymer according to the present invention are aggregated together by interparticle interaction in the thermoplastic resin composition prepared by the present invention to form an aggregate of 1 to 20㎛, thereby showing a significant matt effect.

In order to form such aggregates, the particle size of the alkyl acrylate rubber polymer may be adjusted to 20 to 200 nm during polymerization of the matt graft copolymer, the graft ratio may be lowered as much as possible, the molecular weight may be increased as much as possible, and the vinyl may be used during the graft polymerization (ii). The composition ratio of the cyan compound should be prepared to have a difference of 5 parts by weight or more compared with the composition ratio of the vinyl cyan compound in the copolymer of the aromatic vinyl compound and the vinyl cyan compound of B).

The graft rate is expressed as a percentage of the weight of the copolymer grafted to the rubber lg, by stirring 2g of a powdery matte graft copolymer with 100 ml of acetone for 24 hours to dissolve the ungrafted components in the rubber component, ultracentrifugal After separating the gel and the sol by separation, the weight is calculated according to the following equation (1). The rubber weight of Equation 1 refers to the weight of the alkyl acrylate rubber polymer put in the polymerization step, which is determined by (weight of the matte graft copolymer * percentage of the matte graft copolymer of the alkyl acrylate rubber polymer). Is calculated.

[Equation 1]

Graft ratio = [(gel-rubber weight) / rubber weight] × 100

The graft ratio is preferably 20% or less, and the weight average molecular weight is preferably 150,000 g / mol or more.

If the condition is out of the above conditions, the matting graft copolymer does not appear to aggregate in the thermoplastic resin composition, and thus the gloss reduction effect cannot be expected.

The matte graft copolymer according to the present invention may further include an emulsifier, an initiator, a grafting agent, a crosslinking agent, a molecular weight modifier, an electrolyte material, and the like, which are commonly used in the art, depending on the use.

The matt graft copolymer can be prepared by a conventional emulsion polymerization method.

The matt graft copolymer prepared above may be recovered in the form of a dry powder by coagulation and spray drying as necessary. Specifically, a coagulant may be added to the final matte graft copolymer obtained by the emulsion polymerization to agglomerate polymer particles in latex, and then washed, dehydrated, and dried to obtain a dry powder form.

 The thermoplastic resin composition according to the present invention may further include additives such as a lubricant, an antioxidant, an ultraviolet stabilizer, a dye, a pigment, a flame retardant, or an inorganic filler according to each use.

 The thermoplastic resin composition may be prepared by melt kneading three components of A), B) and C) at the same time, or by further melt kneading the other components into a composition in which any two components are kneaded.

The above-mentioned A) and B) are kneaded, and a commercially available thermoplastic resin particularly suitable for the present invention is an ASA resin commercially available from LG Chemical, and the most preferable resin is LI 912W.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

EXAMPLE

Example  One

Preparation of Matte Graft Copolymer Latex

i) 5 parts by weight of butyl acrylate, 0.6 parts by weight of sodium dodecyl sulfate, 0.02 parts by weight of ethylene glycol dimethacrylate, 0.01 parts by weight of allyl methacrylate, 0.1 parts by weight of sodium hydrogen carbonate and 60 parts by weight of distilled water After heating up to 70 ° C, 0.1 parts by weight of potassium persulfate was added to initiate the reaction. After the reaction for 2 hours to prepare a seed latex, 45 parts by weight of butyl acrylate, 0.3 parts by weight of sodium dodecyl sulfate, 0.02 parts by weight of ethylene glycol dimethacrylate, 0.01 parts by weight of allyl methacrylate, A mixture of 40 parts by weight of distilled water and 0.05 parts by weight of potassium persulfate was continuously added at 70 ° C. for 3 hours, followed by further polymerization for 1 hour to prepare an alkyl acrylate rubber latex. The average particle diameter of the said alkyl acrylate rubber polymer latex was 100 nm.

Ii) 35 parts by weight of styrene, 10 parts by weight of acrylonitrile, 5 parts by weight of methyl methacrylate, 1.5 parts by weight of potassium rosin, 0.1 parts by weight of potassium persulfate and 30 parts by weight of distilled water are mixed with the rubber polymer latex of step i) One mixture was continuously added at 70 DEG C for 3 hours to carry out the polymerization reaction. In addition, in order to increase the polymerization conversion rate, after the addition was completed, the temperature was raised to 75 ° C. and further reacted for 1 hour to prepare a final matt graft copolymer latex.

<Manufacturing Matte Graft Copolymer Powder>

The obtained matt graft copolymer latex was subjected to atmospheric coagulation at 80 ° C. using an aqueous calcium chloride solution, then aged at 95 ° C., washed and dehydrated, and dried for 30 minutes with a hot air at 90 ° C. to obtain a matt graft copolymer. Powder particles were obtained.

The dried matte graft copolymer powder had a water content of less than 0.5% and a powder density of at least 0.4 g / cm 3.

The graft ratio of the dried matt graft copolymer powder was 7.8%, and the weight average molecular weight was 170,000 g / mol.

<Thermoplastic resin composition preparation>

ASA resin as a thermoplastic resin having 20 parts by weight of the obtained graft copolymer (C) powder obtained above, A) and B) are mixed in a ratio of 4: 6, and acrylonitrile is 30 parts by weight in the components forming B). (LG Chemical, product name: LI 912W) Use 80 parts by weight, and 1 part by weight of lubricant (previous chemical, product name: EBS), 1 part by weight of titanium dioxide, and antioxidant (Ciba-Geigy product, product name: Irganox 1076 0.5 parts by weight and 0.5 parts by weight of a UV stabilizer (manufactured by Ciba-Geigy, trade name: Tinuvin 327) were added and mixed. The mixture was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 200 ° C., and injected into the pellet to prepare a white specimen.

The matte graft copolymer in the thermoplastic resin composition formed an aggregate having an average particle diameter of about 16 μm.

Example  2

Example 1 was prepared in the same manner as in Example 1, except that sodium dodecyl sulfate was added in an amount of 1 part by weight in the preparation of the seed latex in step iii) when preparing the matt graft copolymer.

The average particle diameter of the obtained alkyl acrylate rubber polymer latex was 80 nm.

The matte graft copolymer in the obtained thermoplastic resin composition formed an aggregate having an average particle diameter of about 17 μm.

Example  3

In preparing the thermoplastic resin composition of Example 1, it was carried out in the same manner as in Example 1, except that 30 parts by weight of the matt graft copolymer was used and 70 parts by weight of the ASA resin (LI912W).

The matte graft copolymer in the obtained thermoplastic resin composition formed an aggregate having an average particle diameter of about 18 μm.

Comparative example  One

The preparation of the thermoplastic resin composition of Example 1 was carried out in the same manner as in Example 1, except that only the ASA resin (LI912W) was manufactured without using a matt graft copolymer.

Comparative example  2

The manufacturing method of the thermoplastic resin composition of Example 1 was performed in the same manner as in Example 1, except that 60 parts by weight of the matt graft copolymer was used and 40 parts by weight of the ASA resin (LI912W).

Comparative example  3

In preparing the matte graft copolymer of Example 1, sodium dodecyl sulfate was reduced to 0.1 parts by weight in the preparation of the seed latex in step iii).

The average particle diameter of the obtained alkyl acrylate rubber polymer latex was 400 nm.

The matte graft copolymer in the obtained thermoplastic resin composition formed an aggregate having an average particle diameter of about 0.8 m.

The physical properties of the specimens prepared in Examples and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.

A) Gloss-measured according to ASTM D523 at 75 °.

B) Izod impact strength (1/4 "notched at 23 ° C., kg · cm / cm) —measured according to ASTM D256.

C) Tensile strength (50 mm / min, kg / cm 2)-measured according to ASTM D638.

Weather resistance-After 5,000 hours test using Atlas Ci4000 Weather-Ometer (Xenon Lamp, Energy 0.5 w / ㎡), the color change was measured by ΔE.

Through Table 1, the thermoplastic resin composition of Examples 1 to 3 (each 20, 20, 30 parts by weight) including the matte graft copolymer according to the present invention in an appropriate content range is a comparative example outside the appropriate content range Compared with 1 (0 parts by weight) and 2 (60 parts by weight), it was confirmed that the gloss was significantly reduced while the impact strength, the tensile strength and the weather resistance were excellent. In addition, the thermoplastic resin compositions of Examples 1 to 3 (100 nm, 80 nm, and 100 nm, respectively) having an average particle diameter of the alkyl acrylate rubber polymer latex used to prepare the matt graft copolymer have an appropriate range of sizes are suitable ranges. Compared with Comparative Example 3 (400 nm) having a size outside of the excellent impact strength, tensile strength and weather resistance, it was confirmed that the gloss is significantly reduced. That is, since the average particle diameter of the alkyl acrylate rubber polymer latex has an appropriate range of sizes (100 nm, 80 nm, and 100 nm, respectively, in Examples 1 to 3), the matte graft copolymer is titrated in the thermoplastic resin composition. It is possible to form aggregates of size (in Examples 1 to 3, respectively, 16 μm, 17 μm, 18 μm), which has an average particle diameter of 400 nm and a matte graft copolymer As can be seen when compared with Comparative Example 3 forming an aggregate of 0.8 μm, it was confirmed that the size of the formed aggregate is an important feature of obtaining a remarkable matt effect.

Although described in detail above with reference to the specific embodiments of the present invention, it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention, and such modifications and modifications belong to the appended claims. It is also natural.

Claims (20)

A) 20 to 50 parts by weight of a graft copolymer of an acrylate compound, an aromatic vinyl compound and a vinyl cyan compound; B) 40 to 80 parts by weight of the copolymer of the aromatic vinyl compound and the vinyl cyan compound; And C) i) at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate compound is formed by graft polymerization in an alkyl acrylate rubber polymer having an average particle diameter of 20 to 200 nm. 5 to 40 parts by weight of the matte graft copolymer, Matte thermoplastic resin composition, characterized in that the matte graft copolymer forms an aggregate of 1 to 20㎛. The method of claim 1, The graft copolymer of the acrylate compound, the aromatic vinyl compound and the vinyl cyan compound of A) is an acrylate-styrene-acrylonitrile (ASA) graft copolymer, characterized in that the matte thermoplastic resin composition. The method of claim 1, The graft copolymer of the acrylate compound, the aromatic vinyl compound and the vinyl cyan compound of A) is 15 to 55 parts by weight of the aromatic vinyl compound and 5 to 35 parts by weight of the vinyl cyan compound in 30 to 70 parts by weight of the alkyl acrylate rubber polymer. Matte thermoplastic resin composition, characterized in that the graft polymerization. The method of claim 3, wherein The at least one aromatic vinyl compound is selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene. The method of claim 3, wherein The vinyl cyan compound is a matte thermoplastic resin composition, characterized in that selected from acrylonitrile, methacrylonitrile and mixtures thereof. The method of claim 3, wherein The alkyl acrylate rubber polymer is a matte thermoplastic resin composition, characterized in that at least one selected from the group consisting of alkyl acrylate monomer having 2 to 8 carbon atoms of the alkyl group. The method of claim 3, wherein The glass transition temperature of the alkyl acrylate rubber polymer is -70 to -20 ℃ matt thermoplastic resin composition, characterized in that. The method of claim 1, In the copolymer of the aromatic vinyl compound and the vinyl cyan compound of B), the aromatic vinyl compound and the vinyl cyan compound are mixed in a weight ratio of 8: 2 to 6: 4. The method of claim 1, The aromatic vinyl compound of B) is a matte thermoplastic resin composition, characterized in that at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene and vinyl toluene. The method of claim 1, The vinyl cyan compound of B) is a matte thermoplastic resin composition, characterized in that selected from acrylonitrile, methacrylonitrile and mixtures thereof. The method of claim 1, The copolymer of the aromatic vinyl compound and the vinyl cyan compound of the above B) is a styrene-acrylonitrile copolymer, characterized in that the matt thermoplastic resin composition. The method of claim 1, Matte graft copolymer of C) is 30 to 70 parts by weight of i) alkyl acrylate rubber polymer ii) at least one monomer selected from the group consisting of aromatic vinyl compound, vinyl cyan compound and alkyl methacrylate compound 30 to 30 Matte thermoplastic resin composition, characterized in that it is prepared by graft polymerization of 70 parts by weight. The method of claim 1, The alkyl methacrylate compound of C) is a matte thermoplastic resin composition, characterized in that methyl methacrylate, ethyl methacrylate or a mixture thereof. The method of claim 1, The alkyl acrylate rubber polymer of C) is a matte thermoplastic resin composition, characterized in that at least one selected from the group consisting of alkyl acrylate monomer having 2 to 8 carbon atoms of the alkyl group. The method of claim 1, The at least one aromatic vinyl compound of C) is selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyl toluene. The method of claim 1, The vinyl cyan compound of C) is a matte thermoplastic resin composition, characterized in that selected from acrylonitrile, methacrylonitrile and mixtures thereof. The method of claim 1, Matte thermoplastic resin composition, characterized in that the graft rate of the matte graft copolymer of C) is 20% or less. The method of claim 1, Matte thermoplastic resin composition, characterized in that the weight average molecular weight of the matte graft copolymer of C) is 150,000 g / mol or more. The method of claim 1, The composition ratio of the vinyl cyan compound in the graft polymerization of the matte graft copolymer of C) has a difference of 5 parts by weight or more compared to the composition ratio of the vinyl cyan compound in the copolymer of the aromatic vinyl compound and the vinyl cyan compound of B). Matte thermoplastic resin composition, characterized in that. The method of claim 1, The thermoplastic resin composition further comprises an additive, such as a lubricant, antioxidant, ultraviolet stabilizer, dye, pigment, flame retardant or inorganic filler.