KR101056314B1 - Low gloss thermoplastic resin composition having excellent impact resistance and heat resistance - Google Patents

Abstract

More particularly, the present invention relates to a low-gloss thermoplastic resin composition comprising 30 to 70 parts by weight of (a) an ASA copolymer, (b) 5 to 20 parts by weight of a heat resistant copolymer, (c) an acrylonitrile copolymer And (d) 10 to 35 parts by weight of a SAN copolymer. The thermoplastic resin composition is excellent in impact resistance and heat resistance, and at the same time, has low gloss.

Low gloss, thermoplastic resin, ASA copolymer, heat resistant copolymer, low gloss filler, SAN copolymer, impact resistance, heat resistance

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a low-gloss thermoplastic resin composition having excellent impact resistance and heat resistance.

The present invention relates to a low-gloss thermoplastic resin composition, and more particularly, to a thermoplastic resin composition having excellent impact resistance and heat resistance, as well as excellent low-glossiness.

ABS (acrylonitrile / butadiene / styrene), MBS (methyl methacrylate / butadiene / styrene), ASA (acrylate / styrene / acrylonitrile) and AIM (acrylic impact modifier) Has excellent physical properties such as impact resistance, rigidity and fluidity and is widely used as a modifier for various plastics.

In particular, ABS resin has excellent dimensional stability, processability and chemical resistance, and is widely used as a material for monitor housings, game machine housings, home appliances, office equipment, automobile lamp housings, and the like. In recent years, studies have been made on the use of ABS as an automobile interior material by imparting heat resistance to an ABS resin excellent in impact resistance, chemical resistance and processability due to the necessity of lightening automobiles.

However, ABS resins have excellent impact resistance at low temperatures, but have a relatively low weather resistance and aging resistance.

Therefore, when it is intended to produce a product having not only high impact strength but also excellent weather resistance and aging resistance, an ethylenically unsaturated polymer should not be present in the resin. Typically, an ASA resin using a crosslinked alkyl acrylate rubber polymer is suitable Research is underway to replace it with ASA resin.

In recent years, as users' emotional quality levels have increased, there has been an increasing demand for low-gloss resins to produce a more elegant atmosphere. In addition, as environmental problems have arisen, low-gloss coating and padding have been omitted, It is a trend to use directly.

The main principle applied to manufacture such a low-gloss resin is to control the smoothness of the surface of the resin to be larger than the visible light region so that incident light is scattered to exhibit a low light effect. As a specific method, there is a method of improving the ASA resin to make large diameter rubber particles of 1 占 퐉 or larger. However, the resin produced by this method has poor low-gloss effect, and has poor impact strength and heat resistance. As another method, there is a method of adding a matting filler having a particle size of 5 mu m or more to the resin. Although the resin produced by this method shows excellent moldability, the low-glossiness is insufficient, and particularly the impact strength is significantly lowered.

As a conventional method of producing a low-gloss resin, there is a method of embossing the resin surface or coating it with a low-gloss material, but it has a problem that the processing cost is increased and the low gloss effect is lowered due to abrasion during processing.

On the other hand, conventionally, as a method for imparting heat resistance to a resin, there is a method of preparing an? -Methylstyrene-acrylonitrile heat resistant copolymer and kneading with a resin, and U.S. Patent Nos. 3,010,936 and 4,659,790 disclose a heat resistant copolymer Discloses a method for partially or entirely replacing styrene with? -Methylstyrene at the time of production. However, the resin produced by this method has a problem that the heat resistance is excellent, but the impact strength is greatly deteriorated, and the colorability is deteriorated due to the color of the heat-resistant copolymer itself. In addition, a low-gloss filler is added to exhibit low-gloss characteristics, which must also be added in large quantities in order to exhibit low-gloss characteristics, resulting in lowering impact strength and increasing production costs.

Therefore, a resin for satisfying both the impact resistance and the heat resistance as well as for imparting low gloss characteristics is required.

It is an object of the present invention to provide a thermoplastic resin composition which is excellent in impact resistance and heat resistance, and at the same time has excellent low-glossiness.

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

In order to achieve the above object,

(a) 30 to 70 parts by weight of an ASA copolymer;

(b) 5 to 20 parts by weight of a heat-resistant copolymer;

(c) 0.1 to 10 parts by weight of an acrylonitrile copolymer for a low-gloss filler; And

(d) 10 to 35 parts by weight of a SAN copolymer.

Hereinafter, the present invention will be described in detail.

When the maleimide-based copolymer is used as the heat-resistant copolymer together with the ASA resin, the present inventors have found that the maleimide-based heat-resistant copolymer has excellent heat resistance and can impart heat resistance even at a low content during kneading, It is also confirmed that the lowering of the kneading property between the matrix and the maleimide based resin is less depending on the content of the maleimide, and the maleimide based resin forms a domain between the matrix to obtain a low luster effect. .

The low-gloss thermoplastic resin composition of the present invention includes an ASA copolymer, a heat-resistant copolymer, an acrylonitrile copolymer for a low-gloss filler, and a SAN copolymer.

(a) an ASA copolymer

The ASA copolymer of the present invention comprises (i) a polymeric seed, (ii) a crosslinked alkyl acrylate core, and (iii) a graft shell.

(I) 5 to 25 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, an alkyl methacrylate compound and an alkyl acrylate compound, 0.05 to 0.3 parts by weight of an electrolyte, 0.01 to 0.5 parts by weight of a grafting agent, 0.05 to 4 parts by weight of a surfactant, 0.01 to 0.3 parts by weight of a polymerization initiator, and distilled water.

As the aromatic vinyl compound, a styrene derivative is preferably used. Specifically, styrene,? -Methylstyrene,? -Methylstyrene, vinyltoluene, or a substituent thereof may be used.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile or ethacrylonitrile may be used.

As the alkyl methacrylate compound, alkyl methacrylate having an alkyl moiety having 1 to 4 carbon atoms may be used alone or in combination of two or more. Preferably, methyl methacrylate having an alkyl moiety having 1 to 2 carbon atoms Ethyl methacrylate and the like.

As the alkyl acrylate compound, alkyl acrylates having 1 to 4 carbon atoms in the alkyl moiety may be used alone or in admixture of two or more, preferably alkyl acrylates having 4 to 8 carbon atoms in the alkyl moiety, Is to use butyl acrylate or ethylhexyl acrylate.

As the electrolyte, NaHCO ₃ , Na ₂ S ₂ O ₇ or K ₂ CO ₃ can be used, and NaHCO ₃ is preferably used.

Examples of the crosslinking agent include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl Glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, and the like can be used.

As the grafting agent, aryl methacrylate (AMA), triarylisocyanurate (TAIC), triarylamine (TAA) or diarylamine (DAA) may be used.

Examples of the surfactant include, but are not limited to, a fatty acid soap system represented by oleic acid, stearic acid, lauric acid, a sodium or potassium salt of a mixed fatty acid, or a rosin soap system represented by abietic acid salt. They may be used alone or in combination of two or more.

As the polymerization initiator, an inorganic or organic peroxide initiator may be used. Specifically, a water-soluble initiator such as potassium persulfate, sodium persulfate, or ammonium persulfate, or an initiator such as cumene hydroperoxide or benzoyl peroxide may be used have.

An activator may be used to accelerate the initiation reaction of the peroxide with the polymerization initiator. Examples of the activator include sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate or sodium pyrophosphate Sodium sulfate and the like can be used alone or in admixture of two or more, preferably 0.001 to 0.02 part by weight of sodium formaldehyde, 0.001 to 0.02 part by weight of sodium ethylenediamine tetraacetate and 0.0001 to 0.002 part by weight of ferrous sulfate .

The above components may be polymerized by emulsion polymerization alone, or by a combination of emulsion polymerization and non-emulsion polymerization. In this case, the monomers may be added either singly or in combination.

The prepared polymer seeds preferably have an average particle diameter of 150 to 400 nm.

(Ii) the crosslinked alkyl acrylate core comprises 20 to 70 parts by weight of an alkyl acrylate compound, 0.05 to 0.3 part by weight of an electrolyte, 0.1 to 1 part by weight of a crosslinking agent, 0.05 to 0.5 part by weight of a grafting agent 0.05 to 4 parts by weight of a surfactant, 0.01 to 0.3 parts by weight of a polymerization initiator, and distilled water.

The alkyl acrylate compound, the electrolyte, the crosslinking agent, the grafting agent, and the surfactant may be the same as those used in the production of the (i) polymeric seed.

The polymerization method may be the same method as used in the production of the (i) polymer seed.

The alkyl acrylate cores prepared are crosslinked alkyl acrylate rubber polymers and preferably have an eutectic temperature of less than 0 ° C, more preferably a glass transition temperature of from -20 to -70 ° C.

The crosslinked alkyl acrylate core preferably has an average particle diameter of 400 to 800 nm, more preferably 600 to 800 nm. When the average particle diameter is 400 to 800 nm, the low glossiness of the thermoplastic resin composition is improved.

(Iii) The grafted shell is prepared by blending 10 to 50 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyan compound, 0.05 to 5 parts by weight of a surfactant in the presence of (ii) 30 to 80 parts by weight (based on solids) 4 parts by weight, 0.01 to 0.3 parts by weight of a polymerization initiator, and a shell prepared by polymerizing distilled water.

The aromatic vinyl compound and the vinyl cyan compound may be used together with a third monomer such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methylmethacrylate, , Butyl acrylate, acrylic acid, or maleic anhydride can be used in small quantities.

The aromatic vinyl compound, the vinyl cyan compound, and the polymerization initiator may be the same as those used in the production of the (i) polymer seed.

The surfactant may be the same as that used in the production of the polymeric seed (i), and may be a derivative of an alkylsulfosuccinate metal salt having a pH of 3 to 9 and a carbon number of 12 to 18, an alkylsulfuric acid having a carbon number of 12 to 20 Esters, or derivatives of sulfonic acid metal salts.

Examples of the derivative of the alkyl sulfosuccinate metal salt having 12 to 18 carbon atoms include dicyclohexyl sulfosuccinate, dihexyl sulfosuccinate, di-2-ethylhexyl sulfosuccinate sodium salt, di-2-ethylhexyl sulfosuccinate sodium salt , Dioctylsulfosuccinate sodium salt or dioctylsulfosuccinate potassium salt, and the like can be used.

Examples of the alkyl sulfates or sulfonic acid metal salt derivatives having 12 to 20 carbon atoms include sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecylbenzenesulfate, sodium octadecyl sulfate, sodium oleate sulfate, potassium dodecyl sulfate Or potassium octadecyl sulfate may be used.

The polymerization method is preferably an emulsion polymerization method, and the monomer addition method is preferably a continuous introduction method. If a monomer mixture containing a surfactant is added at a time during the production of the graft shell, the pH of the polymerization system is temporarily raised to make the grafting difficult, the stability of the particles is lowered, and the internal structure of the particles is not uniform. Method is preferable.

The ASA copolymer comprising the (i) polymer seed, (ii) the crosslinked alkyl acrylate core, and (iii) graft shell, prepared as described above, is in the latex state and has a total solid content of not less than 35% by weight It is stable. In addition, the pH of the ASA copolymer latex is preferably 8 to 11, more preferably 9 to 10.5.

The latex-state ASA copolymer is formed into a powder by agglomerating, aging, dehydrating, washing, and drying with a widely known flocculant. As the coagulant, sulfuric acid, MgSO ₄ , CaCl ₂ , Al ₂ (SO ₄ ) ₃ and the like can be used, and CaCl ₂ is preferably used. The ASA copolymer latex is aged at 80 ° C at atmospheric pressure using an aqueous solution of CaCl ₂ , aged at 95 ° C, dehydrated and washed, and dried in hot air at 90 ° C for 30 minutes to prepare a powder.

The ASA copolymer is preferably contained in the low-gloss thermoplastic resin composition of the present invention in an amount of 30 to 70 parts by weight.

(b) Heat-resistant copolymer

The heat-resistant copolymer of the present invention is a copolymer produced by polymerizing at most 70 parts by weight of an aromatic vinyl compound, at most 20 parts by weight of a vinyl cyan compound and 10 to 60 parts by weight of a maleimide compound based on 100 parts by weight of the total content.

As the aromatic vinyl compound, styrene,? -Methylstyrene, p-methylstyrene or vinyltoluene may be used, and styrene is preferably used.

As the vinyl cyan compound, acrylonitrile or methacrylonitrile may be used.

The maleimide compound is not particularly limited, but it is preferable to use an N-substituted maleimide represented by the following formula (1). Specifically, there may be mentioned N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, Benzylmaleimide or N-tribromophenylmaleimide is preferably used. In consideration of transparency, low coloring property and heat resistance of the heat-resistant copolymer to be produced, N-cyclohexylmaleimide or N-phenyl Maleimide is used.

In Formula 1, R is hydrogen or an alkyl group, a cycloalkyl group, or an aryl group having 1 to 15 oxygen atoms.

The maleimide compound is preferably used in an amount of 10 to 60 parts by weight based on 100 parts by weight of the heat-resistant copolymer. When the content is 10 to 60 parts by weight, the color stability is easily controlled and the heat resistance is increased while securing polymerization stability.

The above components can be polymerized by a suspension polymerization method or a bulk polymerization method, and a suspension polymerization method is preferable in terms of the color of the heat-resistant copolymer.

The produced heat-resistant copolymer preferably has a weight-average molecular weight of 60,000 to 300,000, and the molecular weight can be controlled using a molecular weight regulator. When the weight average molecular weight is from 60,000 to 300,000, flowability is improved and workability is improved, and the impact strength of the final thermoplastic resin is improved. As the molecular weight regulator, mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan, or n-dodecyl mercaptan can be used.

The heat-resistant copolymer preferably has a glass transition temperature of 130 to 200 ° C.

It is preferable that the heat-resistant copolymer is included in the low-gloss thermoplastic resin composition of the present invention in an amount of 5 to 20 parts by weight.

(c) Acrylonitrile copolymer for low gloss filler

The acrylonitrile copolymer of the present invention is used as a low-gloss filler, and is a copolymer prepared by adding diepoxide, which is an epoxide-based electrolyte, to an acrylonitrile monomer and polymerizing.

The acrylonitrile copolymer may contain at least 5 parts by weight of an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile, or fumaronitrile based on the total amount of 100 parts by weight.

The above components may be polymerized by emulsion polymerization, bulk polymerization, suspension polymerization, bulk-suspension polymerization or solution polymerization.

The acrylonitrile copolymer is preferably included in the low-gloss thermoplastic resin composition of the present invention in an amount of 0.1 to 10 parts by weight.

(d) SAN copolymer

The SAN copolymer of the present invention is composed of a rigid polymer-forming monomer having a glass transition temperature of at least 60 DEG C of at least 60 DEG C, and may be a styrene monomer, an acrylonitrile monomer, a vinyl cyan compound, a compound containing units derived from methyl methacrylate, A compound capable of forming a carbonate polymer, and the like, or a mixture of two or more thereof.

The SAN copolymer preferably has an acrylonitrile content of 24 to 28 parts by weight and a weight average molecular weight of 80,000 to 120,000.

The SAN copolymer is preferably included in the low-gloss thermoplastic resin composition of the present invention in an amount of 10 to 35 parts by weight.

The low-gloss thermoplastic resin composition comprising the components (a) to (d) as described above may be suitably used in the form of dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, An additive such as a plasticizer or a low gloss agent.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

(a) Preparation of ASA Copolymer

(I) Polymer seed

5 parts by weight of butyl acrylate, 0.15 part by weight of NaHCO ₃ , 0.2 part by weight of potassium rosinate, and 0.1 part by weight of ethylene glycol dimethacrylate were added to a nitrogen-substituted polymerization reactor (autoclave), based on 100 parts by weight of the total monomers used in the production of the ASA copolymer. 0.05 part by weight of acrylate, 0.025 part by weight of arylmethacrylate and 60 parts by weight of distilled water were collectively added and the temperature was raised to 70 DEG C, and then 0.05 part by weight of potassium persulfate was added to initiate the reaction. The reaction was continued for 1 hour at 70 DEG C to prepare a polymer seed latex.

The average particle size of the seed latex thus prepared was 253 nm.

(Ii) Preparation of alkyl acrylate cores

45 parts by weight of butyl acrylate, 0.15 part by weight of NaHCO ₃ , 0.5 part by weight of potassium rosinate and 0.5 part by weight of potassium oleate, 0.3 part by weight of ethylene glycol dimethacrylate, 0.1 part by weight of aryl methacrylate 0.15 part by weight of distilled water, 40 parts by weight of distilled water and 0.05 part by weight of potassium persulfate was continuously added at 70 ° C for 3 hours and further polymerized for 1 hour after completion of charging to prepare an alkyl acrylate core latex.

The average particle size of the prepared core latex was 623 nm.

(Iii) Preparation of graft shell

ASA copolymer, 37.5 parts by weight of styrene, 12.5 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosinate, 1.5 parts by weight of potassium (in terms of solids) based on 100 parts by weight of total monomers used in the production of ASA copolymer, 0.05 part by weight of persulfate, 0.1 part by weight of tertiary dodecyl mercaptan and 60 parts by weight of distilled water was continuously added at 70 DEG C for 4 hours to carry out a polymerization reaction. After completion of the addition, the temperature was raised to 78 캜 so as to increase the polymerization conversion rate, and further reacted for 1 hour and cooled to 60 캜. The total solid content in the final ASA copolymer latex obtained after the completion of the reaction was 35%, and the polymerization conversion was 99.5%.

The obtained ASA copolymer latex was subjected to atmospheric pressure agglomeration at 80 ° C using CaCl ₂ aqueous solution, aged at 95 ° C, dehydrated and washed, and dried with hot air at 90 ° C for 30 minutes to obtain ASA copolymer powder particles .

(b1) Production of heat-resistant copolymer

49 parts by weight of styrene, 6 parts by weight of acrylonitrile, 0.1 part by weight of initiator 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 0.2 parts by weight of t- 0.15 part by weight of n-octylmercaptan as a molecular weight regulator and 0.05 part by weight of 2,6-di-t-butyl-p-cresol as an antioxidant were prepared. 30% of the mixed solution was added to a reactor charged with 100 parts by weight of distilled water and 2 parts by weight of a 10% sodium sulfate solution, and the mixture was stirred for 20 minutes. Thereafter, the reactor was heated to 100 DEG C for 1 hour, maintained for 20 minutes, and 2.5 parts by weight of acrylic acid and 2% 2-ethylhexyl acrylate copolymer solution as a dispersant were added thereto. From 25 minutes at 100 DEG C, 45 parts by weight of N-phenylmaleimide was dissolved in 70% of the mixed solution prepared above, and the mixture was continuously added for 3 hours and 30 minutes. After completion of the continuous addition, the mixture was kept for 30 minutes, heated to 120 DEG C for 1 hour and maintained for 3 hours, and then cooled to 40 DEG C for 1 hour. The produced product was dehydrated and dried to obtain a final heat-resistant copolymer.

The heat-resistant copolymer produced had a weight average molecular weight of 150,000 and a glass transition temperature of 175 占 폚.

(b2) Production of heat resistant copolymer

(B1) Heat-resistant copolymer (b1) was prepared in the same manner as in the above (b1) except for using 35 parts by weight instead of 49 parts by weight of styrene, 5 parts by weight instead of 6 parts by weight of acrylonitrile and 60 parts by weight of phenylmaleimide Was carried out in the same manner as in the preparation of the copolymer.

The heat-resistant copolymer produced had a weight average molecular weight of 160,000 and a glass transition temperature of 197 ° C.

(c) acrylonitrile copolymer for low-gloss filler

As the acrylonitrile copolymer for the low-gloss filler, an acrylonitrile resin nonmat (B MAT, GE Co.), which is light yellow powder not containing butadiene, was used.

(d) SAN copolymer

As the SAN copolymer, a styrene-acrylonitrile copolymer (81HR, manufactured by LG Chemical) was used.

≪ Preparation of Low Gloss Thermoplastic Resin Composition >

Example 1

40 parts by weight of the ASA copolymer (a), 10 parts by weight of the heat-resistant copolymer (b1), 5 parts by weight of the acrylonitrile copolymer, and 50 parts by weight of the SAN copolymer (d) 1 part by weight of the lubricant and 0.5 part by weight of the antioxidant were added and then pelletized using a 40 pie extrusion kneader at a cylinder temperature of 220 DEG C and the pellets were injected to prepare physical specimens.

Example 2, Comparative Examples 1 to 3

The procedure of Example 1 was repeated, except that components (a) to (d) were added in the same manner as in Table 1.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (a) an ASA copolymer 40 40 40 40 40 (b) Heat-resistant copolymer b1 10 - - - 30 b2 - 7 - - - (c) acrylonitrile copolymer 5 5 5 10 5 (d) SAN copolymer 50 53 60 60 30 Lubricant One One One One One Antioxidant 0.5 0.5 0.5 0.5 0.5

[Test Example]

The properties of the thermoplastic resin composition specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 2 below.

* Impact strength (1/4 "notched at 23 ° C, kg · cm / cm) - Measured according to ASTM D256.

Tensile strength (kg / cm ² ) - Measured according to ASTM D638.

Flowability (g / cm ² ) - Measured according to ASTM D1238.

* Thermal deformation temperature (1/4 ", 캜) - Measured according to ASTM D648.

* Glossiness (45 DEG) - Measured according to ASTM D523.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength
(1/4 ", kg · cm / cm) 10.3 10.7 10.8 7.4 5.7 Tensile strength (kg / cm ² ) 452 447 445 473 482 Flowability (g / cm ² ) 15.7 15.9 20.3 19.7 8.3 Heat distortion temperature
(1/4 ", ° C) 91 90 85 85 98 Glossiness (45 °) 12 14 20 13 12

As shown in Table 1 above, it was confirmed that the low-gloss thermoplastic resin compositions of Examples 1 and 2 prepared according to the present invention had excellent impact resistance and heat resistance, and excellent low-gloss effect.

On the other hand, Comparative Example 1, which did not contain a heat-resistant copolymer, exhibited reduced heat resistance, increased gloss and lowered low-gloss characteristics, and Comparative Example 2, which contained an excess of acrylonitrile copolymer for low- , The low-gloss effect was improved, but the impact strength was lowered. In addition, Comparative Example 3 containing an excess of the heat-resistant copolymer showed excellent heat resistance, but it was confirmed that the fluidity and impact resistance were lowered.

INDUSTRIAL APPLICABILITY As described above, the present invention provides a thermoplastic resin composition having excellent impact resistance and heat resistance, as well as excellent low-glossiness.

Claims (12)

(a) 30 to 70 parts by weight of an ASA copolymer; (b) 5 to 20 parts by weight of a maleimide-based copolymer; (c) 0.1 to 10 parts by weight of an acrylonitrile copolymer for a low-gloss filler; And (d) 10 to 35 parts by weight of a SAN copolymer, Wherein the SAN copolymer has an acrylonitrile content of 24 to 28 parts by weight and a weight average molecular weight of 80,000 to 120,000 Low gloss thermoplastic resin composition. The method according to claim 1, The (a) ASA copolymer is (I) 5 to 25 parts by weight of at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, alkyl methacrylate compounds and alkyl acrylate compounds, 0.05 to 0.3 parts by weight of an electrolyte, 0.01 to 0.5 parts by weight of a crosslinking agent 0.01 to 0.5 parts by weight of a grafting agent, 0.05 to 4 parts by weight of a surfactant, 0.01 to 0.3 parts by weight of a polymerization initiator, and a polymeric seed prepared by polymerizing distilled water;  (Ii) 20 to 70 parts by weight of an alkyl acrylate compound, 0.05 to 0.3 part by weight of an electrolyte, 0.1 to 1 part by weight of a crosslinking agent, 0.05 to 0.5 part by weight of a grafting agent, 0.05 to 4 parts by weight of a surfactant 0.01 to 0.3 parts by weight of a polymerization initiator, and a crosslinked alkyl acrylate core prepared by polymerizing distilled water; And (Iii) 10 to 50 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyan compound, 0.05 to 4 parts by weight of a surfactant in the presence of 30 to 80 parts by weight (based on solids) of the (ii) alkyl acrylate core, 0.01 to 0.3 parts by weight of an initiator, and a graft shell prepared by polymerizing distilled water Low gloss thermoplastic resin composition. 3. The method of claim 2, (I) the polymer seed has an average particle diameter of 150 to 400 nm Low gloss thermoplastic resin composition. 3. The method of claim 2, (Ii) the crosslinked alkyl acrylate core has a glass transition temperature of less than 0 DEG C and an average particle diameter of 400 to 800 nm Low gloss thermoplastic resin composition. 3. The method according to claim 1 or 2, Wherein the ASA copolymer has a pH of 8 to 11 Low gloss thermoplastic resin composition. delete delete The method according to claim 1, The heat-resistant copolymer (b) has a weight-average molecular weight of 60,000 to 300,000 and a glass transition temperature of 130 to 200 ° C. Low gloss thermoplastic resin composition. The method according to claim 1, The acrylonitrile-based copolymer for the low-gloss filler (c) is prepared by adding diepoxide, which is an epoxide-based electrolyte, to an acrylonitrile monomer and polymerizing Low gloss thermoplastic resin composition. The method according to claim 1, The (d) SAN copolymer is prepared by polymerizing a hard polymer-forming monomer having a glass transition temperature of at least 60 ° C Low gloss thermoplastic resin composition. delete The method according to claim 1, The low gloss thermoplastic resin composition further comprises at least one additive selected from the group consisting of dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers, doing Low gloss thermoplastic resin composition.