KR100988999B1 - Acrylate-styrene-acrylonitrile polymer, method of preparing the same and thermoplastic resin composition containing the same - Google Patents

Abstract

The present invention relates to an acrylate-styrene-acrylonitrile polymer, a method for preparing the same, and a thermoplastic resin composition comprising the same, and more particularly, to an alkylacrylate rubber core having an average particle diameter of 100 to 800 nm prepared by emulsion polymerization. An acrylate-styrene-acrylonitrile polymer comprising latex and crosslinked acrylate-styrene-acrylonitrile particles having an average particle diameter of 1 to 1000 μm prepared by suspension polymerization, including the acrylate rubber core latex, It relates to a preparation method thereof and a thermoplastic resin composition comprising the same.

According to the present invention is excellent in the matt effect when applied to the thermoplastic resin composition, there is an effect of providing an acrylate-styrene-acrylonitrile polymer having excellent weather resistance and impact resistance, a method for producing the same and a thermoplastic resin composition comprising the same.

Emulsion polymerization, suspension polymerization, acrylate-styrene-acrylonitrile, crosslinking, matte, impact resistance, weather resistance

Description

ACRYLATE-STYRENE-ACRYLONITRILE POLYMER, METHOD OF PREPARING THE SAME AND THERMOPLASTIC RESIN COMPOSITION CONTAINING THE SAME}

The present invention relates to an acrylate-styrene-acrylonitrile polymer, a method for preparing the same, and a thermoplastic resin composition comprising the same, and more particularly, to an acrylate having excellent matt effect when applied to the thermoplastic resin composition, and having excellent weather resistance and impact resistance. It relates to a styrene-acrylonitrile polymer, a preparation method thereof and a thermoplastic resin composition comprising the same.

Generally, acrylonitrile-butadiene-styrene (ABS) resins prepared by graft copolymerization of styrene and acrylonitrile monomers on butadiene-based rubbery polymers have impact resistance, processability, beautiful appearance, excellent mechanical strength, And it has high characteristics such as heat deformation temperature and is used for various applications such as automotive parts, electrical and electronic products, building materials.

However, because ABS resin has ethylenically unsaturated polymer in butadiene rubber used as impact modifier, it is easily oxidized by ultraviolet rays, light and heat in the presence of oxygen, so that the resin's appearance and color change and mechanical properties are deteriorated. There is a problem that it is not suitable for outdoor materials.

Therefore, acrylonitrile-styrene-acrylate, which uses acrylic rubber which does not have ethylenically unsaturated polymer instead of butadiene rubber as an impact modifier, in order to obtain a thermoplastic resin having excellent physical properties and excellent weatherability and aging resistance, ASA) terpolymer copolymer resin is used. Such ASA resins are used in various fields such as electronic and electric parts, construction materials, automobiles, ships, leisure goods, horticulture, etc. which are used outdoors. Among them, in the fields of automobile interior parts and building materials for homes, a matte material whose surface gloss is suppressed is demanded, and various studies on the production of matte resins have been conducted.

Conventional methods for producing a matte resin include embossing the surface of the resin or coating with a low gloss material. However, these methods increase the processing cost, there is a problem that the matte effect is reduced by the wear at the time of processing.

U. S. Patent No. 4,612, 347 discloses an acidic and basic graft copolymer, but the yield of condensation reaction is lowered and there is a problem of reproducibility. However, there is a problem that the gloss of the resin surface is not uniform. In addition, there is disclosed a matt appearance molded article comprising a rubber polymer having a μm size by using a matting agent or by suspension polymerization, there is a problem that the impact is not good enough.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide an acrylate-styrene-acrylonitrile polymer having excellent matting effect as well as excellent weather resistance and impact resistance when applied to a thermoplastic resin composition.

Another object of the present invention is to provide a method for producing the acrylate-styrene-acrylonitrile polymer.

Moreover, an object of this invention is to provide the thermoplastic resin composition containing the said acrylate- styrene- acrylonitrile polymer.

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,

Based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer,

(a) 1 to 20 parts by weight of an alkyl acrylate rubber seed formed by emulsion polymerization;

(b) a rubber core surrounding the rubber seed and having an average particle size of 100 to 800 nm formed by emulsion polymerization of 5 to 30 parts by weight of alkyl acrylate; And

(c) 50 to 90 parts by weight of an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate, 0.01 to 3 parts by weight of a crosslinking agent and 0.01 to 3 parts by weight of a grafting agent. Crosslinked acrylate-styrene-acrylonitrile particles having an average particle diameter of 1 to 1000 μm formed by addition suspension polymerization

It provides an acrylate-styrene-acrylonitrile polymer comprising a.

Also,

Based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer,

(a) preparing a rubber seed by emulsion polymerization of 1 to 20 parts by weight of alkyl acrylate;

(b) preparing a rubber core having an average particle diameter of 100 to 800 nm by emulsion polymerization of 5 to 30 parts by weight of alkyl acrylate in the presence of the rubber seed; And

(c) 50 to 90 parts by weight of aromatic vinyl compound and vinyl cyan compound, or aromatic vinyl compound, vinyl cyan compound and alkyl methacrylate, 0.01 to 3 parts by weight of crosslinking agent, and 0.01 to 3 grafting agent in the presence of the rubber core Preparing a crosslinked acrylate-styrene-acrylonitrile particle having an average particle diameter of 1 to 1000 mu m by suspension polymerization by weight part.

It provides a method for producing an acrylate-styrene-acrylonitrile polymer comprising a.

Also,

Thermoplastic resin composition comprising 0.1 to 40 parts by weight of the acrylate-styrene-acrylonitrile polymer according to the present invention, 20 to 60 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer and 40 to 80 parts by weight of the hard matrix resin. To provide.

According to the present invention, by preparing an emulsion-based rubber core latex of nm size and then preparing a micron-sized crosslinked acrylate-styrene-acrylonitrile polymer by suspension polymerization, the flocculation, aging, Simplifies the complex process of dehydration and drying, while having excellent matt effect due to surface light scattering of the copolymer of μm size when applied to the thermoplastic resin composition, and excellent impact by acrylate-styrene of nm size rubber included in the copolymer -There is an effect of providing an acrylonitrile polymer, a method for producing the same and a thermoplastic resin composition comprising the same.

Hereinafter, the present invention will be described in detail.

The acrylate-styrene-acrylonitrile polymer of the present invention is (a) 1 to 20 parts by weight of an alkyl acrylate based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer Rubber seeds formed; (b) a rubber core surrounding the rubber seed and having an average particle size of 100 to 800 nm formed by emulsion polymerization of 5 to 30 parts by weight of alkyl acrylate; And (c) the rubber core, comprising 50 to 90 parts by weight of an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate, 0.01 to 3 parts by weight of a crosslinking agent, and 0.01 to 3 parts by weight of a grafting agent. 3 parts by weight includes crosslinked acrylate-styrene-acrylonitrile particles having an average particle diameter of 1 to 1000 mu m formed by suspension polymerization.

The acrylate-styrene-acrylonitrile polymer of the present invention preferably includes an alkyl acrylate rubber polymer core having an average particle diameter of 100 to 800 nm, and the impact is sharply reduced when the alkyl acrylate rubber polymer core is not included. do.

In addition, it is preferable that the average particle diameter of the acrylate-styrene-acrylonitrile polymer of the present invention is 1 to 1000 μm, and when the particle size is 1 μm or less, sufficient matting effect is not achieved and the impact is poor when the particle size is 1000 μm or more. There is.

In addition, the acrylate-styrene-acrylonitrile polymer of the present invention is preferably crosslinked. By appropriately crosslinking the aromatic vinyl compound and the vinyl cyan compound, or the aromatic vinyl compound, the vinyl cyan compound and the alkyl methacrylate, light scattering occurs on the surface of the copolymer, resulting in a matt effect.

The method for producing the acrylate-styrene-acrylonitrile polymer of the present invention is based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer, (a) 1 to 20 parts by weight of alkyl acrylate. Preparing a rubber seed by emulsion polymerization; (b) preparing a rubber core having an average particle diameter of 100 to 800 nm by emulsion polymerization of 5 to 30 parts by weight of alkyl acrylate in the presence of the rubber seed; And (c) 50 to 90 parts by weight of an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate in the presence of the rubber core, 0.01 to 3 parts by weight of a crosslinking agent, and 0.01 to 3 parts by weight of a grafting agent. Suspending polymerization of 3 parts by weight to prepare crosslinked acrylate-styrene-acrylonitrile particles having an average particle diameter of 1 to 1000 μm.

More specifically, based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer,

(a) 1 to 20 parts by weight of alkyl acrylate monomer, 0.001 to 1 part by weight of electrolyte, 0.01 to 3 parts by weight of crosslinking agent, 0.01 to 3 parts by weight of grafting agent, 0.01 to 3 parts by weight of polymerization initiator, and 0.001 to 3 parts by weight of emulsifier Preparing a rubber seed by emulsion polymerization;

(b) 5 to 30 parts by weight of an alkyl acrylate monomer, 0.01 to 3 parts by weight of crosslinking agent, 0.01 to 3 parts by weight of grafting agent, 0.01 to 3 parts by weight of polymerization initiator, and 0.01 to 5 parts by weight of emulsifier Producing an alkylacrylate rubber core having an average particle diameter of 100 to 800 nm surrounding the seed by polymerization;

 (c) 50 to 90 parts by weight of an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate monomer, 0.01 to 3 parts by weight of a crosslinking agent, and a grafting agent in the prepared alkyl acrylate rubber core After dispersing 0.01 to 3 parts by weight, adding 0.01 to 10 parts by weight of a flocculant, and then suspending polymerization of 0.01 to 7 parts by weight of the polymerization initiator and 0.01 to 10 parts by weight of the dispersion stabilizer to obtain an average of the alkyl acrylate rubber core having the nm size. Preparing a crosslinked acrylate-styrene-acrylonitrile polymer having a particle diameter of 1 to 1000 μm.

The alkyl acrylate of the steps (a) and (b) may be used alone or a mixture of two or more of those having 2 to 8 carbon atoms in the alkyl portion, preferably 4 to 8 carbon atoms in the alkyl portion, more Preferably, butyl acrylate, ethyl acrylate or ethyl hexyl acrylate is used.

As the aromatic vinyl compound of step (c), styrene or a derivative thereof is preferably used, and specifically, styrene, α-methylstyrene, p-methylstyrene, or vinyltoluene may be used alone or in combination of two or more thereof. .

In addition, the vinyl cyan compound of step (c) may be used alone or in combination of two or more acrylonitrile, methacrylonitrile or ethacrylonitrile.

In addition, the alkyl methacrylate of the step (c) may be used by mixing two or more kinds of the alkyl portion of 1 to 4 carbon atoms, preferably methyl methacrylate having 1 to 2 carbon atoms of the alkyl portion or Ethyl methacrylate etc. are used.

The electrolyte used in step (a) is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , Na ₂ S ₂ O ₇ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ or Na ₂ HPO ₄ may be used alone or in combination of two or more thereof.

The crosslinking agent used in steps (a), (b) and (c) is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate , 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane trimethacrylate or trimethylol methane triacrylate and the like are preferably used.

The grafting agent used in steps (a), (b) and (c) is allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallyl amine (TAA) or diallyl amine (DAA) It is preferable to use etc.

The initiator used in the steps (a) and (b) may be a water-soluble initiator such as sodium persulfate, potassium persulfate or ammonium persulfate; Oil-soluble initiators such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobisisobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide; Or a redox-based polymerization initiator in which an oxidation-reducing agent is combined.

An activator may be used to promote the initiation reaction of the peroxide together with the initiator used in steps (a) and (b), and the activator may be sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, and sulfate 1 It is preferable to use iron, dextrose, sodium pyrrolate or sodium sulfite alone or in mixture of two or more thereof.

The emulsifiers used in the above (a) and (b) are not particularly limited in kind, derivatives of alkyl sulfo succinate metal salts; Derivatives of alkyl sulfate esters or sulfonic acid metal salts; Or an emulsifier of a fatty acid soap system or a rosin acid soap system.

The flocculant used in the step (c) is an aqueous solution of an inorganic salt such as aluminum chloride, sodium sulfate, sodium nitrate, calcium chloride, magnesium sulfate or aluminum sulfate; Or an aqueous solution of a flocculant such as sulfuric acid or hydrochloric acid.

The initiator used in the step (c) is a peroxide such as benzoyl peroxide or lauroyl peroxide; Or azo compounds such as azobisisobutylonitrile.

The dispersion stabilizer used in step (c) is starch, gelatin, polyacrylamide, polyvinyl alcohol, polyunsaturated polyvinyl alcohol, polyunsaturated polymethyl methacrylate, polyacrylic acid and salts thereof, cellulose, methylcellulose, hydroxy Natural and synthetic polymer dispersants such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyalkylene oxide, polyvinylpyrrolidone, polyvinylimidazole or sulfonated polystyrene; Alternatively, inorganic dispersants such as magnesium carbonate, calcium carbonate, barium carbonate, barium sulfate, calcium sulfate, tricalcium phosphate or hydroapatite may be used alone or in combination of two or more thereof.

In addition to the above components, mercaptans molecular weight modifiers may be further used in preparing the acrylate-styrene-acrylonitrile polymer.

In the step of preparing the rubber seed and the core of (a) and (b), the batch and continuous dosing method may be used alone or as a mixture of the two methods as a monomer input method.

In preparing the acrylate-styrene-acrylonitrile particles crosslinked by the suspension polymerization of (c), when the flocculant is added in a batch, the stability is drastically lowered to form a coagulated product, and thus it is preferable to use the continuous injection method.

0.1 to 40 parts by weight of the powdered crosslinked acrylate-styrene-acrylonitrile polymer prepared according to the present invention, 20 to 60 parts by weight of acrylate-styrene-acrylonitrile graft copolymer and hard matrix resin 40 To 80 parts by weight may be mixed to prepare a thermoplastic resin composition.

The acrylate-styrene-acrylonitrile graft copolymer has a core-shell structure, is a graft copolymer capable of melt kneading with a hard matrix resin, and preferably has an average particle diameter of 0.1 to 0.6 µm.

The hard matrix resin is composed of a hard polymer-forming monomer having a glass transition temperature of at least 60 ° C. or higher, and an aromatic vinyl compound, a vinyl cyan compound, a compound including a unit derived from methyl methacrylate, and a compound capable of forming a polycarbonate polymer. It is preferable that it is manufactured by mixing single or 2 types or more.

The thermoplastic resin composition may further include additives such as dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers, or matting agents, which are commonly used according to uses.

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

<Acrylic-styrene-acrylonitrile polymer preparation>

1. Preparation of nm butyl acrylate rubber by emulsion polymerization

40 parts by weight of distilled water, 5 parts by weight of butyl acrylate, 0.02 parts by weight of sodium carbonate, ethylene glycol dimethacryl based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer in the nitrogen-substituted polymerization reactor. 0.05 parts by weight of rate, 0.05 parts by weight of allyl methacrylate, and 0.01 parts by weight of sodium lauryl sulfate were collectively administered, and the temperature was raised to 70 ° C. Then, 0.03 parts by weight of potassium persulfate was added to initiate the reaction. After the reaction for 3 hours at 70 ℃ to prepare a rubber seed.

In the presence of the rubber seed latex prepared above, 20 parts by weight of distilled water, 15 parts by weight of butylacrylate, 0.1 parts by weight of ethylene glycol dimethacrylate, 0.1 part by weight of allyl methacrylate, 0.18 parts by weight of potassium persulfate and sodium lauryl sulfate A mixture of 0.18 parts by weight was continuously added at 75 ° C. to prepare a rubber core having an average particle diameter of 350 nm.

2. Preparation of Acrylate-Styrene-Acrylonitrile Polymers of μm Size by Suspension Polymerization

Calcium chloride with stirring 150 parts by weight of distilled water, 54 parts by weight of styrene, 20 parts by weight of acrylonitrile, 0.1 parts by weight of ethylene glycol dimethacrylate and 0.1 parts by weight of allyl methacrylate in the presence of the prepared nm-size rubber core latex After dropping 60 parts by weight (2 wt%) for 2 hours, 0.45 parts by weight of benzoyl peroxide, 6 parts by weight of styrene, and 0.45 parts by weight of polyvinyl alcohol were mixed, and the polymerization was carried out at 85 ° C. for 7 hours. An acrylate-styrene-acrylonitrile polymer particle having 100 μm was obtained.

<Production of the thermoplastic resin composition>

5 parts by weight of the prepared acrylate-styrene-acrylonitrile polymer powder, 40 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer SA927 (manufactured by LG Chemical) and styrene-acrylonitrile in a hard matrix. To 60 parts by weight of copolymer 81HF (manufactured by LG Chemical), 1 part by weight of lubricant, 0.5 part by weight of antioxidant and 0.5 part by weight of UV stabilizer were added and mixed. This was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and injected into the pellet to prepare a physical specimen.

Example  2

In preparing the rubber seed in Example 1, 0.1 parts by weight instead of 0.01 parts by weight of sodium lauryl sulfate was used in the same manner as in Example 1 except that a rubber core having an average particle diameter of 200 nm was manufactured.

Example  3

In preparing the acrylate-styrene-acrylonitrile having a size of μm in Example 1, 0.8 parts by weight instead of 0.45 parts of polyvinyl alcohol was used to prepare acrylate-styrene-acrylonitrile polymer particles having an average particle diameter of 50 μm. The same procedure as in Example 1 was conducted except for the one.

Example  4

Acrylate-styrene-acrylonitrile polymer particles having an average particle diameter of 50 μm using 1 part by weight of apatite hydroxide instead of 0.45 part by weight of polyvinyl alcohol when preparing the acrylate-styrene-acrylonitrile having a size of μm in Example 1 Except that was prepared in the same manner as in Example 1.

Example  5

When preparing the thermoplastic resin composition in Example 1, it was carried out in the same manner as in Example 1 except that 8 parts by weight instead of 5 parts by weight of the prepared acrylate-styrene-acrylonitrile polymer powder. It was.

Comparative example  One

<Acrylic-styrene-acrylonitrile polymer preparation>

1. Preparation of Butyl Acrylate Rubber Seed by Emulsion Polymerization

40 parts by weight of distilled water, 5 parts by weight of butylacrylate, 0.02 parts by weight of sodium carbonate, ethylene glycol dimeth, based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer in the nitrogen-substituted polymerization reactor. 0.05 part by weight of acrylate, 0.1 part by weight of allyl methacrylate, and 0.01 part by weight of sodium lauryl sulfate were collectively administered, and the temperature was raised to 70 ° C. Then, 0.03 part by weight of potassium persulfate was added to initiate the reaction. After the reaction for 3 hours at 70 ℃ to prepare a rubber seed.

2. Preparation of Acrylate-Styrene-Acrylonitrile Polymers of μm Size by Suspension Polymerization

In the presence of the prepared rubber seed latex, 187 parts by weight of distilled water, 75 parts by weight of styrene and 25 parts by weight of acrylonitrile, 0.125 parts by weight of ethylene glycol dimethacrylate and 0.125 parts by weight of allyl methacrylate, 0.563 weight of benzoylperoxide Part and 0.6 parts by weight of polyvinyl alcohol were mixed and polymerized at 85 ° C. for 8 hours to obtain acrylate-styrene-acrylonitrile polymer particles having an average particle diameter of 100 μm.

<Production of the thermoplastic resin composition>

5 parts by weight of the prepared acrylate-styrene-acrylonitrile polymer powder, 40 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer SA927 (manufactured by LG Chemical) and styrene-acrylonitrile in a hard matrix. To 60 parts by weight of copolymer 81HF (manufactured by LG Chemical), 1 part by weight of lubricant, 0.5 part by weight of antioxidant and 0.5 part by weight of UV stabilizer were added and mixed. This was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and injected into the pellet to prepare a physical specimen.

Comparative example  2

In preparing the thermoplastic resin composition in Example 1, except that 5 parts by weight of the matte agent was used instead of 5 parts by weight of the prepared acrylate-styrene-acrylonitrile polymer powder in the same manner as in Example 1 Was carried out.

Comparative example  3

Except for the use of 0 parts by weight instead of 0.1 parts by weight of ethylene glycol dimethacrylate and 0.1 parts by weight of allyl methacrylate in preparing the acrylate-styrene-acrylonitrile having a size of μm in Example 1 It carried out in the same manner as in Example 1.

[Test Example]

The physical properties of the thermoplastic resin compositions prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were measured by the following methods, and the results are shown in Table 1 below.

* Glossiness (75 °)-measured according to ASTM D528.

* Izod impact strength (1/4 notched at 23 ° C., kg · cm / cm)-measured in accordance with ASTM D256.

division Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Glossiness 20.7 21.3 24.8 21.2 17.8 23.1 42.1 82.5 Impact strength
(Kgcm / cm) 19.2 15.2 20.4 18.9 16.8 5.8 7.6 21.6

As shown in Table 1, the thermoplastic resin compositions of Examples 1 to 5 including the acrylate-styrene-acrylonitrile polymer having a size of μm according to the present invention was confirmed that the matte properties and excellent impact resistance. .

In contrast, the thermoplastic resin composition of Comparative Example 1 comprising a styrene-acrylonitrile polymer having a 탆 size without containing butyl acrylate rubber and a comparative example using a matting agent instead of the acrylate-styrene-acrylonitrile polymer having a 탆 size The thermoplastic resin composition of 2 exhibited a slight matte property, but the impact resistance was lowered. Could be confirmed.

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)

Based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer, (a) 1 to 20 parts by weight of an alkyl acrylate rubber seed formed by emulsion polymerization; (b) a rubber core surrounding the rubber seed and having an average particle size of 100 to 800 nm formed by emulsion polymerization of 5 to 30 parts by weight of alkyl acrylate; And (c) 50 to 90 parts by weight of an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate, a crosslinking agent of 0.01 to 3 parts by weight, and a grafting agent of 0.01 to 3, including the rubber core Crosslinked acrylate-styrene acrylonitrile (ASA) particles having an average particle diameter of 1 to 1000 µm formed by suspension polymerization by weight part; Containing Acrylate-styrene-acrylonitrile polymer. The method of claim 1, The alkyl acrylate is an acrylate-styrene-acrylonitrile polymer, characterized in that the alkyl having 2 to 8 carbon atoms alone or in combination of two or more. The method of claim 1, The aromatic vinyl compound is an acrylate-styrene-acrylonitrile polymer, characterized in that styrene, α-methylstyrene, p-methylstyrene or vinyltoluene are used alone or in combination of two or more thereof. The method of claim 1, The vinyl cyan compound is an acrylate-styrene-acrylonitrile polymer, characterized in that acrylonitrile, methacrylonitrile or ethacrylonitrile is used alone or in combination of two or more thereof. The method of claim 1, The alkyl methacrylate is an acrylate-styrene-acrylonitrile polymer, characterized in that alkyl is used alone or in combination of two or more carbon atoms of 1 to 4. Based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer, (a) preparing a rubber seed by emulsion polymerization of 1 to 20 parts by weight of alkyl acrylate; (b) preparing a rubber core having an average particle diameter of 100 to 800 nm by emulsion polymerization of 5 to 30 parts by weight of alkyl acrylate in the presence of the rubber seed; And (c) 50 to 90 parts by weight of an aromatic vinyl compound and a vinyl cyan compound, or an aromatic vinyl compound, a vinyl cyan compound and an alkyl methacrylate, a crosslinking agent of 0.01 to 3 parts by weight, and a grafting agent of 0.01 to 3, including the rubber core Preparing cross-linked acrylate-styrene-acrylonitrile (ASA) particles having an average particle diameter of 1 to 1000 μm formed by suspension polymerization by weight part; Method for producing an acrylate-styrene-acrylonitrile polymer comprising a. The method of claim 6, The alkyl acrylate is characterized in that the alkyl having 2 to 8 carbon atoms alone or in combination of two or more, The aromatic vinyl compound is characterized in that styrene, α-methylstyrene, p-methylstyrene or vinyl toluene is used alone or in combination of two or more, The vinyl cyan compound is characterized in that acrylonitrile, methacrylonitrile or ethacrylonitrile is used alone or in combination of two or more thereof, The alkyl methacrylate is characterized in that the alkyl having 1 to 4 carbon atoms alone or in mixture of two or more kinds Process for the preparation of acrylate-styrene-acrylonitrile polymer. The method of claim 6, The rubber seed of (a) is 0.001 to 1 parts by weight of the electrolyte, 0.01 to 3 parts by weight of the crosslinking agent, and 0.01 to 3 parts by weight of the grafting agent based on 100 parts by weight of the total monomers used to prepare the acrylate-styrene-acrylonitrile polymer. , 0.01 to 3 parts by weight of initiator and 0.001 to 3 parts by weight of emulsifier are further included to polymerize the acrylate-styrene-acrylonitrile polymer. The method of claim 6, The rubber core of (b) is 0.01 to 3 parts by weight of the crosslinking agent, 0.01 to 3 parts by weight of the grafting agent, 0.01 to 3 parts by weight of the initiator with respect to 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile polymer Part and 0.01 to 5 parts by weight of an emulsifier are further included to polymerize the acrylate-styrene-acrylonitrile polymer. The method of claim 6, The crosslinked acrylate-styrene-acrylonitrile particles of (c) are 0.01 to 10 parts by weight of a flocculant, and 0.01 to 7 initiators based on 100 parts by weight of the total monomers used to prepare the acrylate-styrene-acrylonitrile polymer. A method for producing an acrylate-styrene-acrylonitrile polymer, characterized in that the suspension polymerization is further included by weight and 0.01 to 10 parts by weight of the dispersion stabilizer. The method of claim 8, The electrolyte is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , Na ₂ S ₂ O ₇ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ A method for producing an acrylate-styrene-acrylonitrile polymer, characterized in that PO ₄ , K ₂ HPO ₄ or Na ₂ HPO ₄ is used alone or in combination of two or more thereof. The method according to any one of claims 6, 8 and 9, The crosslinking agent is ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol It is characterized by using dimethacrylate, trimethylol propane trimethacrylate or trimethylol methane triacrylate, The grafting agent is characterized by using allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallyl amine (TAA) or diallyl amine (DAA). Process for the preparation of acrylate-styrene-acrylonitrile polymer. The method according to claim 8 or 9, The initiator may be a water-soluble initiator of sodium persulfate, potassium persulfate or ammonium persulfate; Oil-soluble initiators of cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobisisobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide or benzoyl peroxide; Or using a redox-based polymerization initiator in combination with an oxidation-reducing agent, The emulsifier may be a derivative of an alkyl sulfo succinate metal salt, an alkyl sulfate ester or a sulfonic acid metal salt derivative, or a fatty acid soap-based or rosin-acid soap-based emulsifier. Way. The method according to claim 8 or 9, Step (a) or (b) further comprises an activator for promoting the initiation reaction, The activator is characterized in that sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrroline or sodium sulfite is used alone or in combination of two or more thereof Process for the preparation of acrylate-styrene-acrylonitrile polymer. The method of claim 10, The flocculant is characterized by using an aqueous solution of an inorganic salt of aluminum chloride, sodium sulfate, sodium nitrate, calcium chloride, magnesium sulfate or aluminum sulfate, or an aqueous solution of sulfuric acid or hydrochloric acid, The initiator is characterized in that using a peroxide of benzoyl peroxide, lauroyl peroxide, or an azo compound of azobisisobutylonitrile, The dispersion stabilizer is starch, gelatin, polyacrylamide, polyvinyl alcohol, partially unsaturated polyvinyl alcohol, partially unsaturated polymethacrylate, polyacrylic acid and salts thereof, cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose Natural and synthetic polymeric dispersants of hydroxypropylcellulose, polyalkylene oxide, polyvinylpyrrolidone, polyvinylimidazole or sulfonated polystyrene; Or an inorganic dispersant of magnesium carbonate, calcium carbonate, barium carbonate, barium sulfate, calcium sulfate, tricalcium phosphate, or hydroapatite, alone or in combination of two or more thereof. Process for the preparation of acrylate-styrene-acrylonitrile polymer. The method of claim 6, The alkyl acrylate of step (a) and (b) is a method for producing an acrylate-styrene-acrylonitrile polymer, characterized in that the batch method, the continuous method or a mixture of the two methods for the polymerization. The method of claim 10, The flocculant is a method of producing an acrylate-styrene-acrylonitrile polymer, characterized in that the input to the continuous injection method for polymerization. Thermoplastic resin comprising 0.1 to 40 parts by weight of the acrylate-styrene-acrylonitrile polymer according to claim 1, 20 to 60 parts by weight of the acrylate-styrene-acrylonitrile graft copolymer and 40 to 80 parts by weight of the hard matrix resin. Composition. The method of claim 18, The acrylate-styrene-acrylonitrile graft copolymer is a thermoplastic resin composition, characterized in that the average particle diameter of 0.1 to 0.6 ㎛. The method of claim 18, The hard matrix resin is a thermoplastic resin, which is prepared by mixing an aromatic vinyl compound, a vinyl cyan compound, a compound including a unit derived from methyl methacrylate, and a compound capable of forming a polycarbonate polymer, alone or in combination of two or more thereof. Composition.