KR20140046757A - Method of preparing alkyl acrylate-vinyl aromatic compound-vinylcyan compound copolymer and thermoplastic resin composition comprising the same having excellent impact strength - Google Patents

Abstract

The present invention relates to an alkyl acrylate-vinyl aromatic compound-vinyl cyanide compound copolymer wherein the alkyl acrylate-vinyl aromatic compound-vinyl cyanide compound copolymer is produced with the use of a polyalkylene-based crosslinking agent of polyethylene glycol diacrylate or polyethylene glycol dimethacrylate in a shell portion of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide compound copolymer, and the same is applied in a thermoplastic resin composition to exhibit an effect whereby the impact strength of the resin is improved; and the present invention also relates to a thermoplastic resin composition comprising the copolymer.

Description

Method of preparing alkyl acrylate-vinyl aromatic compound-vinylcyan compound copolymer and thermoplastic resin composition comprising the same having excellent impact strength}

The present invention relates to a method for producing an alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer and a thermoplastic resin composition comprising the same, and more particularly, to an acrylate-styrene using a polyethylene-based crosslinking agent in the shell portion of the copolymer. A method for producing an alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer and a thermoplastic comprising the same, by preparing an acrylonitrile copolymer and applying the same to a thermoplastic resin composition, thereby further improving the impact strength of the resin. It relates to a resin composition.

Generally, acrylonitrile-butadiene-styrene (ABS) resins prepared by graft copolymerizing styrene and acrylonitrile monomers to a butadiene rubber polymer have excellent impact resistance, processability, beautiful appearance, High heat distortion temperature, etc., and is used for various purposes such as automobile parts, electrical and electronic products, and building materials.

However, because ABS resin has ethylenically unsaturated polymer in butadiene rubber used as impact modifier, corals are easily generated by ultraviolet rays, light and heat in the presence of oxygen, so 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, in order to obtain a thermoplastic resin excellent in physical properties and excellent in weather resistance and aging resistance, an acrylonitrile-styrene-acrylate (hereinafter referred to as " acrylonitrile- styrene- acrylate "), which uses an acrylic rubber in which an ethylenically unsaturated polymer is not present instead of butadiene rubber as an impact modifier, ASA) terpolymer resin is used. Such ASA resins are used in various fields such as electric and electronic parts used for outdoor use, building materials, automobiles, ships, leisure goods, and gardening.

However, there have been many attempts to improve the impact strength since it tends to be somewhat lower than the ABS impact strength. Attempts have been made to increase the impact strength by making the particle size of the rubber larger than before. However, when the rubber particle size increases, latex stability is lowered, and other physical properties such as tensile strength are inferior.

Therefore, there is a need for an acrylate-styrene-acrylonitrile resin that can improve impact strength without adjusting the particle size of rubber.

Therefore, in the present invention to solve the problems of the prior art as described above, an object of the present invention is to prepare an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer excellent in impact strength and prepared by the method It is to provide a thermoplastic resin composition comprising an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer.

The above object of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention is a vinyl cyan compound-vinylaromatic compound copolymer 40 to 80% by weight; And 20 to 60 wt% of an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer, wherein the alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer comprises (A) a vinyl aromatic compound, a vinyl cyan compound and A seed comprising at least one member selected from the group consisting of alkyl acrylates; (B) a rubber core surrounding the seed and comprising an alkyl acrylate monomer; And (C) a graft shell surrounding the rubber core and selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, and comprising a polyethylene-based crosslinking agent. do.

In addition, the present invention is selected from the group consisting of (a) a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate, based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer. Preparing a seed by polymerizing a monomer mixture including at least one 4 to 30 parts by weight; (b) preparing a rubber core by polymerizing 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a crosslinking agent in the presence of the seed; And (c) a monomer mixture comprising 10 to 70 parts by weight of at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core, and 0.01 to 5 parts by weight of a polyethylene-based crosslinking agent, to be graft shell crosslinked. It provides a method for producing an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer comprising a step of preparing a.

The thermoplastic resin composition comprising the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer prepared according to the present invention has an excellent impact strength.

The thermoplastic resin composition of the present invention for achieving the above object is 40 to 80% by weight of a vinyl cyan compound-vinylaromatic compound copolymer; And 20 to 60 wt% of an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer, wherein the alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer comprises (A) a vinyl aromatic compound, a vinyl cyan compound and A seed comprising at least one member selected from the group consisting of alkyl acrylates; (B) a rubber core surrounding the seed and comprising an alkyl acrylate monomer; And (C) a graft shell surrounding the rubber core and including at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, and a polyethylene-based crosslinking agent.

In addition, the method for producing the alkylacrylate-vinylaromatic compound-vinylcyan compound of the present invention is based on 100 parts by weight of the total monomers used in the preparation of the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer, (a) vinyl Preparing a seed by polymerizing a monomer mixture comprising 4 to 30 parts by weight of at least one selected from the group consisting of an aromatic compound, a vinyl cyan compound and an alkyl acrylate; (b) preparing a rubber core by polymerizing a monomer mixture comprising 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a crosslinking agent in the presence of the seed; And (c) a monomer mixture comprising 10 to 70 parts by weight of at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core, and 0.01 to 5 parts by weight of a polyethylene-based crosslinking agent, to be graft shell crosslinked. To prepare a; characterized in that it comprises a.

Hereinafter, the present invention will be described in more detail.

The thermoplastic resin composition of the present invention is 40 to 80% by weight of a vinyl cyan compound-vinylaromatic compound copolymer; And 20 to 60 wt% of an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer, wherein the alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer comprises (A) a vinyl aromatic compound, a vinyl cyan compound and A seed comprising at least one member selected from the group consisting of alkyl acrylates; (B) a rubber core surrounding the seed and comprising an alkyl acrylate monomer; And (C) a graft shell surrounding the rubber core and comprising at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and a polyethylene-based crosslinking agent.

The alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer is based on 100 parts by weight of the total monomers used in the preparation of the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer, (A) vinyl aromatic compound, vinyl cyan A seed comprising 4 to 30 parts by weight of at least one selected from the group consisting of a compound and an alkyl acrylate; (B) an alkyl acrylate monomer surrounding the seed A rubber core comprising 20 to 80 parts by weight and 0.01 to 3 parts by weight of a crosslinking agent; And (C) at least 10 to 70 parts by weight of one or more selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, And a crosslinked graft shell comprising 0.01 to 3 parts by weight of a crosslinking agent selected from the group consisting of polypropylene glycol dimethacrylate.

The polyethylene-based crosslinking agent may be at least one selected from the group consisting of polyalkylene glycol diacrylate or polyalkylene glycol dimethacrylate, and specifically, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and poly It may be selected from the group consisting of propylene glycol dimethacrylate. For example, polyethylene glycol diacrylate is used, but not limited thereto.

The aromatic vinyl compound may be at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, and vinyltoluene. For example, styrene is used, but is not limited thereto.

The vinyl cyan compound may be selected from one or more selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, and examples thereof include acrylonitrile, but are not limited thereto.

The alkyl acrylate may include an alkyl group having 2 to 8 carbon atoms. For example, methyl acrylate, ethyl acrylate or butyl acrylate having 1 to 4 carbon atoms in the alkyl portion may be used, but is not limited thereto. .

An example of the vinyl cyan compound-vinylaromatic compound copolymer may be an acrylonitrile-styrene (AS) copolymer.

An example of the alkyl acrylate-vinyl aromatic compound-vinyl cyan compound copolymer may be acrylate-styrene-acrylonitrile (ASA).

One specific embodiment of the method for preparing the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer of the present invention is based on 100 parts by weight of the total monomers used to prepare the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer. (a) a monomer comprising 4 to 30 parts by weight of at least one selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate, 0.001 to 1 parts by weight of an electrolyte, 0.01 to 1 parts by weight of a crosslinking agent, and 0.01 to 1 part by weight of a grafting agent. Preparing a seed by polymerizing a monomer mixture comprising 3 parts by weight, 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier; (b) preparing a rubber core by polymerizing a monomer mixture comprising 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier in the presence of the seed. step; And (c) 10 to 70 parts by weight of one or more selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate Preparing a crosslinked graft shell by polymerizing a monomer mixture comprising 0.01 to 3 parts by weight of a crosslinking agent selected from the group consisting of polypropylene glycol dimethacrylate, 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier; Characterized in that comprises a.

The aromatic vinyl compound used in the steps (a) and (c) may be selected from the group consisting of styrene, -methylstyrene, p-methylstyrene and vinyltoluene. Styrene is preferably used, But is not limited thereto.

The vinyl cyan compound used in the steps (a) and (c) may be selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, preferably acrylonitrile , But is not limited thereto.

The alkyl acrylate of step (a) and (b) is characterized in that it comprises an alkyl group having 2 to 8 carbon atoms, preferably methyl acrylate, ethyl acrylate or butyl having 1 to 4 carbon atoms of the alkyl portion An acrylate is used, but is not limited thereto.

In the present invention, the polyethylene-based crosslinking agent having a number average molecular weight of 250 or more may be used in step (c), for example, a crosslinking agent having a number average molecular weight of 250 to 1,000 may be used. Specifically, polyethyleneglycol diacrylate (PEGDA), polyethyleneglycol dimethacrylate (PEGDMA), polypropyleneglycol diacrylate (PPGDA) and polypropyleneglycol dimethacrylate (polypropyleneglycol dimethacrylate). , PPGDMA) using a polyethylene-based crosslinking agent selected from the group consisting of further improving the impact strength of the thermoplastic resin composition comprising an alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer.

In addition, a grafting agent may be further added to the polyethylene-based crosslinking agent. The grafting agent may be allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallylamine (TAA) or diallyl amine (DAA).

In addition, the crosslinking agent used in the step (b) is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate , Ethylene glycol diacrylate, hexanediol ethoxylate diacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacryl Latex, neopentylglycol propoxylate diacrylate, trimethylolpropane trimethacrylate, trimethylolmethane triacrylate, trimethylpropaneethoxylate triacrylate, trimethylpropanepropoxylate triacrylate, pentaerythritol ethoxy Late triacrylate, pentaerythritol propoxylate tri Methacrylate and vinyl triethoxysilane may be one or more selected from the group consisting of silane, preferably a single use of divinylbenzene, and the like.

The emulsifier used in the above steps (a), (b) and (c) is not particularly limited, but an anionic surfactant, a nonionic surfactant, a cationic surfactant, a positive surfactant and the like can be used .

Of these, anionic surfactants selected from the group consisting of alkenyl succinate metal salts, alkyl benzene sulfonic acid salts, aliphatic sulfonic acid salts, sulfuric acid ester salts of higher alcohol,? -Olefin sulfonic acid salts and alkyl ether sulfuric acid ester salts are particularly preferably used .

In the electrolyte is _{KCl, NaCl, KHCO 3, NaHCO} 3, K 2 CO 3, Na 2 CO 3, KHSO 3, NaHSO 4, Na 2 S 2 O 7, K 4 P 2 O 7, K 3 PO 4, Na ₃ PO ₄ or Na ₂ HPO _4, etc. alone, or two or more kinds may be mixed.

The initiator used in the above steps (a), (b) and (c) is not particularly limited, but a radical initiator can be preferably used. Examples of the radical initiator include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide; t-butyl peroxide, cumene hydroperoxide, p-menthol hydroperoxide, di-t-butyl peroxide, t-butyl cumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide Organic peroxides such as oxides, 3,5,5-trimethylhexanol peroxide, t-butyl peroxyisobutyrate; At least one member selected from the group consisting of azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and azobisisobutyric acid (butyl acid) methyl, Inorganic peroxides are more preferable, and persulfates are particularly preferably used.

An activator may be used to promote 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 or sodium sulfite, etc. are preferably used alone or in combination of two or more.

The grafting agent in the step (a) may be allyl methacrylate (AMA), triallyl isocyanurate (TAIC), triallylamine (TAA) or diallylamine (DAA).

Although the polymerization temperature at the time of the said emulsion polymerization is not specifically limited, Usually, 50-85 degreeC, Preferably it is 60-80 degreeC.

The alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer of the present invention preferably includes a seed having an average particle diameter of 0.1 to 0.3 µm, and an impact strength is lowered at an average particle diameter of less than 0.1 µm, and more than 0.3 µm. There is a problem that the latex stability is poor. Moreover, it is preferable that the alkylacrylate-vinylaromatic compound-vinyl cyan compound copolymer of this invention contains the rubber core whose average particle diameter is 0.15-0.5 micrometer.

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.

Including the thermoplastic resin composition according to the present invention can be prepared an exterior material, specifically, it can be usefully manufactured as a vehicle exterior material or a mobile phone exterior material.

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 scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example  One

Hard  Step of polymer seed preparation

40 parts by weight of distilled water was added to the polymerization reactor purged with nitrogen and the temperature was raised to 75 캜. Then, 0.025 part by weight of potassium persulfate was added thereto in a total amount of 5 parts by weight. Styrene 5 parts by weight, Na ₂ CO ₃ 0.05 parts by weight, 0.025 part by weight of acrylate, 0.025 part by weight of allyl methacrylate and 0.05 part by weight of sodium laurylsulfate were continuously added at 75 DEG C to prepare a hard polymer seed having an average particle diameter of 0.1 mu m.

Rubber polymer core preparation step

In the presence of the prepared hard polymer seed latex, 60 parts by weight of distilled water, 55 parts by weight of butyl acrylate, 0.3 parts by weight of divinylbenzene, 0.3 parts by weight of allyl methacrylate, 0.5 parts by weight of cumene hydroperoxide and sodium lauryl sulfate A mixture of 0.5 parts by weight was continuously added at 75 ° C. to prepare a rubber polymer core having an average particle diameter of 0.3 μm.

Bridged Graft  Shell manufacturing step

In the presence of the prepared rubber polymer core, 50 parts by weight of distilled water, 30 parts by weight of styrene, 10 parts by weight of acrylonitrile, 0.5 parts by weight of polyethylene glycol diacrylate (molecular weight 258), 0.5 parts by weight of cumene hydroperoxide and lauryl The polymerization reaction was carried out while continuously introducing a mixture of 0.65 parts by weight of sodium sulfate at 75 ° C. After the addition of the mixture was completed, the mixture was further reacted at 75 DEG C for 1 hour and cooled to 60 DEG C to complete the polymerization reaction, thereby preparing a graft copolymer latex. The polymerization conversion ratio of the prepared graft copolymer latex was 98% and the solid content was 40%.

Graft  Preparation of Copolymer Powder

The prepared acrylate-styrene-acrylonitrile graft copolymer latex was subjected to atmospheric coagulation using an aqueous sulfuric acid solution at 80 ° C., and then aged at 95 ° C., dehydrated and washed, and dried for 30 minutes with 90 ° C. hot air. To prepare an acrylate-styrene-acrylonitrile graft copolymer powder.

Example  2

A graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 parts by weight of polyethylene glycol dimethacrylate (molecular weight 330) was used instead of PEGDA in the preparation of the rubber polymer shell of Example 1. .

Example  3

The graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 parts by weight of PEGDA (molecular weight 575) was used instead of PEGDA (molecular weight 258) in the preparation of the rubber polymer shell of Example 1.

Example  4

Graft copolymer powder was prepared in the same manner as in Example 1, except that 0.3 parts by weight of PEGDA (molecular weight 700) was used instead of PEGDA (molecular weight 258) in the preparation of the rubber polymer shell of Example 1.

Comparative Example  One

Graft copolymer powder was prepared in the same manner as in Example 1, except that 0.3 parts by weight of ethylene glycol dimethacrylate (EGDMA) was used instead of PEGDA (molecular weight 258) in the preparation of the rubber polymer shell of Example 1. Was prepared.

Comparative Example  2

Graft copolymer was prepared in the same manner as in Example 1 except that 0.6 parts by weight of allyl methacrylate (AMA) was used instead of PEGDA (molecular weight 258) in the preparation of the rubber polymer shell of Example 1. Powder was prepared.

[Test Example]

<ASA resin manufacturing>

40 parts by weight of graft copolymer powder prepared in Examples 1 to 5 and Comparative Examples 1 to 3, 2 parts by weight of lubricant, 60 parts by weight of styrene-acrylonitrile copolymer 90HR (manufactured by LG Chemical) as a hard matrix, and oxidation 2 weight part of inhibitors, and 3 weight part of ultraviolet stabilizers were added and mixed. This was molded into a pellet shape at a cylinder temperature of 300 DEG C using a 40 pie extrusion kneader and then injected with the pellet to prepare a physical property specimen.

* Izod impact strength (1/8 ", 1/4" notched at (23 ° C), kg cm / cm)-was measured according to ASTM D256.

Tensile strength (50 mm / min, kg / cm ² ): Measured according to ASTM D638.

Test Example One 2 3 4 5 6 Graft copolymer
(ASA) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 The tensile strength
(kg / cm ² ) 425 425 420 416 403 404 Impact strength
(1/8 "
(kg · cm / cm) 21.0 22.0 21.4 22.1 17.6 16.4 Impact strength
(1/4 "
(kg · cm / cm) 15.2 15.7 15.4 15.6 14.1 14.8

When the acrylonitrile-styrene resin according to Test Examples 1 to 4 contains an acrylate-styrene-acrylonitrile copolymer prepared by using a crosslinking agent such as PEGDA in the shell portion, the polyethylene-based crosslinking agent is not used. It can be seen that the effect of increasing the impact strength of the resin compared to Test Examples 5 to 6 that do not, and can be maintained without lowering the physical properties such as tensile strength.

Claims (16)

40 to 80% by weight of vinyl cyan compound-vinylaromatic compound copolymer; And
20 to 60 wt% of an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer;
The alkyl acrylate-vinyl aromatic compound-vinyl cyan compound copolymer
(A) a seed comprising at least one member selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate;
(B) a rubber core surrounding the seed and comprising an alkyl acrylate monomer; And
(C) a graft shell surrounding the rubber core and comprising at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and a polyethylene-based crosslinking agent. The method of claim 1,
The alkyl acrylate-vinyl aromatic compound-vinyl cyan compound copolymer
To 100 parts by weight of the total monomers used in the preparation of the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer,
(A) a seed comprising 4 to 30 parts by weight of at least one selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate;
(B) an alkyl acrylate monomer surrounding the seed A rubber core comprising 20 to 80 parts by weight and 0.01 to 3 parts by weight of a crosslinking agent; And
(C) at least 10 to 70 parts by weight of at least one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound and the polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and poly A crosslinked graft shell comprising 0.01 to 3 parts by weight of a crosslinking agent selected from the group consisting of propylene glycol dimethacrylate; thermoplastic resin composition comprising a. The method of claim 1,
The polyethylene-based crosslinking agent is selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate and polypropylene glycol dimethacrylate and has a number average molecular weight of 250 to 1,000. Thermoplastic resin composition, characterized in that. The method of claim 1,
The polyethylene-based crosslinking agent further comprises a grafting agent, wherein the grafting agent is a thermoplastic resin, characterized in that at least one selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallyl amine and diallyl amine Composition. The method of claim 1, wherein
The aromatic vinyl compound is a 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 is at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. The method of claim 1,
The alkyl acrylate is a thermoplastic resin composition comprising an alkyl group having 2 to 8 carbon atoms. To 100 parts by weight of the total monomers used in the preparation of the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer,
(a) preparing a seed by polymerizing a monomer mixture comprising 4 to 30 parts by weight of at least one selected from the group consisting of a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate;
(b) preparing a rubber core by polymerizing a monomer mixture comprising 20 to 80 parts by weight of an alkyl acrylate monomer and 0.01 to 3 parts by weight of a crosslinking agent in the presence of the seed; And
(c) a monomer mixture comprising 10 to 70 parts by weight of one or more selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core and polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol Preparing a crosslinked graft shell by polymerizing 0.01 to 3 parts by weight of a crosslinking agent selected from the group consisting of diacrylate and polypropylene glycol dimethacrylate; alkylacrylate-vinylaromatic compound- Method for producing vinyl cyan compound copolymer. The method of claim 8,
The aromatic vinyl compound is a method for producing an alkylacrylate-vinylaromatic compound-vinyl cyan compound copolymer, characterized in that at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene and vinyl toluene. The method of claim 8,
The vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. The method of claim 8,
The alkyl acrylate is a method for producing an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer, characterized in that it comprises an alkyl group having 2 to 8 carbon atoms. The method of claim 8,
The crosslinking agent of (b) is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate, ethylene glycol diacrylate , Hexanediol ethoxylate diacrylate, hexanediol ethoxylate diacrylate, hexanediol propoxylate diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol ethoxylate diacrylate, neopentyl glycol pro Foxylate Diacrylate, Trimethylolpropane Trimethacrylate, Trimethylolmethane Triacrylate, Trimethyl Propane Ethoxylate Triacrylate, Trimethyl Propane Propoxylate Triacrylate, Pentaerythritol Ethoxylate Triacrylate, Penta Erythrotol Propoxylate Triacrylate and Vinyl Tree Ethoxy one alkyl acrylate, characterized in that more than species selected from the group consisting of silane-vinyl aromatic compound process for producing a vinyl cyan compound copolymer. The method of claim 8,
The monomer mixture 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 with respect to 100 parts by weight of the total monomers used to prepare the acrylate-styrene-acrylonitrile copolymer. A method for producing an alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer, further comprising: by weight, 0.01 to 3 parts by weight of initiator and 0.01 to 5 parts by weight of emulsifier. The method of claim 8,
The monomer mixture of (b) further comprises 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier based on 100 parts by weight of the total monomers used in the preparation of the alkylacrylate-vinylaromatic compound-vinylcyan compound copolymer. Method for producing an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer, characterized in that. The method of claim 8,
The monomer mixture of (c) further comprises 0.01 to 3 parts by weight of an initiator and 0.01 to 5 parts by weight of an emulsifier based on 100 parts by weight of the total monomers used in the preparation of the acrylate-styrene-acrylonitrile copolymer. Method for producing an alkyl acrylate-vinylaromatic compound-vinyl cyan compound copolymer. A packaging material comprising the thermoplastic resin composition according to claim 1.