KR101549290B1 - 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 a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer by using a polyethylene-based crosslinking agent such as polyethylene glycol diacrylate or polyethylene glycol dimethacrylate in the shell part of an alkyl acrylate-vinyl aromatic compound- Vinyl aromatic compound-vinyl cyanide copolymer which exhibits an effect of further improving the impact strength of a resin by preparing a compound copolymer and applying it to a thermoplastic resin composition, and a method for producing a thermoplastic resin composition containing the same .

Description

TECHNICAL FIELD The present invention relates to a method for preparing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer having excellent impact strength and a thermoplastic resin composition containing the same. impact strength}

TECHNICAL FIELD The present invention relates to a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer and a thermoplastic resin composition containing the same. More specifically, the present invention relates to a process for producing an acrylate-styrene Vinyl aromatic compound-vinyl cyanide copolymer which exhibits an effect of further improving the impact strength of a resin by preparing an acrylonitrile copolymer and applying it to a thermoplastic resin composition, and a thermoplastic 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, since ABS resin is an ethylenically unsaturated polymer used in the butadiene rubber used as an impact modifier, it is easily corroded by ultraviolet rays, light, and heat in the presence of oxygen, so that appearance and color of resin are changed, and mechanical properties are deteriorated There is a problem that it is not suitable as an outdoor material.

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 has been a lot of attempts to improve the impact strength because it tends to be somewhat lower than the ABS impact strength. There is an attempt to increase the impact strength by making the particle size of the rubber larger than the conventional one. However, as the particle size of the rubber increases, the latex stability deteriorates and other physical properties such as tensile strength deteriorate.

Therefore, there is a demand for an acrylate-styrene-acrylonitrile resin which can improve the impact strength without controlling the particle size of the rubber.

Korean Patent Publication No. 10-2009-0040111 (published on April 23, 2009)

SUMMARY OF THE INVENTION Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a process for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer excellent in impact strength, And a thermoplastic resin composition comprising an alkyl acrylate-vinyl aromatic compound-vinyl cyanide 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 relates to a cyan ink composition comprising 40 to 80% by weight of a vinyl cyan compound-vinyl aromatic compound copolymer; And an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, wherein the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer comprises (A) a vinyl aromatic compound, a vinyl cyan compound, An alkyl acrylate, and the like; (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 crosslinking agent. do.

The present invention also relates to a process for the preparation of an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, comprising, for 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, (a) a vinyl aromatic compound, a vinyl cyan compound and an alkyl acrylate Preparing a seed by polymerizing a monomer mixture comprising at least one and 4 to 30 parts by weight; (b) 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 to produce a rubber core; And (c) 0.01 to 5 parts by weight of a monomer mixture comprising 10 to 70 parts by weight of at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core and a polyethylene crosslinking agent to form a crosslinked graft shell Vinyl aromatic compound-vinyl cyanide copolymer, wherein the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is prepared by reacting an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer.

The thermoplastic resin composition comprising the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer prepared according to the present invention has an excellent impact strength.

To achieve the above object, the thermoplastic resin composition of the present invention comprises 40 to 80% by weight of a vinyl cyan compound-vinyl aromatic compound copolymer; And an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, wherein the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer comprises (A) a vinyl aromatic compound, a vinyl cyan compound, An alkyl acrylate, and the like; (B) a rubber core surrounding the seed and comprising an alkyl acrylate monomer; And (C) a graft shell which surrounds the rubber core and comprises at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, and a polyethylene crosslinking agent.

In addition, the method for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide compound of the present invention is characterized in that (a) vinyl acetate is added to 100 parts by weight of the total monomers used in the production of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer, Preparing a seed by polymerizing a monomer mixture comprising at least 4 to 30 parts by weight of at least one member selected from the group consisting of an aromatic compound, a vinyl cyan compound and an alkyl acrylate; (b) polymerizing from 0.01 to 3 parts by weight of a monomer mixture comprising from 20 to 80 parts by weight of an alkyl acrylate monomer in the presence of said seed and of a crosslinking agent to form a rubber core; And (c) 0.01 to 5 parts by weight of a monomer mixture comprising 10 to 70 parts by weight of at least one member selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core and a polyethylene crosslinking agent to form a crosslinked graft shell The method comprising the steps of:

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

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

The above-mentioned alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is obtained by copolymerizing (A) a vinyl aromatic compound, a vinyl cyanide compound and a vinyl cyanide compound with respect to 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound- And 4 to 30 parts by weight of at least one member selected from the group consisting of alkyl acrylates; (B) encapsulating the seed and adding an alkyl acrylate monomer 20 to 80 parts by weight of a crosslinking agent and 0.01 to 3 parts by weight of a crosslinking agent; And (C) 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 at least one member selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, And a crosslinked grafted 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 selected from the group consisting of polyalkylene glycol diacrylate or polyalkylene glycol dimethacrylate, and specifically includes polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and poly Propylene glycol dimethacrylate, and 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,? -Methylstyrene, p-methylstyrene, and vinyltoluene. For example, styrene is used, but the present invention is not limited thereto.

The vinyl cyan compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. For example, acrylonitrile may be used, but the present invention is not limited thereto.

The alkyl acrylate may include an alkyl group having 2 to 8 carbon atoms. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate and butyl acrylate having an alkyl moiety having 1 to 4 carbon atoms, but are not limited thereto .

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

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

One specific example of the method for producing the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention is a method for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer by adding 100 parts by weight of the total monomers used for the preparation of the alkyl acrylate- (a) 0.001 to 1 part by weight of an electrolyte, 0.01 to 1 part by weight of a crosslinking agent, 0.01 to 1 part by weight of a crosslinking agent, 0.01 to 1 part by weight of a crosslinking agent, 3 to 3 parts by weight of an initiator, 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier to prepare a seed; (b) 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; (C) 10 to 70 parts by weight of at least one selected from the group consisting of aromatic vinyl compounds and vinyl cyan compounds in the presence of the rubber core, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate 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, to obtain a crosslinked grafted shell; And a control unit.

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 in the above steps (a) and (b) is characterized by containing an alkyl group having 2 to 8 carbon atoms, preferably methyl acrylate having 1 to 4 carbon atoms in the alkyl moiety, ethyl acrylate or butyl Acrylate, but is not limited thereto.

In the present invention, a polyethylene-based crosslinking agent having a number average molecular weight of 250 or more may be used in step (c), and for example, a crosslinking agent having a number average molecular weight of 250 to 1,000 may be used. Specific examples of the polymer include polyethyleneglycol diacrylate (PEGDA), polyethyleneglycol dimethacrylate (PEGDMA), polypropyleneglycol diacrylate (PPGDA) and polypropyleneglycol dimethacrylate , PPGDMA), the impact strength of the thermoplastic resin composition comprising the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is further improved.

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

The crosslinking agent used in the step (b) may be selected from the group consisting of 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 Acrylate, trimethylolpropane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylpropane propoxylate triacrylate, pentaerythritol ethoxy 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).

The polymerization temperature during the emulsion polymerization is not particularly limited, but is usually from 50 to 85 캜, preferably from 60 to 80 캜.

The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention preferably contains a seed having an average particle diameter of 0.1 to 0.3 탆. When the average particle diameter is less than 0.1 탆, the impact strength is poor. When the average particle diameter is less than 0.3 탆 There is a problem that the stability of the latex is deteriorated. In addition, the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer of the present invention preferably includes a rubber core having an average particle diameter of 0.15 to 0.5 μm.

The thermoplastic resin composition may further comprise additives such as dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers or matting agents which are conventionally used depending on the application.

The exterior material can be manufactured by including the thermoplastic resin composition according to the present invention, and specifically, it can be usefully manufactured as an automobile 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 batch to initiate the reaction. Then, 5 parts by weight of styrene, 0.05 parts by weight of Na ₂ CO ₃ , 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

60 parts by weight of distilled water, 55 parts by weight of butyl acrylate, 0.3 part by weight of divinylbenzene, 0.3 part by weight of allyl methacrylate, 0.5 part by weight of cumene hydroperoxide, and 5 parts by weight of sodium laurylsulfate And 0.5 parts by weight of the mixture was continuously charged at 75 占 폚 to prepare a rubber polymer core having an average particle diameter of 0.3 占 퐉.

Bridged Graft  Shell manufacturing step

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 0.65 parts by weight of sodium sulfate was continuously added to the mixture at 75 캜 to carry out the polymerization reaction. 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 pressure agglomeration at 80 ° C using an aqueous solution of sulfuric acid, aged at 95 ° C, dehydrated and washed, dried with hot air at 90 ° C for 30 minutes To prepare an acrylate-styrene-acrylonitrile graft copolymer powder.

Example  2

Except that 0.3 part 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, to prepare a graft copolymer powder .

Example  3

A graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 part 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

A graft copolymer powder was prepared in the same manner as in Example 1 except that 0.3 part by weight of PEGDA (molecular weight: 700) was used in place of PEGDA (molecular weight 258) in the preparation of the rubber polymer shell of Example 1.

Comparative Example  One

Except that 0.3 part by weight of ethylene glycol dimethacrylate (EGDMA) was used instead of PEGDA (molecular weight 258) in the production step of the rubber polymer shell of Example 1 to prepare a graft copolymer powder .

Comparative Example  2

Except that 0.6 weight part of allyl methacrylate (AMA) was used in place of PEGDA (molecular weight 258) in the preparation step of the rubber polymer shell of Example 1, to prepare a graft copolymer Powder.

[Test Example]

<ASA resin production>

To 40 parts by weight of the graft copolymer powder prepared in Examples 1 to 5 and Comparative Examples 1 to 3 and 60 parts by weight of styrene-acrylonitrile copolymer 90HR (manufactured by LG Chemical Co., Ltd.) as a hard matrix, 2 parts by weight of a lubricant, 2 parts by weight of an inhibitor and 3 parts by weight of a UV stabilizer 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) - 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

Styrene-acrylonitrile copolymer prepared by using a crosslinking agent such as PEGDA in the shell portion of the acrylonitrile-styrene resin according to Test Examples 1 to 4, it was found that the use of the polyethylene-based crosslinking agent It is possible to confirm the effect of increasing the impact strength of the resin as compared with those of Test Examples 5 to 6, and it is possible to maintain the same without deteriorating physical properties such as tensile strength.

Claims (16)

From 40 to 80% by weight of a vinyl cyan compound-vinyl aromatic compound copolymer; And
From 20 to 60% by weight of an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer,
The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer is a copolymer comprising (A) a vinyl aromatic compound-containing seed; (B) a rubber core surrounding the seed and comprising an alkyl acrylate monomer; And (C) a graft shell which surrounds the rubber core and comprises a vinyl cyan compound, or one selected from the group consisting of an aromatic vinyl compound and a vinyl cyan compound, and a crosslinking agent,
Wherein the cross-linking agent is at least one selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate and polypropylene glycol dimethacrylate. The method according to claim 1,
The alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer
Based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer,
(A) 4 to 30 parts by weight of a vinyl aromatic compound;
(B) encapsulating the seed and adding an alkyl acrylate monomer 20 to 80 parts by weight of a crosslinking agent and 0.01 to 3 parts by weight of a crosslinking agent; And
(C) 10 to 70 parts by weight of one kind selected from the group consisting of a vinyl cyan compound or an aromatic vinyl compound and a vinyl cyan compound, and at least one member selected from the group consisting of polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol 0.01 to 3 parts by weight of a crosslinking agent selected from the group consisting of polyacrylonitrile, diacrylate, and polypropylene glycol dimethacrylate. The method according to claim 1,
Wherein the cross-linking agent has a number average molecular weight of from 250 to 1,000. The method according to claim 1,
Wherein the crosslinking agent further comprises a grafting agent, wherein the grafting agent is selected from the group consisting of allyl methacrylate, triallyl isocyanurate, triallyl amine, and diallylamine. The method of claim 1, wherein
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene. The method according to claim 1,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method according to claim 1,
Wherein the alkyl acrylate comprises an alkyl group having 2 to 8 carbon atoms. Based on 100 parts by weight of the total monomers used in the preparation of the alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer,
(a) preparing a seed by polymerizing 4 to 30 parts by weight of a monomer containing a vinyl aromatic compound;
(b) 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 cross-linking agent in the presence of the seeds; And
(c) a monomer mixture comprising 10 to 70 parts by weight of a vinyl cyan compound or an aromatic vinyl compound and a vinyl cyan compound in the presence of the rubber core, and a mixture of polyethylene glycol diacrylate and polyethylene glycol dimethacrylate Polymerizing 0.01 to 3 parts by weight of a crosslinking agent selected from the group consisting of polypropylene glycol diacrylate and polypropylene glycol dimethacrylate, A process for producing a vinyl aromatic compound-vinyl cyanide copolymer. 9. The method of claim 8,
Wherein the aromatic vinyl compound is at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, and vinyltoluene. 9. The method of claim 8,
Wherein the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 9. The method of claim 8,
Wherein the alkyl acrylate comprises an alkyl group having 2 to 8 carbon atoms. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; 9. The method of claim 8,
The crosslinking agent of (b) is preferably selected from the group consisting of 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 Trimethylolpropane triacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate triacrylate, pentaerythritol trimethacrylate triacrylate, pentaerythritol trimethacrylate triacrylate, pentaerythritol trimethacrylate triacrylate, Erythritol propoxylate triacrylate and vinyl tri 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. 9. The method of claim 8,
The monomer (a) is used in an amount of 0.001 to 1 part by weight of an electrolyte, 0.01 to 3 parts by weight of a crosslinking agent, 0.01 to 3 parts by weight of a grafting agent 0.01 to 3 parts by weight of an initiator, and 0.01 to 5 parts by weight of an emulsifier. The method for producing an alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer according to claim 1, 9. The method of claim 8,
The monomer mixture (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 alkyl acrylate-vinyl aromatic compound-vinyl cyanide copolymer Vinyl aromatic compound-vinyl cyanide copolymer. 9. The method of claim 8,
The monomer mixture (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 Vinyl aromatic compound-vinyl cyanide copolymer. An exterior material comprising the thermoplastic resin composition according to claim 1.