KR20030027478A - Methylmethacrylate-butadiene-styrene copolymer and method for preparing the same - Google Patents

Abstract

The present invention relates to a methyl methacrylate-butadiene-styrene copolymer composition and a method for producing the same, and particularly, to a polyvinyl chloride resin (PVC) which is made of dimethylsilicone and has impact resistance, transparency and processability. Provided are methylmethacrylate-butadiene-styrene copolymer compositions which can be used, and methods for their preparation.

Description

Methyl methacrylate-butadiene-styrene copolymer and preparation method thereof {METHYLMETHACRYLATE-BUTADIENE-STYRENE COPOLYMER AND METHOD FOR PREPARING THE SAME}

The present invention relates to a methyl methacrylate-butadiene-styrene copolymer composition and a method for preparing the same, and in particular, used in a vinyl chloride resin composition, a methyl methacrylate-butadiene-styrene copolymer composition in which impact resistance, transparency and processability are harmonized. And a method for producing the same.

In a method for producing a methyl methacrylate-butadiene-styrene copolymer prepared by graft polymerization of monomers such as alkyl methacrylate, acrylate, and ethylenically unsaturated aromatic compounds to rubber latex, linear having a viscosity of 20 to 1,000 cs. The present invention relates to a method for producing a methyl methacrylate-butadiene-styrene copolymer having excellent impact resistance including dimethylsilicone.

Polyvinyl chloride (PVC) is a polymer containing 50% by weight or more of vinyl chloride, which is excellent in transparency but has a disadvantage of being very weak against external impact.

Methods to compensate for this disadvantage have been studied for a long time, for example graft monomers such as styrene and methyl methacrylate on rubber latex based on styrene and butadiene To improve impact resistance while maintaining transparency.

It is known that the properties of methylmethacrylate-butadiene-styrene (MBS) resins are affected by the content of each monomer grafted, the polymerization method, and the content and particle size of the rubber latex used as the substrate. . It is a very common method to increase the rubber latex content and the particle size in order to improve the impact strength, but the increase of light scattering due to the increase of the particle size of the graft particles mixed with the vinyl chloride resin not only impairs the transparency, but also the excessive amount of rubber In the case of using, the bonding strength between the methyl methacrylate-butadiene-styrene resin and the vinyl chloride resin is weakened due to the reduction of the graft rate, thereby lowering the impact strength.

To date, there have been many studies on rubber particle content, size, graft polymerization method, composition, etc. in order to maintain the transparency while improving impact resistance.In particular, a method of enlarging rubber latex by adding a weakly acidic substance and using a water-soluble electrolyte In addition, a method of improving impact strength by enlarging rubber latex by adding water-soluble latex has been generalized. In addition, Will and Christopher's European Patent Publication No. 0,527,605, A1 discloses a method for growing particles by agglomeration, which grows through partial agglomeration by controlling the growth-out and the salt concentration and acidity. However, the methyl methacrylate-butadiene-styrene resin prepared according to the method proposed above has a slight improvement in transparency and impact strength. There is a problem that it takes a lot of time.

The present invention provides a methyl methacrylate-butadiene-styrene copolymer composition excellent in transparency and processability and excellent impact resistance in order to solve the problems of the prior art.

In addition, an object of the present invention is to provide a method for producing a methyl methacrylate-butadiene-styrene copolymer, which requires little time for the preparation of the methyl methacrylate-butadiene-styrene copolymer and is easy to manufacture.

In order to achieve the above object, the present invention provides a methyl methacrylate-butadiene-styrene copolymer comprising rubber latex, alkyl methacrylate, acrylate, ethylenically unsaturated aromatic compound, and linear dimethylsilicone.

The present invention also provides a method for producing a methyl methacrylate-butadiene-styrene copolymer comprising graft polymerization by adding an alkyl methacrylate, an acrylate, and an ethylenically unsaturated aromatic compound to the rubber latex, the graft polymerization It provides a method for producing a methyl methacrylate-butadiene-styrene copolymer which is carried out by adding linear dimethylsilicon having a viscosity of 20 to 1,000 cs (centistokes).

In addition, the present invention comprises the steps of preparing a rubber latex; And graft polymerization by adding an alkyl methacrylate, an acrylate, and an ethylenically unsaturated aromatic compound to the rubber latex, the method of producing a methylmethacrylate-butadiene-styrene copolymer comprising: Provided is a method for preparing a methyl methacrylate-butadiene-styrene copolymer which is carried out by adding linear dimethylsilicone having a viscosity of 20 to 1,000 cs (centistokes).

Hereinafter, the present invention will be described in detail.

In order to achieve the above object, the present invention provides a methyl methacrylate-butadiene-styrene copolymer comprising rubber latex, alkyl methacrylate, acrylate, ethylenically unsaturated aromatic compound, and linear dimethylsilicone.

The linear dimethylsilicone preferably has a viscosity of 20 to 1,000 cs (centistokes).

The present invention also provides a method for producing a methyl methacrylate-butadiene-styrene copolymer comprising graft polymerization by adding an alkyl methacrylate, an acrylate, and an ethylenically unsaturated aromatic compound to the rubber latex, the graft polymerization It provides a method for producing a methyl methacrylate-butadiene-styrene copolymer which is carried out by adding linear dimethylsilicon having a viscosity of 20 to 1,000 cs (centistokes).

In addition, the present invention comprises the steps of preparing a rubber latex; And graft polymerization by adding an alkyl methacrylate, an acrylate, and an ethylenically unsaturated aromatic compound to the rubber latex, wherein the preparation of the rubber latex is carried out in the manufacturing method of the methyl methacrylate-butadiene-styrene copolymer. Provided is a method for preparing a methyl methacrylate-butadiene-styrene copolymer which is carried out by adding linear dimethylsilicone having a viscosity of 20 to 1,000 cs (centistokes).

Hereinafter, the present invention will be described in detail.

The methyl methacrylate-butadiene-styrene copolymer of the present invention is 70 to 80 parts by weight of rubber latex, 5 to 25 parts by weight of alkyl methacrylate, 0.0001 to 5 parts by weight of acrylate, 5 to 30 parts by weight of ethylenically unsaturated aromatic compound, And 0.001-1.0 parts by weight of linear dimethylsilicone.

The methyl methacrylate-butadiene-styrene copolymer of the present invention is 70 to 80 parts by weight of rubber latex, 5 to 25 parts by weight of alkyl methacrylate, 0.0001 to 5 parts by weight of acrylate, and linear dimethyl having a viscosity of 20 to 1,000 cs. One step graft polymerization is performed by adding 0.001 to 1.0 parts by weight of silicon, followed by two step graft polymerization by adding 5 to 30 parts by weight of an ethylenically unsaturated aromatic compound thereto.

In another method, 5 to 25 parts by weight of alkyl methacrylate and 0.0001 to 5 parts by weight of acrylate are added to 70 to 80 parts by weight of rubber latex, followed by one step graft polymerization, and then 5 to 30 parts by weight of ethylenically unsaturated aromatic compound. Part, and 0.001 to 1.0 parts by weight of linear dimethylsilicon having a viscosity of 20 to 1,000 cs is added to prepare by two step graft polymerization.

The linear dimethylsilicone is preferably a viscosity of 20 to 1,000 cs, depending on the molecular weight of the linear dimethylsilicone polymer, the content is preferably 0.001 to 1.0 parts by weight.

In addition, the linear dimethylsilicone may be added to any stage as long as it has an appropriate viscosity and content, and a part of the content may be used as a method of adding the remaining amount to the two-stage graft polymerization.

The rubber latex is preferably styrene-butadiene rubber, and can be prepared by emulsion polymerization including butadiene or isoprene as a main component and one to three other vinyl monomers by a conventional emulsion polymerization method. Vinyl monomers that can be used for copolymerization are used to control the refractive index of the copolymer or to make the copolymer into a crosslinked structure. The content and type of vinyl monomer used in the copolymerization can be changed depending on the desired degree of physical properties, but can usually be used in the range of 35% by weight or less in the final copolymer.

Specifically, styrene-butadiene copolymer rubber

V) 65 to 85 parts by weight of butadiene; And

Ii) 5 to 35 parts by weight of vinyl monomers;

Iii) 0.1 to 5 parts by weight of monomer used as a graft crosslinking agent, if necessary

It is preferable to include.

The vinyl monomer of ii) in the styrene-butadiene rubber includes styrene, acrylonitrile, divinylbenzene, alkyl acrylate-based ethyl acrylate, or butyl acrylate, and these monomers are one or more, mainly two or more. Mixed to use.

In addition, the graft crosslinking agent in the styrene-butadiene rubber is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol di It can be used one or more selected from the group consisting of methacrylate, aryl methacrylate, and 1,3-butylene glycol diacrylate, and is used in 0.1 to 5.0 parts by weight, but the transparency and the whitening of the vinyl chloride resin It is preferable to use 0.1-2.0 weight part for improvement.

In addition, the methyl methacrylate-butadiene-styrene copolymer of the present invention is prepared by adding: i) 65 to 85 parts by weight of butadiene, 5 to 35 parts by weight of vinyl monomer, and 0.001 to 1.0 parts by weight of linear dimethyl silicone having a viscosity of 20 to 1,000 cs. An alkyl methacrylate and an acrylate are added to one rubber latex to prepare a one step graft polymerization, and an ethylenically unsaturated aromatic compound is added to prepare a two step graft polymerization.

When preparing the rubber latex, 0.1 to 5 parts by weight of the monomer used as the graft crosslinking agent may be added.

The production method of the present invention can improve the impact strength while maintaining the transparency by sequentially performing the graft polymerization in two steps. In addition, transparency and impact strength can be simultaneously improved by additives without increasing the particle size of the rubber latex, as well as saving the complicated process and time required for increasing the particle size.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Example 1

(Manufacture of rubber latex)

180 parts by weight of ion-exchanged water in a 40 L high-pressure polymerization vessel equipped with a stirrer, 0.5 parts by weight of a buffer solution as an additive, 1.15 parts by weight of potassium oleate, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, 0.003 parts by weight of ferrous sulfate, sodium form 0.02 parts by weight of aldehyde sulfoxylate and 0.11 parts by weight of diisopropylbenzene hydroperoxide were initially charged.

23 parts by weight of butadiene, 17 parts by weight of styrene, and 0.2 parts by weight of divinylbenzene were added thereto in one step to polymerize at 40 ° C. for 3 hours, 53 parts by weight of butadiene, 6 parts by weight of styrene, and 0.8 parts of divinylbenzene in two steps. Parts by weight, and potassium oleate 0.7, 0.002 parts by weight of ethylenediamine tetrasodium acetate, 0.002 parts by weight of ferrous sulfate, 0.01 parts by weight of sodium formaldehyde sulfoxylate, and 0.05 parts by weight of diisopropylbenzene hydroperoxide for 10 hours. After the polymerization, 1.0 part by weight of potassium oleate was added as a stabilizing emulsifier to obtain a styrene-butadiene rubber latex having a particle size of 850 mm 3, and the final polymerization conversion thereof was 98%.

(1 step polymerization)

75 parts by weight of the obtained rubber latex (solid) was charged to a closed reactor, and charged with nitrogen, 10 parts by weight of methyl methacrylate and 2 parts by weight of ethyl acrylate, and 0.2 parts by weight of potassium oleate as an additive. 0.01 parts by weight of sodium formaldehyde sulfoxylate, and 0.15 parts by weight of t-butyl hydroperoxide were added to the rubber latex continuously at 40 ° C. for 5 minutes, and then polymerized for 1 hour.

(Two stage polymerization)

13 parts by weight of styrene and 0.5 parts by weight of dimethylsilicone (Dow Corning 200F) having a viscosity of 20 cs in the first stage polymer, and 0.2 parts by weight of potassium oleate as an additive, 0.01 parts by weight of sodium formaldehyde sulfoxylate, and t-butyl hydroper 0.15 parts by weight of oxide was added to the rubber latex continuously at 50 ° C. for 10 minutes, and then polymerized for 1 hour.

As a result of the polymerization in the above manner, 100 parts by weight of the same amount of the added latex monomer could be obtained.

Example 2

In the two-step polymerization of Example 1, except that 0.5 parts by weight of dimethylsilicone having a viscosity of 100 cs was prepared in the same manner as in Example 1.

Example 3

In the two-step polymerization of Example 1, it was prepared in the same manner as in Example 1 except that 0.5 parts by weight of dimethylsilicone having a viscosity of 1,000 cs was used.

Example 4

In the two-step polymerization of Example 1, it was prepared in the same manner as in Example 1 except that 0.01 parts by weight of dimethylsilicone having a viscosity of 100 cs was used.

Example 5

(Manufacture of rubber latex)

180 parts by weight of ion-exchanged water in a 40 L high-pressure polymerization vessel equipped with a stirrer, 0.5 parts by weight of a buffer solution as an additive, 1.15 parts by weight of potassium oleate, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, 0.003 parts by weight of ferrous sulfate, sodium form 0.02 parts by weight of aldehyde sulfoxylate and 0.11 parts by weight of diisopropylbenzene hydroperoxide were initially charged.

23 parts by weight of butadiene, 17 parts by weight of styrene, and 0.2 parts by weight of divinylbenzene were added thereto in one step to polymerize at 40 ° C. for 3 hours, 53 parts by weight of butadiene, 6 parts by weight of styrene, and 0.8 parts of divinylbenzene in two steps. Parts by weight, 0.67 parts by weight of dimethylsilicone having a viscosity of 100 cs, and 0.7 parts by weight of potassium oleate, 0.002 parts by weight of ethylenediamine tetrasodium acetate, 0.002 parts by weight of ferrous sulfate, 0.01 parts by weight of sodium formaldehyde sulfoxylate, and diiso After addition of 0.05 parts by weight of propylbenzene hydroperoxide and polymerization for 10 hours, 1.0 parts by weight of potassium oleate was added with a stabilizing emulsifier to obtain a styrene-butadiene rubber latex having a particle size of 850 mm 3, and a final polymerization conversion thereof was 98%.

(1 step polymerization)

75 parts by weight of the obtained rubber latex (solid) was charged to a closed reactor, and charged with nitrogen, and 10 parts by weight of methyl methacrylate, 2 parts by weight of ethyl acrylate and 0.2 parts by weight of potassium oleate as an additive, sodium 0.01 parts by weight of formaldehyde sulfoxylate and 0.15 parts by weight of t-butyl hydroperoxide were added to the rubber latex continuously at 40 ° C. for 5 minutes, and then polymerized for 1 hour.

(Two stage polymerization)

13 parts by weight of styrene and 0.2 parts by weight of potassium oleate, 0.01 parts by weight of sodium formaldehyde sulfoxylate and 0.15 parts by weight of t-butyl hydroperoxide were added to the first-stage polymer at 50 ° C. for 10 minutes. After the addition, the polymerization was carried out for 1 hour.

Example 6

(1 step polymerization)

75 parts by weight of the rubber latex prepared in Example 1 (solid) was charged into a sealed reactor, and charged with nitrogen, and 10 parts by weight of methyl methacrylate, 2 parts by weight of ethyl acrylate, and dimethylsilicone having a viscosity of 100. 0.5 parts by weight, and 0.2 parts by weight of potassium oleate, 0.01 parts by weight of sodium formaldehyde sulfoxylate and 0.08 parts by weight of t-butyl hydroperoxide were added to the rubber latex continuously at 40 ° C. for 5 minutes, and then 1 Polymerized for time.

(Two stage polymerization)

13 parts by weight of styrene and 0.2 parts by weight of potassium oleate, 0.01 parts by weight of sodium formaldehyde sulfoxylate and 0.08 parts by weight of t-butyl hydroperoxide were added to the first-stage polymer at 50 ° C. for 10 minutes. After the addition, polymerization was carried out for 1 hour.

[Comparative Example]

Comparative Example 1

In Example 1, dimethylsilicone was prepared in the same manner as in Example 1 except that it was not used.

Comparative Example 2

In Example 1, except that 0.5 parts by weight of dimethylsilicon having a viscosity of 10 was prepared in the same manner as in Example 1.

Comparative Example 3

In Example 1, except that 0.5 parts by weight of dimethylsilicon having a viscosity of 30,000 was prepared in the same manner as in Example 1.

Comparative Example 4

In Example 1, except that 2.0 parts by weight of dimethylsilicon having a viscosity of 100 was used in the same manner as in Example 1.

Comparative Example 5

(Manufacture of rubber latex)

It was manufactured in the form of a glow-out during the rubber latex manufacturing process, 180 parts by weight of ion-exchanged water, 1.1 parts by weight of a buffer solution and 0.35 parts by weight of potassium oleate were used as a high-pressure reactor, 0.0047 parts by weight of ethylenediamine tetrasodium acetate, and No. 1 sulfate. 0.003 parts of iron, 0.02 parts of sodium formaldehyde sulfoxylate and 0.11 parts of diisopropylbenzene hydroperoxide were initially charged.

23 parts by weight of butadiene, 17 parts by weight of styrene, and 0.2 parts by weight of divinylbenzene were added thereto in one step to polymerize at 40 ° C. for 7 hours, and 53 parts by weight of butadiene, 6 parts by weight of styrene, and 0.8 parts of divinylbenzene in two steps. By weight, potassium oleate 0.7, 0.002 parts by weight of ethylenediamine tetrasodium acetate, 0.002 parts by weight of ferrous sulfate, 0.01 parts by weight of sodium formaldehyde sulfoxylate and 0.05 parts by weight of diisopropylbenzene hydroperoxide were added and polymerized for 15 hours. . 1.0 parts by weight of potassium oleate was then added as a stabilizing emulsifier to obtain a styrene-butadiene rubber latex with a particle size of 1900 mm 3, with a final polymerization conversion of 95%.

(1 step polymerization)

It carried out in the same manner as in Example 1.

(Two stage polymerization)

In the two-step polymerization of Example 1, dimethylsilicone was carried out in the same manner as in Example 1 except that it is not used.

Comparative Example 6

(Manufacture of rubber latex)

After the rubber latex manufacturing process, a large particle of rubber was produced by the agglomeration method.

75 parts by weight of the rubber latex prepared in Example 1 was taken into a reactor, and 0.2 parts by weight of sodium lauryl salt emulsifier was added as a stabilizer, and 0.05 parts by weight of 3% acetic acid solution was added while stirring for about 10 minutes. At this time, the latex of rubber latex partially increased the particle size and the final particle size was 2000 mm 3. After the desired particle size was reached, the acidity was restored to 0.05% by weight of 2% aqueous sodium hydroxide solution.

(1 step polymerization)

The same procedure as in Example 1 was carried out except that the above-mentioned particle size rubber rubber latex was used.

(Two stage polymerization)

In the two-step polymerization of Example 1, dimethylsilicone was carried out in the same manner as in Example 1 except that it is not used.

Experimental Example

The graft copolymers prepared in Examples 1 to 6 and Comparative Examples 1 to 6 were added with acid and heat while stirring with an antioxidant to separate the polymer and water, followed by dehydration and drying to obtain MBS powder, which was obtained by vinyl chloride resin. The physical properties were evaluated by mixing with, and the results are shown in Table 1 below.

The vinyl chloride masterbatch includes 100 parts by weight of vinyl chloride resin (polymerization degree 800), 1.5 parts by weight of tin-based heat stabilizer, 1.0 part by weight of internal lubricant, 0.5 part by weight of external lubricant, 0.2 part by weight of processing aid, and 0.3 part by weight of pigment. The product was sufficiently mixed at a temperature of 130 ° C. using a high speed stirrer and cooled.

Property evaluation

1) Light transmittance, haze value-To evaluate the properties of vinyl chloride resin, 7 parts by weight of impact modifier was added to 100 parts by weight of vinyl chloride resin, and 0.5 mm thick using a roll of 190 ° C. The sheet was prepared, and a sheet having a thickness of 3 mm was prepared using a heating press. The prepared 3 mm sheet was exquisitely cut to measure light transmittance and haze value using a haze meter to measure optical properties of ASTM standards.

2) Saw blade impact strength-The impact strength of the 0.5 mm sheet obtained by the roll processing in 1) above is relative to the original when the rotation speed of the saw blade is changed by using the saw blade having the number of saw blades 6 per unit inch of diameter 200 mm. The rotation rate was about 50%.

division transparency Haze Saw Blade Impact Strength (23 ℃) Saw Blade Impact Strength (-10 ℃) Etc Example 1 73.0 3.2 850 450 - Example 2 73.5 3.0 820 460 - Example 3 72.5 3.5 850 430 - Example 4 73.6 3.0 800 420 - Example 5 72.6 3.3 850 450 - Example 6 73.0 3.2 850 450 - Comparative Example 1 73.3 3.0 600 300 - Comparative Example 2 72.4 4.2 800 400 Thermochromic Comparative Example 3 72.5 4.3 820 400 - Comparative Example 4 70.6 6.3 730 400 Reduced transparency Comparative Example 5 68.7 7.2 850 480 Reduced transparency Comparative Example 6 70.1 6.8 900 500 Reduced transparency

As shown in Table 1, the graft copolymers of Examples 1 to 4 containing 0.001 to 10 parts by weight of linear dimethylsilicon having a viscosity of 20 to 1,000 cs had higher impact resistance, transparency, and haze value than those of Comparative Example 1. It was found to be excellent. In addition, it can be seen from Example 5 or 6 that the impact strength was improved while maintaining the transparency when using 0.001 to 1.0 parts by weight of linear dimethyl silicone of 20 to 1,000 cs regardless of the addition time.

On the other hand, in Comparative Example 2 containing a linear dimethylsilicon having a viscosity of less than 20 cs it can be seen that the phenomenon of discoloration due to a decrease in thermal stability, a comparative example containing a linear dimethylsilicon having a viscosity of 30,000 cs In the case of 3, the impact strength was maintained, but the transparency and the haze value were found to be inhibited. In addition, in the case of Comparative Example 4 in which the linear dimethylsilicon content of 20 to 1,000 cs exceeded 1.0 part by weight, the transparency and the haze of the vinyl chloride resin composition were inhibited through Comparative Example 4.

Through Comparative Examples 5 or 6, compared to the method for increasing the size of rubber latex, the present invention was able to confirm that the use of a small amount of additives not only shortened many times and complicated processes required for increasing the size, but also had excellent transparency and haze value. .

As described above, according to the present invention, a methyl methacrylate-butadiene-styrene copolymer composition having excellent impact resistance, transparency, and processability can be prepared, and ultimately, vinyl chloride resin having excellent impact resistance can be prepared. have. In addition, it is possible to improve transparency and impact strength at the same time by adding a small amount of additives without increasing the particle size of the rubber latex, as well as to save the complicated process and time required to increase the particle size.

Claims (10)

Methyl methacrylate including 70 to 80 parts by weight of rubber latex, 5 to 25 parts by weight of alkyl methacrylate, 0.0001 to 5 parts by weight of acrylate, 5 to 30 parts by weight of ethylenically unsaturated aromatic compound, and 0.001 to 1.0 parts by weight of linear dimethylsilicone. Late-butadiene-styrene copolymer. The method of claim 1, Methyl methacrylate-butadiene-styrene copolymer having a viscosity of 20 to 1,000 cs (centistokes) of the linear dimethylsilicone. In the method of preparing a methyl methacrylate-butadiene-styrene copolymer comprising the step of graft polymerization by adding alkyl methacrylate, acrylate, and ethylenically unsaturated aromatic compound to the rubber latex, the graft polymerization has a viscosity of 20 A method for producing a methyl methacrylate-butadiene-styrene copolymer, which is carried out by adding linear dimethyl silicone of ˜1,000 cs (centistokes). The method of claim 3, wherein a) 5 to 25 parts by weight of alkyl methacrylate and 70 to 80 parts by weight of rubber latex Linear dimethylsilicone having 0.0001-5 parts by weight and a viscosity of 20-1,000 cs Add 0.001 to 1.0 parts by weight and graft polymerization to prepare a one-step polymer. The step; And b) an ethylenically unsaturated aromatic compound in the first polymer prepared in step a) To prepare a two-stage polymer by adding 5 to 30 parts by weight and graft polymerization system Method for producing a methyl methacrylate-butadiene-styrene copolymer comprising a. The method of claim 3, wherein a) 5 to 25 parts by weight of alkyl methacrylate and 70 to 80 parts by weight of rubber latex, and arc 0.0001-5 parts by weight of grate is added and graft polymerization is carried out to obtain the first stage polymer. Manufacturing; And b) an ethylenically unsaturated aromatic compound in the first polymer prepared in step a) 5 to 30 parts by weight, and linear dimethyl silicone having a viscosity of 20 to 1,000 cs 0.001 to 1.0 Adding two parts by weight and graft polymerizing to prepare a two-stage polymer Method for producing a methyl methacrylate-butadiene-styrene copolymer comprising a. Preparing a rubber latex; And graft polymerization by adding an alkyl methacrylate, an acrylate, and an ethylenically unsaturated aromatic compound to the rubber latex, wherein the preparation of the rubber latex is performed in the manufacturing method of the methyl methacrylate-butadiene-styrene copolymer. A process for producing a methyl methacrylate-butadiene-styrene copolymer, which is carried out by adding linear dimethyl silicone having a viscosity of 20 to 1,000 cs (centistokes). 4. The method of claim 3 wherein the manufacture of the rubber latex V) 65 to 85 parts by weight of butadiene; Ii) 5 to 35 parts by weight of vinyl monomers; And Iii) in 0.001-1.0 linear dimethyl silicone having a viscosity of 20-1,000 cs (centistokes) Part A method for producing a methyl methacrylate-butadiene-styrene copolymer by emulsion polymerization. 8. The method according to claim 7, wherein the emulsion polymerization further comprises 0.1 to 5.0 parts by weight of a graft crosslinking agent. The method of claim 8, wherein the graft crosslinking agent is divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, A method for producing a methyl methacrylate-butadiene-styrene copolymer selected from the group consisting of aryl methacrylate and 1,3-butylene glycol diacrylate. The vinyl chloride resin containing the copolymer of methylmethacrylate-butadiene-styrene of Claim 1.