KR20120061173A - Method for Preparing Graft-copolymer Latex Having GoodThermo Stability - Google Patents

Abstract

PURPOSE: A manufacturing method of graft latex is provided to manufacture an acrylonitrile-butadiene-styrene based graft having excellent polymerization stability, mechanical property and thermal stability in high rubber content without using an emulsifier. CONSTITUTION: A manufacturing method of graft latex comprises: a step of manufacturing graft copolymer latex by graft-polymerizing 70-75 weight% of butadiene based rubber, 20-25 weight% of a mixture of a hydrophilic monomer, a styrene based monomer, and an acrylonitrile based monomer without addition of an emulsifier. The hydrophilic monomer is one or more selected from acrylic acid, methacrylic acid, sodium p-styrenesulfonate, sodium slat of 2-sulfoethylmethacrylate, sodium undecylenic isetionate, sodium metharyl sulfonate, etc.

Description

Method for preparing graft copolymer latex having excellent thermal stability {Method for Preparing Graft-copolymer Latex Having GoodThermo Stability}

The present invention relates to a method for producing acrylonitrile-butadiene-styrene graft copolymer latex, and more particularly, acrylonitrile-butadiene-styrene graft air that can prevent thermal stability deterioration due to the use of an emulsifier. It relates to a method for producing coalesced latex

As one of the methods of manufacturing the ABS resin, a method of mixing and extruding a high rubber content ABS graft copolymer powder produced by emulsion polymerization and a SAN resin produced by bulk polymerization is known. This method can freely adjust the content of the rubber according to the blending ratio, it is possible to produce a variety of grade products, which is advantageous for the production method of small quantity multi-products.

The graft ABS copolymer is mainly prepared by graft polymerization of styrene and acrylonitrile together with an initiator and an emulsifier in a rubber latex prepared by emulsion polymerization to prepare a graft copolymer latex, and coagulation drying to prepare a powder form. Used. However, a large amount of emulsifier used in the manufacturing process remains in the product, which is a major cause of lowering the thermal stability of the final product.

Accordingly, a method of reducing the amount of the emulsifier was also considered, but when the amount of the emulsifier is reduced, the stability of the reaction is decreased, the emulsion system is broken, and there is a problem in which aggregates are formed in the form of a residue. Therefore, the thermal stability of the final product is to introduce the antioxidant in the process of extruded by mixing the graft copolymer powder and SAN, or to increase the washing time of the powder in the process of coagulation drying the latex to increase the residual amount of the emulsifier Reducing measures have been used.

In order to improve such a problem, Korean Patent Laid-Open Publication No. 10-2004-0057408 attempted to improve thermal stability by introducing a reactive emulsifier, but the reactive product has a higher price than a low molecular weight emulsifier commonly used in the final product. Not only is it a price increase factor, but there is a problem in that it contains the emulsifier.

Accordingly, there is a continuing need for a new method that can more fundamentally solve the problems caused by the use of emulsifiers.

The technical problem to be solved in the present invention is to provide a new manufacturing method that does not use an emulsifier in the graft polymerization process.

Another technical problem to be solved in the present invention is to provide a new manufacturing method that can prevent the destabilization of the polymerization or degradation of the physical properties of the final product generated when the emulsifier is not used in the graft polymerization process.

In addition, another problem to be solved by the present invention is to provide a new ABS resin having good thermal stability and excellent physical properties by not using an emulsifier in the graft polymerization process.

In order to achieve the above object, the graft copolymer production method of the present invention grafts 20-25% by weight of a mixture of hydrophilic monomer, styrene monomer, and acrylonitrile monomer in 70-75% by weight of butadiene rubber. It is characterized by superposing | polymerizing.

Although not limited in theory, the hydrophilic monomer is grafted to butadiene rubber together with styrene and acrylonitrile, thereby increasing the stability of the polymerized particles, and graft polymerization is performed without adding an emulsifier.

In the present invention, the hydrophilic monomer refers to a monomer copolymerizable with SAN and having a solubility in water of at least 5 g per 100 g of water. For example, 1 type from the group which consists of acrylic acid, methacrylic acid, sodium parastyrene sulfonate, the sodium salt of 2-sulfoethyl methacrylate, sodium undecylenic isethionate, sodium metaaryl sulfonate, etc. Is chosen. Particularly preferably, sodium parastyrenesulfonate may be used, which includes a benzene group similar to styrene and has good compatibility with the SAN forming the matrix, which may prevent degradation of physical properties.

In the practice of the present invention, the hydrophilic monomer may be used in the graft copolymer of 0.05-3 parts by weight, more preferably 0.1-2 parts by weight, even more preferably in the range of 0.2-1.0 parts by weight. good. If the content of the hydrophilic monomer exceeds the above range, the compatibility with the SAN matrix may be lowered and the physical properties may be lowered.If the content of the hydrophilic monomer does not reach the above range, the stability of the particles during the polymerization process is lowered, causing unwanted aggregates. Will be formed.

In the present invention, the butadiene-based rubber is made of a latex form dispersed in a rubber particle is prepared by emulsion polymerization. In the present invention, the butadiene rubber refers to a rubber obtained by copolymerizing a butadiene monomer, a small amount of vinyl monomer copolymerizable with butadiene and butadiene. The vinyl monomer copolymerizable with the butadiene is, for example, styrene or acrylonitrile, but is not limited thereto. The monomer copolymerizable with butadiene in the butadiene-based rubber is included in 30 wt% or less, more preferably 25 wt% or less, even more preferably 20 wt% or less, most preferably 10 wt% or less.

In the present invention, the butadiene-based rubber is preferably used as 70 to 75 parts by weight of the total monomers during graft polymerization, when less than 70 parts by weight, the efficiency of the thermoplastic resin is low, not only increases the production cost, but also the reaction system is unstable. There is a problem of deterioration, and when it exceeds 75 parts by weight, there is a problem in that the amount of monomer that can be grafted is insufficient and the graft rate is lowered.

In the present invention, the monomer grafted to the butadiene-based rubber is preferably a semi-continuous type in which some monomers are initially added in a batch, and the remaining monomers are continuously added to maintain the stability of the reaction system.

In the practice of the present invention, the monomer to be grafted is a mixed monomer of styrene and acrylonitrile that is added in a batch, so that a relatively small amount of hydrophilic monomer can effectively participate in the stability of the reaction system. The monomer to be added and continuously added is preferably a mixture of hydrophilic monomers.

In the present invention, it is preferable to stabilize the reaction using a monomer to be batch-injected using a hydrophilic initiator to be ionized, such as sodium potassium sulfate, and the monomer containing the hydrophilic monomer is a redox-based initiator, for example It is better to use peroxide based catalyst.

According to a preferred aspect of the present invention, a styrene monomer and an acrylonitrile monomer are added to a butadiene rubber in a batch to polymerize with a hydrophilic initiator, and a hydrophilic monomer, a styrene monomer, and an acrylonitrile are mixed and continuously polymerized with a peroxide catalyst. Consists of steps.

The present invention relates to a method for producing acrylonitrile-butadiene-styrene graft copolymer latex, and more particularly, to a method for preparing acrylonitrile-butadiene-styrene graft copolymer prepared by emulsion polymerization. Content is 70% or more, does not include an emulsifier, and a batch administration of a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a hydrophilic initiator, an activator and a molecular weight regulator to initiate a reaction, after completion of the reaction aromatic vinyl compound And a method of preparing a graft copolymer and a graft copolymer prepared by the method comprising the step of continuously reacting a monomer made of a vinyl cyan compound, a redox initiator, and a hydrophilic monomer. It relates to a composition.

The graft copolymer latex prepared according to the present invention is optionally mixed with a styrene-acrylonitrile copolymer prepared by continuous emulsion polymerization in a proportion to prepare a powder in a conventional manner, and then bulk styrene-acrylic used in the related art. Extrusion and injection molding with a copolymer of ronitrile can produce an acrylonitrile-butadiene-styrene copolymer resin that maintains excellent mechanical properties such as impact resistance and tensile strength and natural color.

In order to achieve the above object, the present invention is characterized by using a hydrophilic monomer and a hydrophilic initiator in acrylonitrile-butadiene-styrene graft copolymer having a high rubber content of 70% or more without using an emulsifier It provides a method for producing an acrylonitrile-butadiene-styrene graft copolymer.

In addition, the present invention provides a thermoplastic resin composition

a) graft copolymer prepared by the above method;

b) styrene-acrylonitrile (emulsified SAN) resin prepared by emulsion polymerization and

c) Styrene-acrylonitrile (bulk SAN) resins prepared by bulk or solution polymerization

It provides an acrylonitrile-butadiene-styrene-based thermoplastic resin composition comprising a

In order to achieve the above object, the present invention in the production of acrylonitrile-butadiene-styrene graft copolymer latex a) the average particle diameter of 0.30 ~ 0.35㎛, gel content of 80 ~ 95% by weight rubber latex Administering 70 to 75 parts by weight, including 1 to 15 parts by weight of a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound, a hydrophilic initiator, an activator and a molecular weight modifier in a batch to initiate a reaction, without including an emulsifier,

b) reacting the reactant of step a) by continuously administering 10 to 29 parts by weight of a monomer composed of an aromatic vinyl compound and a vinyl cyan compound, and a hydrophilic monomer that plays the same role as a redox initiator and an emulsifier. It provides a method for producing a graft copolymer.

In the present invention, the aromatic vinyl compound is at least one selected from the group consisting of styrene, alphamethylstyrene, alphaethylstyrene, and paramethylstyrene, and preferably styrene. In the present invention, the vinyl cyan compound is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile, preferably acrylonitrile.

In the present invention, the hydrophilic initiator is at least one selected from the group consisting of sodium persulfate, caloric persulfate and ammonium persulfate, preferably potassium persulfate is preferably potassium persulfate.

In the present invention, the redox initiator is at least one selected from the group consisting of tertiary butyl hydroperoxide, cumene hydroperoxide, isopropylbenzene hydroperoxide, preferably the hydroperoxide redox initiator.

In the present invention, the activator is selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium lirronate, sodium sulfate and the like.

In the present invention, the molecular weight regulator is preferably mercaptans.

The graft copolymer prepared in the present invention is characterized in that the graft ratio is 30% to 45%.

Hereinafter, the present invention will be described in detail.

a) reaction initiation step

70 to 75 parts by weight of a rubber latex having an average particle diameter of 0.30 to 0.35 μm and a gel content of 80 to 95 wt% was maintained at 55 to 65 ° C. through a heat exchanger, and did not contain an emulsifier, i) a) aromatic 1 to 15 parts by weight of a monomer mixture consisting of a vinyl compound and i) b) a vinyl cyan compound, ii) a hydrophilic initiator, iii) an activator, and iv) a molecular weight modifier are administered in a batch to maintain the reaction time for 10 to 60 minutes to initiate the reaction. It's a step.

The average particle diameter of the rubber latex is 0.30 ~ 0.35㎛, gel content is preferably 80 to 95% by weight. If the average particle diameter is less than 0.30㎛, there is a problem of lowering the impact strength according to the small rubber particle diameter, if the average particle diameter exceeds 0.35㎛ there is a problem that the surface gloss is lowered, if the gel content is less than 80% by weight surface graft lowering As a result, the overall mechanical properties are lowered, and when it exceeds 95% by weight, the impact strength according to the graft reduction and the glass transition temperature is lowered.

The input temperature of the rubber latex using the heat exchanger is preferably maintained at 55 ~ 65 ℃. When the reaction temperature is lower than 55 ° C., the reaction time may be long due to the low reaction temperature. If the reaction temperature is higher than 65 ° C., there is difficulty in controlling the process due to a large amount of reaction heat in the subsequent reaction initiation step.

As the aromatic vinyl compound, styrene, alphamethyl styrene, paramethyl styrene, or the like may be used, and styrene is particularly preferable.

As the vinyl cyan compound, acrylonitrile or ethacrylonitrile may be used, and in particular, acrylonitrile is preferably used.

It is preferable to mix and use the monomer mixture ratio of the said aromatic vinyl compound and a vinyl cyan compound in 70-80: 20-30 weight ratio. When the vinyl cyan compound is less than 20 parts by weight, it is difficult to knead when mixing with the SAN resin produced by bulk or solution polymerization, and the impact strength is significantly lowered. When the vinyl cyan compound exceeds 30 parts by weight, it is also produced by bulk or solution polymerization. Kneading with the SAN is difficult, and there is a problem that the natural color becomes yellow.

As mentioned above, the monomer mixture which consists of an aromatic vinyl compound and a vinyl cyan compound is a maleimide, N-methyl maleimide, N-ethyl maleimide, N-propyl maleimide, N-phenyl maleimide, methyl methacrylate other than the said component. , Vinyl monomers such as methyl acrylate, butyl acrylate, acrylic acid, maleic anhydride, or mixtures thereof can be further used. At this time, it can be used in a small amount in the vinyl monomer mixture.

The monomer mixture of i) preferably comprises 1 to 15 parts by weight of 25 to 30 parts by weight based on 100 parts by weight of the total monomers used in preparing the graft copolymer. If it is less than 1 part by weight, there is a problem of lowering mechanical properties, and if it exceeds 15 parts by weight, there is a problem that control of reaction heat is difficult.

The hydrophilic initiator of ii) is preferably included in a total of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total monomers used in preparing the graft copolymer. If the content is less than 0.05 parts by weight, there is a problem that the graft is lowered, and when the content is more than 0.5 parts by weight, the graft copolymer of a low molecular weight is produced, there is a problem that the mechanical properties are lowered.

The said ii) hydrophilic initiator can be used individually or in mixture from the group which consists of sodium persulfate, potassium persulfate, and ammonium persulfate.

The activator of iii) is used together with the hydrophilic initiator and redox initiator of ii) to enable the polymerization reaction even below 50 ° C, and to promote the polymerization reaction according to the amount used, and to improve the graft rate. Do it.

The activating agent may be sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium lirroline, or sodium sulfate, preferably lactose, sodium pyrrolate And ferrous sulfate.

The activator is preferably included in a total of 0.051 to 0.51 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer, more preferably 0.03 to 0.3 parts by weight of lactose, 0.02 to 0.2 parts by weight of sodium phosphate Parts and 0.001 to 0.01 parts by weight of ferrous sulfate. If the content is less than 0.051 or more than 0.51, there is a problem that it is difficult to balance the mechanical properties.

Mercaptans may be used as the molecular weight regulator of iv), and in particular, tertiary dodecyl mercaptan is preferably used.

The molecular weight modifier is preferably included in 0.1 to 0.5 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer production.

b) continuous administration of monomers

This step is a step in which the reaction of step a) is terminated and the monomers consisting of aromatic vinyl compound and vinyl cyan compound, i) redox initiator, and ii) hydrophilic monomer are continuously reacted with the reactants.

Specifically, in this step, the monomer mixing ratio of the aromatic vinyl compound and the vinyl cyan compound is a total of 10 to 29 parts by weight of the monomer mixture consisting of 70 to 80: 20 to 30 parts by weight, 0.01 to 0.5 parts by weight of hydroperoxide redox initiator, hydrophilic monomer The reaction is carried out while maintaining the polymerization temperature at 65 ~ 80 ℃ while continuously administered 0.05 to 0.5 parts by weight for 2 to 4 hours.

The redox initiator of i) is selected from the group consisting of tertiary butyl hydroperoxide, cumene hydroperoxide and isopropylbenzene hydroperoxide, preferably the hydroperoxide redox initiator.

The redox initiator is preferably included in a total of 0.01 to 0.5 parts by weight based on 100 parts by weight of the total monomers used in preparing the graft copolymer. If the content is less than 0.01 parts by weight, there is a problem that the graft is lowered, and if the content is more than 0.5 parts by weight, the graft copolymer of a low molecular weight is produced, there is a problem that the mechanical properties are lowered.

Examples of the hydrophilic monomer of ii) include acrylic acid, methacrylic acid, sodium parastyrene sulfonate, sodium salt of 2-sulfoethyl methacrylate, sodium undecylenic isethionate, sodium metaaryl sulfonate, and the like. 1 or more types are selected from the group which consists of. Preferably sodium parastyrenesulfonate.

The hydrophilic monomer is preferably included in a total of 0.05 to 0.5 parts by weight based on 100 parts by weight of the total monomer used in the graft copolymer production. If the content is less than 0.05 parts by weight, there is a problem that the polymerization stability is lowered, and if the content exceeds 0.5 parts by weight, the content of expensive hydrophilic monomer is increased to increase the manufacturing cost.

The final graft ratio of the graft copolymer of the present invention prepared by the above method is preferably 25% or more, more preferably 30% to 45%.

In the present invention, the weight part of the rubber latex is based on the solid rubber contained in the latex.

The present invention also provides a thermoplastic resin composition comprising a graft copolymer prepared as described above and a styrene-acrylonitrile (bulk SAN) resin prepared by bulk or solution polymerization.

a) graft copolymer prepared by the above method;

b) styrene-acrylonitrile (emulsified SAN) resin prepared by emulsion polymerization and

c) Styrene-acrylonitrile (bulk SAN) resins prepared by bulk or solution polymerization

It provides an acrylonitrile-butadiene-styrene-based thermoplastic resin composition comprising a

In the present invention, a) graft copolymer 72 to 93 parts by weight, b) 7 to 28 parts by weight of styrene-acrylonitrile (emulsion SAN) prepared by emulsion polymerization having a rubber content of 50 to 65% by weight Prepare ABS powder. When manufacturing the ABS powder with rubber content of 65% or more, the apparent specific gravity decreases, which leads to high packaging and logistics costs. The ABS powder with rubber content of 50% or less becomes expensive due to the high powder content in the final ABS product.

 It is used together with the bulk SAN and the ABS powder to produce the final ABS product, the type and content of the bulk SAN is determined according to the use, in general, it is good for mechanical properties to use a bulk SAN of 50 to 80% by weight. In the present invention, SAN326 of Kumho Petrochemical was used.

The ABS powder prepared by the above method is preferably included in an amount of 20 to 50 parts by weight based on 100 parts by weight of the thermoplastic resin composition. When the content is less than 20 parts by weight, the impact strength is lowered. And a decrease in surface glossiness.

According to the present invention, there is an effect of providing an acrylonitrile-butadiene-styrene-based graft copolymer having excellent polymerization stability and excellent thermal stability without using an emulsifier and a thermoplastic resin composition comprising the same.

The present invention in one aspect of the graft polymer, graft air consisting of 70-75% by weight of butadiene-based rubber, SAN 20-25% by weight of the styrene monomer and acrylonitrile monomer in a weight ratio of 70:30 to 80:20 The copolymer provides a graft copolymer comprising 0.01-3% by weight of parastyrenesulfonate and having a graft ratio of 25-45%.

The present invention is a high rubber content of the hyava ABS, comprising 72-93 parts by weight of the graft copolymer according to the invention and SAN 7-28 parts by weight, the content of butadiene is characterized in that 50-65% by weight Hyava provides ABS powder.

According to the present invention, there is an effect of providing an acrylonitrile-butadiene-styrene-based graft copolymer having excellent polymerization stability and excellent thermal stability without using an emulsifier and a thermoplastic resin composition comprising the same.

Example 1

In a nitrogen-substituted polymerization reactor, 70 parts by weight of butadiene rubber latex having an average particle diameter of 0.33 μm and a gel content of 85% was introduced at 62 ° C. through a heat exchanger, and 9 parts by weight of styrene, 3 parts by weight of acrylonitrile, and 0.25 weight of potassium persulfate were added. Part, 0.12 parts by weight of lactose, 0.05 parts by weight of sodium pyrolate, 0.002 parts by weight of ferrous sulfide, and 0.2 parts by weight of tertiary dodecyl mercaptan were continuously or collectively administered, and after 45 minutes, the temperature in the reactor was 65 ° C.

Since 13.5 parts by weight of styrene, 4.5 parts by weight of acrylonitrile, 0.085 tertiary butyl hydroperoxide, 0.3 parts by weight of sodium parastyrenesulfonate was continuously administered for 180 minutes. At this time, the reaction temperature was raised from 65 ℃ to 75 ℃.

The graft rate of the polymerized graft copolymer latex was 35%, the polymerization conversion was 99.5%, and the polymerization coagulum was 0.01%.

Then, a graft copolymer latex having a rubber content of 60.2% was prepared by mixing an emulsified SAN at a ratio of 86:14 to the polymerization latex, agglomerated with MgSO ₄ , and dried to obtain a powdered ABS powder.

The graft rate is 2g of powdered graft copolymer resin with 100 mL of acetone for 24 hours to dissolve the grafted styrene copolymer in the rubber component, and then separate the gel and the sol by ultracentrifugation in accordance with Equation 1 Calculated.

[Equation 1]

Graft ratio = [(gel-rubber weight)] / rubber weight] / 100

Examples 2 to 3

The graft copolymer was prepared by converting the content as shown in Table 1, but using the same composition as in Example 1.

[Comparative Example]

Comparative Example 1

The graft copolymer was prepared in the same manner as in Example 1, except that the initiator type was used as the reaction type in the reaction initiation step.

Comparative Example 2

A graft copolymer was prepared in the same manner as in Example 1 except that sodium parastyrenesulfonate was not used in the monomer continuous administration step.

Comparative Example 3

The graft copolymer was prepared in the same manner as in Example 1 except that the initiator was used as potassium persulfate in the monomer continuous administration step.

Comparative Example 4

The graft copolymer was prepared in the same manner as in Example 1, except that sodium parastyrene sulfonate was not used in the monomer continuous administration step and potassium oleate was used.

It was confirmed that the graft copolymer latex stability prepared in Comparative Examples 1 and 2 was significantly lower than those of Examples 1 to 3 above.

The graft copolymer prepared in Comparative Example 3 was confirmed that the final graft ratio is 23% inferior mechanical properties of the acrylonitrile-butadiene-styrene thermoplastic resin.

The graft copolymer prepared in Comparative Example 4 was excellent in mechanical properties, it was confirmed that the thermal stability is poor.

30 parts by weight of the graft copolymer resin prepared in Examples 1 to 3 and Comparative Examples 1 to 4, 75 parts by weight of a SAN resin having a weight average molecular weight of 100,000 and an acrylonitrile content of 25% and a lubricant 0.75, a heat stabilizer 0.25 After adding the parts by weight and mixing, extrusion and injection molding to prepare a specimen that becomes 18% by weight of the final rubber. Using the specimen, the content of coagulated product, Izod impact strength, tensile strength and injection residence thermal stability were measured by the following method, and the results are shown in Table 2 below.

A) Content of the coagulum: The prepared acrylonitrile-styrene-acrylonitrile graft copolymer latex was filtered through a 200 mesh wire mesh to dry the coagulum that did not pass through the mesh at 150 ° C. for 30 minutes, and then weighed. The content of coagulant for

B) Izod impact strength test: measured according to the method of ASTM D256. At this time, the thickness of the specimen was 1/4 inch.

C) Tensile strength: Tensile strength was measured by ASTM D638 method.

D) Thermal stability of injection flow: After the resin was held for 15 minutes in the injection screw set at 250 ° C, the molded specimen exhibited a discoloration degree (? E) as shown in Equation 1 below, wherein ΔE was a hunter before and after staying. It is the arithmetic mean value of the Hunter Lab value, and the closer to 0, the better the thermal stability.

Equation 1

ΔE = ((L-L ') ² + (a-a') ² + (b-b ') ² } ^1/2

Through Table 2, the thermoplastic resin prepared by using the graft copolymers of Examples 1 to 3 prepared according to the present invention has mechanical strength and thermal stability while maintaining latex stability as compared to Comparative Examples 1 to 4. It was confirmed that excellent.

Claims (19)

A graft copolymer latex is prepared by graft polymerizing 20-25% by weight of a mixture of hydrophilic monomer, styrene monomer, and acrylonitrile monomer in 70-75% by weight of butadiene-based rubber without further addition of an emulsifier. Way. The method of claim 1, wherein the hydrophilic monomer is acrylic acid, methacrylic acid, sodium parastyrene sulfonate, sodium salt of 2-sulfoethyl methacrylate, sodium undecylenic isethionate, sodium metaaryl sulfonate, and the like. At least one selected from the group consisting of. The method of claim 1 wherein the hydrophilic monomer is parastyrenesulfonate. 4. The method of claim 3, wherein the parastyrenesulfonate is used in an amount of 0.05-3 parts by weight based on 100 parts by weight of the graft copolymer. The method of claim 1, further comprising mixing the graft copolymer latex into a SAN latex to produce a powder in a rubber content of 60-65%. The method of claim 5, further comprising mixing the powder with a bulk polymerized SAN to produce a rubber content of 10-30 wt% ABS resin. a) Monomer mixture 1 to 70 to 75 parts by weight of a rubber latex having an average particle diameter of 0.30 to 0.35 µm and a gel content of 80 to 95% by weight, containing no emulsifier, and containing an aromatic vinyl compound and a vinyl cyan compound Administering 15 parts by weight of a hydrophilic initiator, an activator and a molecular weight modifier in a batch to initiate a reaction;
b) reacting the reactant of step a) by continuously administering 10 to 29 parts by weight of a monomer composed of an aromatic vinyl compound and a vinyl cyan compound, and a hydrophilic monomer that plays the same role as a redox initiator and an emulsifier;
Method for producing a graft copolymer latex comprising a. The method of claim 7, wherein
The step a) is carried out by maintaining the rubber latex at 55 ~ 65 ℃ through a heat exchanger, the reaction time after the start of the reaction is terminated for 10 to 60 minutes;
In step b), the reaction mixture of step a) is terminated and the monomer mixture ratio of the aromatic vinyl compound and the vinyl cyan compound is 70 to 80: 20 to 30 parts by weight of the total monomer mixture of 10 to 29 parts by weight, hydroperoxide redox Reacting while maintaining the polymerization temperature at 65 to 80 ° C. while continuously administering 0.01 to 0.5 parts by weight of the initiator and 0.05 to 0.5 parts by weight of the hydrophilic monomer for 2 to 4 hours;
Method for producing a graft copolymer latex, characterized in that. The method according to claim 7 or 8,
The aromatic vinyl compound is one or more selected from the group consisting of styrene, alphamethyl styrene, or paramethyl styrene. The method according to claim 7 or 8,
The vinyl cyan compound is one or more selected from the group consisting of acrylonitrile or ethacrylonitrile. The method according to claim 7 or 8,
Maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methyl methacrylate, methyl acrylate, butyl acrylate, acrylic acid, other than the above components of the monomer mixture, A method for producing a graft copolymer latex further comprising a vinyl monomer such as maleic anhydride or a mixture thereof. The method according to claim 7 or 8,
The hydrophilic initiator is used in the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate alone or mixed, the method for producing a graft copolymer latex. The method according to claim 7 or 8,
Wherein the activator is selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, lactose, dextrose, sodium lilolate, sodium sulfate, and the like. Process for producing graft copolymer latex The method according to claim 7 or 8,
The redox initiator is a method for producing a graft copolymer latex, characterized in that at least one selected from the group consisting of tertiary butyl hydroperoxide, cumene hydro peroxide, isopropylbenzene hydro peroxide. The method according to claim 7 or 8,
Examples of the hydrophilic monomers include acrylic acid, methacrylic acid, sodium, and the above-mentioned parastyrene sulfonate, sodium salt of 2-sulfoethyl methacrylate, sodium undecylenic isethionate, sodium metaaryl sulfonate, and the like. Method for producing a graft copolymer latex, characterized in that more than one species selected. The method according to claim 7 or 8,
The said molecular weight modifier is a mercaptan, The manufacturing method of the graft copolymer latex characterized by the above-mentioned. The method according to claim 7 or 8,
Method for producing a graft copolymer latex, characterized in that the graft ratio is 30% ~ 45%. A graft copolymer comprising 70-75% by weight of butadiene rubber and 20-25% by weight of styrene monomer and acrylonitrile monomer in a SAN 20-25% by weight ratio of 70:30 to 80:20, wherein parastyrenesulfonate is 0.01-3. Graft copolymer comprising a weight percent, graft rate is 25-45%. ABS powder comprising 72-93 parts by weight of the graft copolymer according to claim 18 and 7-28 parts by weight of SAN, the content of butadiene is 50-65% by weight.