KR20130057139A - Method of preparing graft copolymer - Google Patents

Abstract

PURPOSE: A manufacturing method of a graft copolymer is provided to be attach functional groups of a reactive emulsifier on the surface thereof without burying, thereby obtaining a graft copolymer with excellent glossy. CONSTITUTION: A manufacturing method of a graft copolymer comprises a step of manufacturing seeds by polymerizing an ethylene unsaturated monomer, crosslinking agent, emulsifier, polymerization initiator, and ion exchange water; a step of polymerizing a conjugated diene monomer, emulsifier, polymerization initiator, molecular weight controller, electrolyte, and ion exchange water to manufacture a large sized rubber latex including the seed and core; and a step of injecting the large sized rubber latex and injecting the monomer mixture, emulsifier, molecular weight controller, and polymerization initiator to conduct a graft copolymerization and obtaining an ABS graft copolymer.

Description

Method for preparing graft copolymers {Method of preparing graft copolymer}

The present invention relates to a method for producing a graft copolymer, and more particularly, in order to solve the problem of deterioration of glossiness or increase in gas generation amount due to desorption of a general emulsifier, a large diameter rubber latex including a seed and a core is added. In addition, a monomer mixture containing an aromatic vinyl compound and a vinyl cyan compound, an emulsifier, a molecular weight modifier and a polymerization initiator are added and graft copolymerized to prepare an ABS graft copolymer, wherein the reactive emulsifier is converted to 80 to 90%. Method to manufacture the graft copolymer with excellent gloss by improving the effect of latex stability or buried phenomenon by maximizing the effect by binding the functional group of the reactive emulsifier to the surface without buried in the particles It is about.

Emulsifiers in emulsion polymerization control particle size and latex stability. However, conventional surfactants can cause various problems because they do not covalently bond with the particles. For example, stability may be poor in extreme environments such as high shearing, freezing, or high ionic strength, and films made of latex may have poor adhesion in high humidity environments. . This is a problem caused by the emulsifier falling off the particle surface or the emulsifier is moved to the film surface. Therefore, the best way to solve this problem is to introduce a reactive surfactant that has the ability to chemically bind in the polymerization (polymerization). Responsive emulsifiers can be classified according to the point of time they participate in the reaction, insurfing the emulsifier that reacts at the beginning of the reaction, and surfmers and delivery of the emulsifiers involved in the reaction in the propagation process. Emulsifiers that react to a transfer reaction are called transsurfs, and the types of surfers include allyllic, maleic, styrenic, and acrylic systems. In addition, insurfs include azo compounds, and transsurfs include thiol compounds.

It has been stated that the reactivity ratio optimized for the reactive emulsifier to bind particles most efficiently is 0.5 <r comonomer <10, r surfactant-> 10 (HAS, Schoonbrood and JM Asua, Macromolecules, 30, 6034 (1997). However, this reactivity is effective only at the beginning of the reaction, and the reactivity of the emulsifier should increase gradually during the reaction. However, many researchers conclude that it is practically difficult to measure the value of the reactivity ratio between each emulsifier and comonomer before the reaction, and to find an emulsifier that increases itself during the reaction.

Thus, for efficient dosing of reactive emulsifiers, the reactivity of reactive emulsifiers can be changed by (a) adding less reactive monomers at the end of the process, or (b) changing reaction conditions such as temperature, pH, etc. Attempts have been made to change the profile of the emulsifier, such as to increase the rate of addition, (c) to increase the rate of addition over time, (d) to inhibit the possible growth of the particle size in the miniemulsion polymerization (HAS, Schoolbrood and JM Asua). , ibid). However, there is a problem in that the above method is not effective in terms of cost-effectiveness for industrial applications.

The present invention is to solve the problems of the prior art as described above, an object of the present invention is to determine the timing of the addition of the reactive emulsifier so that the functional group of the reactive emulsifier is attached to the surface without buried in the particles (buried) By maximizing the effect.

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 comprises the steps of (a) preparing a seed by polymerizing an ethylenically unsaturated monomer, a crosslinking agent, an emulsifier, a polymerization initiator and ion-exchanged water; (b) preparing a core by polymerizing a conjugated diene monomer, an emulsifier, a polymerization initiator, a molecular weight regulator, an electrolyte, and ion-exchanged water in the presence of the seed to prepare a large diameter rubber latex comprising the seed and the core; (c) A method for producing an ABS graft copolymer by adding the large-diameter rubber latex, adding a monomer mixture, an emulsifier, a molecular weight modifier, and a polymerization initiator containing an aromatic vinyl compound and a vinyl cyan compound, and graft copolymerization. In the step (c) it provides a method for producing an ABS graft copolymer, characterized in that to add a reactive emulsifier in a conversion rate of 80 to 90%.

The method for producing the ABS graft copolymer according to the present invention can improve the gloss value lowered due to the generation of gas generated by the general emulsifier falling off in the air, and has a problem of having a reactive reactive emulsifier having high reactivity due to the appropriate timing. That is, there is an effect that can solve the problem of degradation or buried phenomenon of latex stability due to the generation of polymer electrolyte.

When using a reactive emulsifier (0.1 ~ 0.5 parts by weight), the amount can be reduced than a general emulsifier (0.6 ~ 2.0 parts by weight). Also, when the emulsifier was added in a shot at a certain time, it was confirmed that the gloss value was improved compared to the case where the emulsifier was added in the form of a monomer mixture from the beginning.

ABS graft copolymer production method according to the present invention for achieving the above object comprises the steps of (a) preparing a seed by polymerizing an ethylenically unsaturated monomer, a crosslinking agent, an emulsifier, a polymerization initiator and ion-exchanged water; (b) preparing a core by polymerizing a conjugated diene monomer, an emulsifier, a polymerization initiator, a molecular weight regulator, an electrolyte, and ion-exchanged water in the presence of the seed to prepare a large diameter rubber latex comprising the seed and the core; (c) A method for producing an ABS graft copolymer by adding the large-diameter rubber latex, adding a monomer mixture, an emulsifier, a molecular weight modifier, and a polymerization initiator containing an aromatic vinyl compound and a vinyl cyan compound, and graft copolymerization. In step (c), the reactive emulsifier is characterized in that the conversion to 80 to 90%.

Responsive emulsifiers on the market are disadvantageous in terms of cost than general emulsifiers. Nevertheless, many attempts have been made because the use of reactive emulsifiers has better physical properties by overcoming the disadvantages of general emulsifiers, namely, deterioration of glossiness or increase in gas generation due to desorption. However, due to its reactivity, the reactive emulsifier having a double bond is already buried at the beginning of the reaction, or on the contrary, a large amount of polyelectrolyte is formed after the reaction, which may cause latex instability. Therefore, there is a need for a strategy that must be properly deposited on the surface so as not to cause the above problems.

By monitoring the graph of particle size, you can find out the interval where particles no longer grow. If the emulsifier is added at this time, the problem of buried emulsifier can be solved while the particle size is growing. Also, if the conversion rate is about 70-80%, the reactive emulsifier reacts by itself in water and the polymer electrolyte The problem of forming a solution may also be solved. Therefore, particle size and conversion are monitored over time to determine when to add emulsifier.

Hereinafter, the present invention will be described in detail.

In the present invention, when introducing a reactive emulsifier, an appropriate time point for determining the maximum surface deposition thereof is determined based on the conversion rate and particle size data over time.

And a smaller amount of reactive emulsifiers than conventional emulsifiers are added.

This can improve the gloss value lowered due to the generation of gas generated by the general emulsifier falling off during the process, and due to the input at the appropriate time, the problem of the reactive reactive emulsifier with high reactivity, that is, the formation of polymer electrolyte The problem of degradation or buried can be solved.

a) seed manufacturing

The seed is in the reactor i) 100 parts by weight of ethylenically unsaturated monomer, ii) 0.1 to 10 parts by weight of crosslinking agent, iii) 4.5 to 10 parts by weight of emulsifier, iv) 0.01 to 3 parts by weight of polymerization initiator and v) 300 to 450 weight of ion-exchanged water. It can be prepared by the method of batch administration of the part to react for 1 to 3 hours at a temperature of 60 ~ 90 ℃.

As said ethylenically unsaturated monomer, an aromatic vinyl compound, a vinyl cyan compound, an acrylic acid ester, and methacrylic acid ester can be used individually or in mixture of 2 or more types.

The crosslinking agent may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of an ethylenically unsaturated monomer, and examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1, 4- butylene glycol dimethacrylate, aryl methacrylate, divinylbenzene, etc. can be used.

The emulsifier may be used in an amount of 4.5 to 10 parts by weight based on 100 parts by weight of an ethylenically unsaturated monomer, and examples thereof include alkylarylsulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, or alkali salts of rosin acid. Etc.

The polymerization initiator may be used in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of an ethylenically unsaturated monomer, and examples thereof include a water-soluble persulfate, a peroxy compound, a redox system, and the like. Specifically, water-soluble persulfates such as sodium or potassium persulfate, cumene hydroperoxide, diisopropylbenzene hydroxide peroxide, azobis isobutylonitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, benzoyl peroxide, etc. Fat-soluble polymerization initiators; Water-soluble radical initiators, fat-soluble radical initiators and mixtures;

It is preferable that the average particle diameter of the emulsion-polymerized seed under the conditions described above is 500 ~ 1000Å.

b) core production and large diameter rubber polymer production

I) 60 to 80 parts by weight of ii) 100 parts by weight of the conjugated diene monomer in the presence of 0.1 to 3 parts by weight of the seed, iii) 1 to 3 parts by weight of the emulsifier, iv) 0.1 to 3 parts by weight of the polymerization initiator, v) molecular weight regulator 0.1 to 1 parts by weight, vi) 0.1 to 3 parts by weight of the electrolyte, vii) 40 to 80 parts by weight of ion-exchanged water, followed by emulsion polymerization at 65 to 75 ° C. for 6 to 15 hours; And viii) 20-40 parts by weight of the remaining conjugated diene monomer, and ix) 0.05-1 part by weight of the molecular weight modifier, x) 0.1-2 parts by weight of the seed, for 10-20 hours at a temperature of 75-90 ° C. It can be prepared by a method comprising the step of emulsion polymerization.

As the conjugated diene monomer, 1,3-butadiene, isoprene, chloroprene, pyrrylene, or comonomers thereof may be used. As the monomer copolymerizable with the conjugated diene monomer, an aromatic vinyl compound such as styrene or α-methylstyrene, or a vinyl cyan compound such as acrylonitrile may be used, and the content thereof is preferably used within 20 parts by weight of the total monomer mixture. Do. The emulsifier polymerization initiator may be the same as those used in the preparation of the seed. As the molecular weight regulator, mercaptans are mainly used, and tertiary dodecyl mercaptan is particularly preferable.

In the present invention, it is preferable that the monomer is emulsion-polymerized by partial batch administration during core preparation, and then the emulsion is polymerized by batch or continuous administration of the remainder to the reaction product. When the entire amount of the monomer is administered in a batch, there is a problem in that a phenomenon in which a perfect core is not formed on the surface of the seed, that is, the average particle diameter of the rubber polymer is much smaller than the desired average particle diameter occurs.

It is preferable that the average particle diameter of the rubber polymer containing the seed and core manufactured by this invention is 2000-5000 mm <3>.

c) Graft  Copolymer production

Into the nitrogen-substituted polymerization reactor i) 50 to 80% by weight of a large diameter rubber latex, ii) 20 to 50% by weight of a monomer mixture consisting of an aromatic vinyl compound and a vinyl cyan compound were added to prepare a graft copolymer. The monomer mixture is graft copolymerized by continuous dosing in an emulsified state. At this time, iii) 0.2-2 parts by weight of an emulsifier, iv) 0.1-0.5 parts by weight of a molecular weight modifier, v) 0.1-0.5 parts by weight of a polymerization initiator and the like are preferably prepared by graft copolymerization.

At this time, the polymerization temperature is suitable 45 ~ 80 ℃, the polymerization time is suitable 3 ~ 6 hours.

Styrene, α-methylstyrene, vinyltoluene, etc. may be used as the aromatic vinyl compound, and acrylonitrile or methacrylonitrile may be used as the vinyl cyan compound.

The reactive emulsifiers include sodium 11-methacryloyl undecane-1-yl sulfate (MET) and sodium 11-crotonoyl undecane as anionic surfactants. Can-1-yl sulfate (sodium 11-crotonoyl undecane-1-yl sulfate, CRO), sodium 3-sulfopropyl tetradodecyl maleate (M14), dodecyl sulfopropyl maleate (dodecyl sulfopropyl maleate (M12), 4-vinylbenzyl maleate (VBM) and the like, and cationic surfactants are 2- (N, N-diethylammonio) ethylalkyl maleate chloride (2- (N, N-diethylammonio) ethyl alkyl maleate chloride), 2- (N, N, N-triethylammonio) ethylalkyl maleate iodide (2- (N, N, N-triethylammonio) ethyl alkyl maleate iodide ), 2- (N-allyl-N, N-diethylammonio) ethyl hexadecyl maleate bromide (2- (N-allyl-N, N-diethylammonio) ethyl hexa decyl maleate bromide), 2- (N, N-diethylamino) ethyl alkyl maleate (2- (N, N-diethylammonio) ethyl alkyl maleate), maleate nonionic (MALPEO), acrylated poly (Ethylene oxide) -b-poly (butylene oxide) (acrylated poly (ethylene oxide) -b-poly (butylenes oxide), hexadecylmaleate N- (2-hydroxylethyl) amide (hexadecylmaleate N- (2- hydrocylethyl) amide, hexadecylmaleate N-tris (hydroxylmethyl) methylamide, and the zwitterionic surfactant includes 3- (N, N-dimethyl- N- (sulfopropyl) ammonio) propyl alkyl maleate (3- (N, N-dimethyl-N- (sulfopropyl) ammonio) propyl alkyl maleate). It is very important to select an emulsifier to secure the latex stability when preparing a graft copolymer having a high rubber content.

The reactive emulsifier is a mixture of monomers and emulsifiers in an emulsion form and then shot or charged in one shot, instead of feeding or continuously dispensing water in which the emulsifier is dissolved. Can be put into.

Mercaptans are mainly used as the molecular weight modifier, and tertiary dodecyl mercaptan is particularly preferable.

The polymerization initiators include cumene hydroperoxide, diisopropyl benzene hydroperoxide, persulfate, peroxide, sodium formaldehyde siloxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrroline sodium, sulfite Oxidation-reduction catalyst systems in admixture with reducing agents such as sodium or the like can be used.

The polymerization conversion rate of the latex obtained after completion of the polymerization is 98% or more.

In addition, the antioxidant and stabilizer by the multilayered ABS graft polymer prepared as described above may be administered to aggregate into an aqueous sulfuric acid solution at a temperature of 90 ° C. or higher, and then dehydrated and dried to obtain a powdery ABS graft polymer. .

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  1-2: particle size and conversion over time

2 g of latex is sampled during the reaction to prepare the graft copolymer on the already prepared seed, and then quenched by immersion in ice water to prevent further reaction from proceeding. To prevent side effects of the analysis due to contamination, hydroquinone and quenchable compounds were not added.

Conversion rate and particle size over time Sample time Particle Size (nm) Conversion Rate (%) DI Dn PDI PBL 3000 0 300.7 292.3 1.03 PBL 5000 0 298.3 295.3 1.01 Average 299.5 293.8 1.02 Theoretical value 344.4 337.9 1.02 Example 1 0 60.00 15 296.1 257.4 1.15 62.17 30 295.1 292.6 1.01 68.41 45 305 241 1.27 74.95 60 310.3 295.3 1.05 79.50 75 314.4 299.9 1.05 83.80 90 313.2 277.9 1.13 87.17 105 323.4 300 1.08 90.88 120 318.7 298.9 1.07 94.45 140 320 268.9 1.19 97.04 160 318.5 299 1.07 98.13 180 323.5 313.2 1.03 98.38 Example 2 0 65.00 15 290.7 290.6 65.81 30 293.3 279 1.05 66.75 45 299.7 269.6 1.11 70.44 60 299 261.8 1.14 76.32 75 305.2 296.9 1.03 81.15 90 306.2 244.8 1.25 85.06 105 316.2 314 1.01 89.97 120 309.4 309.1 1.00 94.61 140 321.6 290.9 1.11 96.44 160 312.1 251.2 1.24 97.44 180 318.9 286.9 1.11 98.22

As shown in Table 1 above, the change of the particle size was not very large at some point or more, and an emulsifier was added at a time when the conversion rate was 80 to 90%.

Example  3

Preparation of Seeds

100 parts by weight of ethylene which is an ethylenically unsaturated monomer, 0.2 parts by weight of crosslinking agent divinylbenzene, 2 parts by weight of potassium rosinate emulsifier, 0.3 parts by weight of potassium persulfate polymerization initiator, and 200 parts by weight of ion-exchanged water at a temperature of 70 ° C. Emulsification polymerization was carried out for 6 hours. The average particle diameter of the prepared seeds was 1,000 mm 3.

Core Manufacturing and Large Diameter Rubber Polymer Manufacturing

70 parts by weight of 100 parts by weight of butadiene as a conjugated diene monomer in the presence of 5 parts by weight of the seed in the reactor, 1.5 parts by weight of potassium emulsifier emulsifier, 0.3 parts by weight of potassium persulfate polymerization initiator, 0.2 parts by weight of molecular weight tertiary dodecyl mercaptan, electrolyte 0.5 parts by weight of potassium carbonate and 100 parts by weight of ion-exchanged water were emulsified and polymerized at 65 ° C. for 10 hours, and 30 parts by weight of the remaining conjugated diene monomer butadiene, 0 parts by weight of a molecular weight regulator, and 5 parts by weight of the seed were collectively administered. Emulsion polymerization for 15 hours at a temperature of 80 ℃. The average particle diameter of the rubber polymer including the prepared seed and core was 3,100 mm 3.

Graft  Copolymer production

65% by weight of the large-diameter rubber latex was added to the nitrogen-substituted polymerization reactor, 35% by weight of the monomer mixture consisting of 22.5% by weight of styrene, which is an aromatic vinyl compound, and 7.5% by weight, of acrylonitrile, which is a vinyl cyan compound, were continuously added in an emulsified state. , When the polymerization conversion rate is 75% to 90%, 0.2 part by weight of the emulsifier HeBA (CH ₂ = CHCOO (CH ₂ ) ₄ COCH = CHCOOH) having a double bond with the reactive emulsifier carboxyl group, and 0.3 part by weight of the molecular weight modifier tertiary dodecyl multicaptan , 0.12 parts by weight of a polymerization initiator potassium persulfate was added to prepare a graft copolymer. Here, the reactive emulsifier was added in the form of a shot charge, which means that the water in which the emulsifier is dissolved is continuously added at a time, rather than continuously.

Comparative example  One

Except that 0.6 parts by weight of fatty acid was added in a mixed form instead of 0.2 part by weight of the reactive emulsifier in the graft copolymer preparation step of Example 3. Here, the mixed form means that the monomer and the emulsifier are mixed together to form an emulsion and then fed.

Example  4

The graft copolymer preparation step of Example 3 was carried out in the same manner as in Example 3, except that 0.2 parts by weight of the reactive emulsifier was added in a mixed form. Here, the mixed form means that the monomer and the emulsifier are mixed together to form an emulsion and then fed.

Example  5

In the graft copolymer manufacturing step of Example 3 was carried out in the same manner as in Example 3 except that the reactive emulsifier was added in 0.4 parts by weight instead of 0.2 parts by weight in a mixed form instead of a shot charge form. Here, the shot charge means that the water in which the emulsifier is dissolved is added at one time, not continuously at a certain time.

[Test Example]

The gloss of the graft copolymer prepared in Examples 3 to 5 and Comparative Example 1 was measured and summarized in Table 2 below. Glossmeter (Glossmeter, Toyoseiki) was used for the gloss measurement. Turn on the power, then zero and wait for it to stabilize. Once stabilized, set 87.3 (at 45 °) with a gloss standard specimen and measure the gloss of the specimens drawn from the injection machine.

Example 3 Example 4 Example 5 Comparative Example 1 Emulsifier type Responsive Emulsifier Responsive Emulsifier Responsive Emulsifier Fatty acid Emulsifier content
(Parts by weight) 0.2 0.2 0.4 0.6 input
(feeding) method Short charge Mixed form Mixed form Mixed form Gloss 120 105 100 97

As shown in Table 2 above, when a smaller amount of reactive emulsifier was added than the general emulsifier of Comparative Example 1, the stability of the latex was still maintained and the gloss was higher. This is presumed to be due to less desorption to the water, resulting in reduced gas generation.

Comparing Examples 4 and 5, even when the content of the reactive emulsifier is used in half of the existing it was confirmed that the stability is maintained and the gloss value is increased.

In addition, when comparing the Examples 3 and 4, when the polymerization conversion rate is 80 to 90% when the reactive emulsifier is added (as a one shot), the gloss value is increased than when the same amount of the reactive emulsifier is added in a mixed form. I could confirm that.

Claims (10)

(a) polymerizing an ethylenically unsaturated monomer, a crosslinking agent, an emulsifier, a polymerization initiator and ion-exchanged water to prepare a seed;
(b) preparing a core by polymerizing a conjugated diene monomer, an emulsifier, a polymerization initiator, a molecular weight regulator, an electrolyte, and ion-exchanged water in the presence of the seed to prepare a large diameter rubber latex comprising the seed and the core;
(c) A method for producing an ABS graft copolymer by adding the large-diameter rubber latex, adding a monomer mixture, an emulsifier, a molecular weight modifier, and a polymerization initiator containing an aromatic vinyl compound and a vinyl cyan compound, and graft copolymerization.
Method of producing an ABS graft copolymer, characterized in that in the step (c) the reaction type emulsifier is added to the conversion rate of 80 to 90%. The method of claim 1,
(a) 100 parts by weight of an ethylenically unsaturated monomer, 0.1 to 10 parts by weight of a crosslinking agent, 4.5 to 10 parts by weight of an emulsifier, 0.01 to 3 parts by weight of a polymerization initiator and 300 to 450 parts by weight of ion-exchanged water at a temperature of 60 to 90 ° C. Preparing a seed by polymerization for 1 to 3 hours;
(b) 60 to 80 parts by weight, 1 to 3 parts by weight of an emulsifier, 0.1 to 3 parts by weight of a polymerization initiator, 40 to 80 parts by weight of a molecular weight regulator, and an electrolyte of 0.05 parts by weight of 100 parts by weight of the conjugated diene monomer in the presence of 0.1 to 3 parts by weight of the seed. ~ 1 part by weight, 40-80 parts by weight of ion-exchanged water, emulsified and polymerized at 65-75 ° C. for 6-15 hours, 20-40 parts by weight of the remaining conjugated diene monomer, 0.05-1 parts by weight molecular weight regulator and seed 0.1 Preparing a large-diameter rubber latex comprising a seed and a core by emulsifying and polymerizing at a temperature of 75-90 ° C. for 10-20 hours in a batch dose of 2 parts by weight;
(c) 50 to 80% by weight of the large-diameter rubber latex is added, 20 to 50% by weight of a monomer mixture containing an aromatic vinyl compound and a vinyl cyan compound, 0.2 to 2 parts by weight of a reactive emulsifier, and 0.1 to 0.5 parts by weight of a molecular weight regulator. And 0.1 to 0.5 parts by weight of a polymerization initiator and graft copolymerization at a temperature of 45 to 80 ° C. for 3 to 6 hours to prepare an ABS graft copolymer, in which the reactive emulsifier is converted to 80 to 90% in step (c). Method for producing an ABS graft copolymer, characterized in that added to. 3. The method according to claim 1 or 2,
The reactive emulsifier is sodium 11-methacryloyl undecane-1-yl sulfate (MET), sodium 11-crotonoyl undecane-1-yl sulfate (sodium 11 -crotonoyl undecane-1-yl sulfate (CRO), sodium 3-sulfopropyl tetradodecyl maleate (M14), dodecyl sulfopropyl maleate (M12), 4-vinyl Benzyl maleate (VBM), 2- (N, N-diethylammonio) ethylalkyl maleate chloride, 2- (N, N, N-triethylammonio) ethylalkyl maleate iodide (2- (N, N, N-triethylammonio) ethyl alkyl maleate iodide), 2- (N-allyl-N, N-diethylammonio) ethyl hexa Decyl maleate bromide (2- (N-allyl-N, N-diethylammonio) ethyl hexadecyl maleate bromide), 2- (N, N-diethylamino) ethyl alkyl maleate (2- (N, N-diethylammonio) ethyl alkyl malea te), maleate nonionic (MALPEO), acrylated poly (ethylene oxide) -b-poly (butylenes oxide), hexadecylmalee Hexadecylmaleate N- (2-hydrocylethyl) amide, hexadecylmaleate N-tris (hydroxylmethyl) methylamide and 3- (N, N-dimethyl-N- (sulfopropyl) ammonio) propyl alkyl maleate (3- (N, N-dimethyl-N- (sulfopropyl) ammonio) propyl alkyl maleate) at least one selected from the group consisting of Method for producing an ABS graft copolymer, characterized in that. The method of claim 1,
The ethylenically unsaturated monomer is a method for producing an ABS graft copolymer, characterized in that at least one selected from the group consisting of aromatic vinyl compound, vinyl cyan compound, acrylic acid ester and methacrylic acid ester. The method of claim 1,
The crosslinking agent is ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, aryl methacrylate and divinylbenzene Method for producing an ABS graft copolymer, characterized in that at least one selected from the group consisting of. The method of claim 1,
Wherein said emulsifier is at least one selected from the group consisting of alkylarylsulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid. The method of claim 1,
The conjugated diene monomer is 1,3-butadiene, isoprene, chloroprene, pyrrylene, and at least one selected from the group consisting of comonomers of the method for producing an ABS graft copolymer. The method of claim 1,
Method for producing an ABS graft copolymer, characterized in that the average particle diameter of the seed of step (a) is 500 ~ 1000Å. The method of claim 1,
Method for producing an ABS graft copolymer, characterized in that the average particle diameter of the large-diameter rubber latex comprising the seed and the core of step (b) is 2000 ~ 5000Å. The method of claim 1,
The aromatic vinyl compound is at least one selected from the group consisting of styrene, α-methylstyrene and vinyl toluene, the vinyl cyan compound is a method for producing an ABS graft copolymer, characterized in that acrylonitrile or methacrylonitrile. .