KR100530999B1 - Method of Preparing High Impact Strenth and High Flow ABS Resin Using Agglomerated Rubber Latex - Google Patents

Abstract

The method for producing ABS resin using agglomerated rubber latex of the present invention comprises the steps of: (1) pre-treating seed synthetic rubber latex by adding an anionic emulsifier and a nonionic emulsifier to seed synthetic rubber latex; (2) a second step of pretreating the particle size-enhancing agent by mixing the unsaturated acid-containing copolymer latex with ion-exchanged water, a nonionic emulsifier and an electrolyte to adjust the solids content to 1 to 10% by weight and the pH to 5 to 11; (3) The particle size-adding agent pretreated in the seed synthetic rubber latex pre-treated in a batch of the particle size-adding agent in a range of 0.1 to 7 parts by weight based on the solids content of 100 parts by weight of the seed synthetic rubber latex and the pH to 9 to 12 Re-conditioning to produce agglomerated rubber latex; And (4) a fourth step of graft polymerization by adding a monomer mixture consisting of acrylonitrile and styrene to the agglomerated rubber latex prepared above.

Description

Method of preparing high impact, high flow ABS resin using agglomerated rubber latex {Method of Preparing High Impact Strenth and High Flow ABS Resin Using Agglomerated Rubber Latex}

Field of invention

The present invention relates to a method for producing a high impact, high flow ABS resin having excellent physical properties using agglomerated rubber latex. More specifically, the present invention relates to agglomerated rubber latex prepared by adding seed content rubber latex pretreated with anionic emulsifier and nonionic emulsifier to a solid content 1-10 wt%, particle size thickener pretreated at pH 5-11. It relates to a high-impact, high flow acrylonitrile-butadiene-styrene copolymer (hereinafter, referred to as ABS resin), characterized in that the monomer mixture consisting of acrylonitrile and styrene monomer is prepared at a predetermined ratio.

Background of the Invention

ABS resin is a copolymer of acrylonitrile monomer and butadiene monomer styrene monomer. They are in harmony with various physical properties such as stiffness, weather resistance, chemical resistance, impact resistance, glossiness, moldability in ABS resin.

In general, the ABS resin manufacturing process polymerizes butadiene monomer through conventional emulsion polymerization, and then performs graft polymerization with a certain amount of styrene, acrylonitrile, and dispersion in order to secure compatibility of butadiene rubber with styrene and acrylonitrile. It is obtained through an extrusion process of mixing at a constant temperature with the styrene and acrylonitrile copolymer obtained through the polymerization or bulk polymerization.

Butadiene rubber in ABS resin improves the impact resistance, but in the entire ABS resin manufacturing process, since it is manufactured by a conventional emulsion polymerization method with a long polymerization time, the ABS resin manufacturing time is influenced. In addition, butadiene rubber should have a particle size of a predetermined size or more in order to exhibit impact resistance in the ABS resin, but when prepared by the usual emulsion polymerization requires a long polymerization reaction time to polymerize the butadiene rubber of a predetermined particle size or more.

In order to reduce the production time of the rubber latex, the polymerization time has been shortened by copolymerization with styrene or acrylic monomers, but the polymerization time has not been drastically reduced.

Accordingly, various methods of enlarging the particle size in a short time after preparing the small butadiene rubber latex or copolymer rubber latex having a relatively short polymerization time have been proposed. These methods are freeze-incorporation of small particle rubber latex or enlarging the particle size by mechanical or chemical methods.

These methods are well known methods, but there is a problem that the stability after the particle size enlargement, or change over time occurs, and coagulum occurs a lot. In addition, even if these problems are solved, synthetic rubber latex having a large particle size in a short time expresses high impact physical properties when applied to ABS resin, but has problems such as deterioration in fluidity or gloss.

In order to solve the above problems, the present inventors, by appropriately adjusting the coagulation rubber latex production conditions and graft polymerization conditions using the same, such as impact resistance, fluidity and glossiness deterioration generated when applying agglomerated rubber latex to ABS resin In addition to improving the physical properties, it has led to the development of a high impact, high flow ABS resin manufacturing method that shortens the overall polymerization time.

An object of the present invention is to provide a method for producing an ABS resin having excellent reaction stability in the production of agglomerated rubber latex.

Another object of the present invention is to provide a method for producing an ABS resin in which coagulation product is reduced during the production of agglomerated rubber latex.

Still another object of the present invention is to provide a method for producing an ABS resin having a small change in particle diameter with time after aggregation.

Another object of the present invention is to provide a method for producing an ABS resin that shortens the overall polymerization time.

Another object of the present invention is to provide a method for producing an ABS resin that improves physical properties such as fluidity, impact strength and gloss.

The above and other objects of the present invention can be achieved by the present invention described below. Hereinafter, the details of the present invention will be described below.

The method for producing ABS resin of the present invention comprises the steps of: (1) pre-treating seed synthetic rubber latex by adding an anionic emulsifier and a nonionic emulsifier to seed synthetic rubber latex; (2) a second step of pretreating the particle size-enhancing agent by mixing the unsaturated acid-containing copolymer latex with ion-exchanged water, a nonionic emulsifier and an electrolyte to adjust the solids content to 1 to 10% by weight and the pH to 5 to 11; (3) The particle size-enhancing agent pre-treated in the pretreated seed synthetic rubber latex is added to the particle size-enhancing agent in a range of 0.1 to 7 parts by weight based on 100 parts by weight of solids of the seed synthetic rubber latex, and the pH is 9 to 12. Re-conditioning to produce agglomerated rubber latex; And (4) a fourth step of graft polymerization by adding a monomer mixture consisting of acrylonitrile and styrene to the agglomerated rubber latex prepared above. Hereinafter, a detailed description of each of these steps is as follows.

(1) First step: pretreatment of seed synthetic rubber latex

Seed synthetic rubber latex used in the present invention is prepared by a conventional emulsion polymerization method. The emulsifier used in the polymerization step may be used by mixing an anionic emulsifier and a nonionic emulsifier, at least one anionic emulsifier is used.

Examples of the seed synthetic rubber latex include, but are not limited to, polybutadiene, butadiene-styrene copolymer, butadiene-α-methylstyrene copolymer, butadiene-acrylate copolymer, butadiene-methacrylate copolymer, and the like. .

The particle size of the seed synthetic rubber latex is preferably in the range of 800 to 1,600 kPa. If the particle size is 800 Å or less, the viscosity of the rubber latex is increased, so that it is not easy to transport the synthetic rubber latex, and when the particle size increasing agent is added, there is a problem that only a uniform particle size is formed without uniform particle size enlargement. On the other hand, if the particle size is more than 1,600Å, the polymerization time of the seed synthetic rubber latex is increased.

In addition, the solid content of the seed synthetic rubber latex of the present invention is preferably 30 to 50 weight percent. If the solid content is less than 30% by weight, the solid content of the aggregated final synthetic rubber latex is low, which is disadvantageous for commercial ABS resin production. On the other hand, if the solid content of the seed synthetic rubber latex is 50% by weight or more, it is not only a problem of polymerization stability, but also a high viscosity after polymerization, which causes local large particle curing or coagulation.

The pretreatment of the seed synthetic rubber latex of the present invention comprises 1: 9 to 9: 1 weight ratio of anionic emulsifier and nonionic emulsifier in the seed synthetic rubber latex having the solid content of 30 to 50% by weight, preferably 2: Pretreatment is carried out by adding and stirring at a ratio of 8 to 8: 2.

The anionic emulsifier used in pretreatment of the seed synthetic rubber latex is rosin acid soap, sodium lauryl sulfate, sodium oleate, potassium oleate, dodecyl Sodium dodecyl benzene sulfonate and aerosols, which are succinic acid derivatives of various sulfonic acids.

The nonionic emulsifier may be a polyethylene oxide condensate, a polyethylimide condensate, a fatty acid ester of a polyoxy compound, or the like.

(2) Second step: pretreatment of particle size increasing agent

As the particle size increasing agent used in the present invention, copolymer latex containing unsaturated acid is applied. As the monomer for producing the copolymer latex, an unsaturated acid monomer having a carboxyl group is preferable.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, methyl acrylic acid, itaconic acid, crotonic acid, fumaric acid, Methylene unsaturated carboxylic acids such as maleic acid; Acrylate monomers such as methyl methacrylate, methyl acrylate and ethyl acrylate copolymerizable with these; C _4-6 conjugated double bond monomers such as butadiene and isoprene; Monovinyl aromatic hydrocarbon monomers such as styrene, α-methylstyrene, vinyltoluene, and chlorostyrene; And acrylonitrile, methacrylonitrile monomers. The particle size-enhancing agent is preferably prepared by copolymerizing at least one or more unsaturated acid monomers.

In addition, the unsaturated acid monomer content in the unsaturated acid-containing copolymer latex of the present invention is preferably 1 to 20% by weight. When the unsaturated acid content is 1% by weight or less, the function as a particle size enlargement material is lowered, and when 20% by weight or more, the reaction time is long during copolymerization, and there is a problem that a lot of coagulum is generated.

The unsaturated acid-containing copolymer latex is mixed with an appropriate amount of ion-exchanged water, a nonionic emulsifier, and an electrolyte, followed by pretreatment by adjusting the solids content of the copolymer latex to 1 to 10% by weight and the pH to 5 to 11. It is preferable that the particle size-enhancing agent adjust the pH to 5 to 11 because it is most stable when the pH is in the above range.

As the nonionic emulsifier used to pretreat the unsaturated acid-containing copolymer latex, a polyethylene oxide condensate, a polyethylimide condensate, and a fatty acid ester of a polyoxy compound may be used.

In addition, it is preferable to use an aqueous potassium carbonate solution (2%) as the electrolyte.

(3) Step 3: Preparation of agglomerated rubber latex (enlarge particle size of seed synthetic rubber latex)

Agglomerated rubber latex of the present invention is prepared by a method of batch-injecting the particle size-adding agent pretreated in the second step to the seed synthetic rubber latex pretreated in the first step.

At this time, it is preferable to use the particle size-enhancing agent in the range of 0.1 to 7 parts by weight based on 100 parts by weight of the solid content of the seed synthetic rubber latex. If less than 0.1 parts by weight of the rubber latex synthetic rubber latex has a lot of PASS latex, there is a disadvantage that the particle size is small. In addition, when used in excess of 7 parts by weight, the gloss is lowered and the object according to the present invention cannot be achieved. More preferably, it is good to use in the range of 1-6 weight part.

The large particle size of the present invention was prepared by re-adjusting the pH from 9 to 12 with a batch of a particle size-enhancing agent adjusted to a solid content of 1 to 10% by weight and a pH of 5 to 11 in a pretreated seed synthetic rubber latex as described above. Synthetic rubber latex having can be prepared.

When the particle size-enhancing agent whose solid content is adjusted to 1 to 10% by weight and the pH is adjusted to 5 to 11 is added to the pretreated seed synthetic rubber latex, it is preferable to rapidly add within 1 to 10 minutes.

In addition, when the particle size-adding agent is added to the seed synthetic rubber latex, the temperature is preferably maintained at 40 ° C to 90 ° C. When the temperature is 40 ° C. or lower, the particle size-enhancing ability is lowered, and thus, the particle size-enhancing agent should be added. If the temperature is 90 ° C. or higher, the stability of the agglomerated rubber latex is lowered to form a large amount of coagulum.

The time for increasing the particle size is preferably 10 minutes to 4 hours, and the pH is preferably adjusted to 9 to 12 while the particle size is enlarged.

(4) 4th step: Graft polymerization of agglomerated rubber latex

Polymerization of the cohesive rubber latex of the present invention is polymerized by mixing 5 to 20 parts by weight of acrylonitrile monomer and 20 to 50 parts by weight of styrene monomer to 40 to 70 parts by weight of the agglomerated rubber latex prepared in the third step. At this time, the composition of the mixture of acrylonitrile monomer and styrene monomer preferably has 30 to 50 parts by weight.

When the content of the agglomerated rubber latex in the graft polymerization is 40 parts by weight or less, the graft SAN on the rubber surface may be uniform, thereby providing excellent fluidity and glossiness. However, the rubber efficiency may be lowered and the amount of free-SAN is increased. There is a problem of lowering the graft copolymer production efficiency. On the other hand, when the content of agglomerated rubber latex is 70 parts by weight or more, due to the lack of a monomer forming graft copolymerization, the rubber surface cannot be uniformly graft-polymerized, thereby causing entanglement between rubbers and deterioration of compatibility with SAN in the manufacture of ABS resin. Problems occur such as to lower the overall physical properties of the ABS resin.

In the graft polymerization of agglomerated synthetic rubber latex, a mixture of monomers composed of acrylonitrile and styrene is added to the reactor with a molecular weight modifier, an emulsifier, a polymerization initiator, ion-exchanged water and a reducing agent. After raising the temperature, the catalyst compound is added to form a first graft polymerization, and then a residual amount of the monomer mixture is gradually added for 1 to 3 hours to form a second graft polymerization.

If the monomer mixture in the first graft polymerization is less than 15% of the total monomer mixture, the efficiency decreases due to the increase in the total polymerization time due to the increase in the amount of the monomer mixture used for the second graft polymerization. On the other hand, when 55% or more of the monomer mixture is added during the first graft polymerization, it is difficult to control the molecular weight of the graft polymerization SAN, which causes a decrease in physical properties when applied to the ABS resin.

However, when the amount of the monomer mixture added to the first graft polymerization is increased, the monomer mixture used in the second graft polymerization is reduced, thereby reducing the total graft polymerization time.

Therefore, only when the content of the monomer mixture, the molecular weight regulator, the initiator, and the like is properly adjusted during the first graft polymerization, the total graft polymerization time can be minimized without deteriorating the physical properties of the ABS resin.

Specific examples of the molecular weight adjusting agent introduced during the first graft polymerization in the present invention include mercaptans such as alpha methyl styrene duplex or tertiary dodecyl mercaptan. The molecular weight modifier may be added in the range of 0.02% to 0.5% of the monomer used in the first graft polymerization to minimize the graft polymerization time without deteriorating the physical properties of the ABS resin, and the second graft polymerization sheet It is preferable that the dosage of frostidodecyl mercaptan is 0.1 to 0.25% by weight.

In addition, specific examples of the initiator include tertiary butyl peroxide, tertiary butyl peroxy benzoate, cumene hydroperoxide, and the like, in the range of 0.03% to 1.0% of the monomer used for the first graft polymerization. It is possible to minimize the total graft polymerization time without deteriorating the physical properties of the ABS resin to be added in the range of 0.5 times to 2.0 times based on the molecular weight regulator.

When graft polymerizing agglomerated rubber latex, the stirring conditions and polymerization temperature of the reactor change the graft copolymerization behavior. In the present invention, the graft polymerization of the agglomerated rubber latex is preferably stirred in the range of 130 to 400 rpm, and the polymerization temperature is preferably in the range of 50 ° C to 75 ° C.

In the case of graft polymerization, when the stirring rpm is 130 or less, stirring is locally performed to reduce the uniformity of the graft polymerization, and when the rpm is 400 or more, the polymerization graft polymerization stability is rapidly lowered to generate a coagulated product.

In addition, when the polymerization temperature is 50 ℃ or less, the polymerization stability is excellent, but the polymerization rate is reduced to reduce the graft polymerization production efficiency. The higher the polymerization temperature, the shorter the graft polymerization time. However, the polymerization stability of 80 ° C. or higher is 77.3 degrees at the boiling point of acrylonitrile, resulting in the breakdown of micelles due to the foaming, resulting in reduced polymerization stability.

In the stirring conditions of 130rpm to 400rpm, because the agglomerated rubber latex is metastable and the particle size is enlarged, the agglomerated particles are loosened depending on the stirring conditions and temperature, or the reaggregation phenomenon is caused by the activity of the particle size increasing agent. It can give a particle diameter change of 10Å to 2000Å depending on the temperature. The particle size change of the agglomerated rubber latex during the graft polymerization has a great influence on the physical properties of the ABS resin.

The present invention will be further illustrated by the following examples, which are only described for the purpose of illustrating the present invention and are not intended to limit the protection scope of the present invention.

Example

Example 1

(1) Step 1: Preparation and pretreatment of seed synthetic rubber latex

Seed synthetic rubber latex is 130 parts by weight of ion-exchanged water, 100 parts by weight of butadiene, 0.7 parts by weight of t-dodecyl mercaptan (t-DDM), 3.0 parts by weight of sodium lauryl sulfate, 1.0 parts by weight of potassium carbonate, and potassium persulfate 0.5 The weight part was prepared by polymerization at a reaction temperature of 70 ° C. for 9 hours. The seed synthetic rubber latex prepared had a particle size of 1450 Å and a solid content of 45% by weight. It was.

To 100 parts by weight of the seed synthetic rubber latex prepared above (solid content of 45% by weight), 1.0 parts by weight of rosin acid anionic emulsifier was added, and 0.2 parts by weight of polyethylimide condensate as a nonionic emulsifier. Was pretreated.

(2) second step: preparation and pretreatment of particle size increasing agent

Copolymer latex, a particle size-enhancing agent, contains 185 parts by weight of ion-exchanged water, 10 parts by weight of butadiene, 10 parts by weight of methacrylic acid, 80 parts by weight of ethyl acrylate, 5.0 parts by weight of sodium dodecylbenzenesulfonate, 0.5 parts by weight of potassium carbonate and potassium per 0.5 parts by weight of sulfate was polymerized at a reaction temperature of 70 ° C. for 6 hours to prepare a copolymer latex having a particle size of 750 mm 3, a solid content of 35% by weight, and a pH of 2.5.

To 100 parts by weight (35% by weight of solid content) of copolymer latex, the particle size-enhancing agent prepared above, 0.5 parts by weight of sodium dodecylbenzenesulfonate as an anionic emulsifier and 0.1 parts by weight of polyethylimide condensate as a nonionic emulsifier, ion exchange 150 parts by weight of water and an aqueous potassium carbonate solution (2%) were mixed and stirred to adjust the solids content to 10% by weight and the pH to 7.0 ± 0.5.

(3) Step 3: Preparation of Cohesive Rubber Latex (Enlarged Particle Size)

100 parts by weight of the pretreated seed synthetic rubber latex was added to the reactor, the temperature was raised to 65 ° C. while stirring at 150 rpm, and 5 parts by weight of the pretreated particle size-enhancing agent was added in a batch for 5 minutes. The aggregated particle diameter was measured by NICOMP 370 (particle size analyzer) from 1 hour to 96 hours after the particle size increasing agent is shown in Table 1 below.

Pretreated Seed Synthetic Rubber Latex Pretreated Particle Expense Agent pH control Size increase P / size (Å) 1hr 4hr 12hr 48hr 96hr 100 parts by weight 5 parts by weight 11.0 3562 3615 3624 3684 3698

(4) Step 4: Graft Polymerization of Cohesive Rubber Latex

60 parts by weight of the coagulated rubber latex prepared above in the graft polymerization reactor, 3.3 parts by weight of acrylonitrile monomer, 10.5 parts by weight of styrene monomer, 0.14 parts by weight of terceridodecylmercaptan, 0.2 parts by weight of cumene hydroperoxide, potassium stearate After adding 0.2 parts by weight, 0.3 parts by weight of sodium hydroxide and 140 parts by weight of ion-exchanged water, the temperature of the reactor was increased to 60 ° C, 0.003 parts by weight of ferrous sulfate and 0.15 parts by weight of tetrasodium parophosphate were added. Graft polymerization was performed.

The secondary graft polymerization was continuously performed immediately after the reactor temperature reached 70 ° C. due to the heat of polymerization generated during the first graft polymerization. 6.7 parts by weight of acrylonitrile monomer, 19.5 parts by weight of styrene monomer and 0.1 parts by weight of terceridodecylmercaptan were added to the primary graft polymer, and 0.2 parts by weight of cumene hydroperoxide was added while stirring. The reaction proceeded.

At this time, the graft polymerization was performed at a stirring speed of 220 rpm.

After the completion of the second polymerization, natural cooling was performed for 1 hour, and then the graft polymerization was terminated by adding an antioxidant along with forced cooling. After polymerization, the latex was added and solidified in a 1.0% aqueous solution of sulfuric acid with high speed stirring to obtain graft-ABS powder after washing and drying.

Example 2-4

Example 4 was carried out in the same manner as in Example 1, except that 0.15, 0.20, and 0.25 parts by weight of tersarydodecyl mercaptan were added during the second graft polymerization.

The physical properties of the latex prepared in the above Example are shown in Table 2 below.

Example Secondary graft polymerization sheet frost dodecyl mercaptan input amount (part by weight) Latex Properties after Graft Polymerization Coagulum (wt.%) Graft Efficiency (%) Particle diameter One 0.10 0.131 93.5 3748 2 0.15 0.128 91.6 3732 3 0.20 0.121 87.3 3725 4 0.25 0.090 84.4 3693

Comparative Example 1

The same procedure as in Example 3 was carried out except that graft polymerization was carried out using a general rubber latex (particle size 3200 mm 3) obtained through conventional emulsion polymerization instead of the agglomerated rubber latex of the example.

Comparative Example 2-4

The same procedure as in Example 1 was carried out except that tersoridodecyl mercaptan was changed to 0.05, 0.30, and 0.40 parts by weight, respectively, in the fourth graft polymerization.

The physical properties of the latex prepared in the comparative example are shown in Table 3 below.

Comparative example Rubber Latex Secondary Graphite Polymerization Sheet Cerdoridodecylmercaptan Input (parts by weight) Latex Properties after Graft Polymerization Coagulum (wt.%) Graft Efficiency (%) Particle diameter One Normal 0.20 0.124 89.2 3751 2 Cohesion 0.05 0.128 91.6 3785 3 Cohesion 0.30 0.121 89.0 3725 4 Cohesion 0.40 0.090 84.4 3693

ABS resin composition preparation and evaluation

In order to evaluate the physical properties of the ABS resin using the graft-ABS resin prepared in Examples 1-4 and Comparative Examples 1-4, an ABS resin composition was prepared by the following method.

30 parts by weight of the graft copolymer, 27 parts by weight of acrylonitrile content, weight average molecular weight of 120,000, and 70 parts by weight of SAN copolymer having a molecular weight distribution of 1.88, 23 parts by weight of flame retardant, 1 part by weight of calcium stearate as stabilizer and ethylene 1 part by weight of bis steroidoid was mixed and extruded to prepare a test piece for measuring physical properties. The physical properties of each prepared specimen were evaluated and shown in Table 4 below.

IZOD impact strength Flow index Glossiness Heat deflection temperature Specimen Surface Condition Example One 23.9 6.2 89.8 87.6 A 2 22.7 6.5 99.2 87.6 A 3 21.2 6.7 99.3 87.3 A 4 21.0 6.9 99.6 87.1 A Comparative example One 19.8 6.2 99.1 87.2 A 2 23.4 4.6 86.4 88.7 C 3 18.1 7.0 99.5 86.8 B 4 16.8 7.4 99.8 86.1 B

Test Methods

(1) Izod impact strength: 1/4 "notched test piece was measured by ASTM D256 method.

(2) Flow index: measured by ASTM D1238 method.

(3) Glossiness: It was measured by ASTM D523 method.

(4) Heat deflection temperature was measured by ASTM D1525 method.

(5) Specimen surface state: The sheet was molded to a thickness of 2 mm, a width of 50 cm, and a length of 100 cm to evaluate the state of the surface (A: good B: normal C: bad).

The present invention not only improves the physical properties such as impact resistance, fluidity and glossiness deterioration generated by applying the cohesive rubber latex to the ABS resin by appropriately adjusting the preparation of the cohesive rubber latex and graft polymerization conditions using the same. It has the effect of providing the manufacturing method of ABS resin which shortens an overall superposition | polymerization time.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (6)

(1) a first step of pretreating the seed synthetic rubber latex by adding an anionic emulsifier and a nonionic emulsifier to the seed synthetic rubber latex; (2) a second step of pretreating the particle size-enhancing agent by mixing the unsaturated acid-containing copolymer latex with ion-exchanged water, a nonionic emulsifier and an electrolyte to adjust the solids content to 1 to 10% by weight and the pH to 5 to 11; (3) The particle size-enhancing agent pre-treated in the pretreated seed synthetic rubber latex is added to the particle size-enhancing agent in a range of 0.1 to 7 parts by weight based on 100 parts by weight of solids of the seed synthetic rubber latex, and the pH is 9 to 12. Re-conditioning to produce agglomerated rubber latex; And (4) a fourth step of adding a monomer mixture consisting of acrylonitrile and styrene to the cohesive rubber latex prepared above, and polymerizing primary and secondary grafts; It includes, and the method of producing an ABS resin, characterized in that the molecular weight modifier is added at 0.1 to 0.25% by weight during the second graft polymerization of the fourth step. The method of claim 1, wherein the seed synthetic rubber latex has a particle size of 800 to 1600 mm 3, the solid content is 30-50% by weight, the unsaturated acid-containing copolymer latex is characterized in that the solid content of 1-20% by weight. The manufacturing method of ABS resin made into. The method of claim 1, wherein the anionic emulsifier is a rosin acid soap, sodium lauryl sulfate, sodium oleate, potassium oleate, dodecylbenzenesulfonate (sodium oleate) sodium dodecyl benzene sulfonate) and aerosol series which are succinic acid derivatives of various sulfonic acids; The nonionic emulsifier is selected from the group consisting of polyethylene oxide condensates, polyethylimide condensates, fatty acid esters of polyoxy compounds, and the like. The method of claim 1, wherein the ratio of the anionic emulsifier and the nonionic emulsifier of the first step is 1: 9 to 9: 1. The method according to claim 1, wherein when the pretreated particle size-adding agent is added to the pretreated seed synthetic rubber latex of the third step, the particle size-adding agent is added within 1 to 10 minutes with respect to 100 parts by weight of the solid content of the seed synthetic rubber latex. The temperature is maintained at 50 to 90 ° C., and the time for enlarging the particle size is 10 minutes to 4 hours. The graft polymerization of the cohesive synthetic rubber latex of the fourth step is performed by adding only about 15% to 55% of the total monomer mixture to the reactor to form a first graft polymerization, and then adding the remaining monomer mixture to 1 graft. Method of producing an ABS resin, characterized in that consisting of a secondary graft polymerization by slowly adding for 3 hours.