KR20080017640A - Methods for preparing and coagulating graft rubber latex having high thermal stability - Google Patents

Abstract

A method for preparing a graft rubber latex, a method for coagulating a graft rubber latex, and a method for preparing a graft rubber resin composition by using the graft rubber latex coagulated by the method are provided to improve thermal stability even without the injection of additional a heat stabilizer. A method for preparing a graft rubber latex comprises the step of polymerizing a monomer mixture comprising at least one selected from the group consisting of a rubber latex, an aromatic vinyl compound, a vinyl cyano compound and acrylate compound, wherein a first oil-soluble peroxide-based polymerization initiator is applied when the conversion rate of polymerization of the monomer mixture is within 50 %, and a second oil-soluble peroxide-based polymerization initiator is applied when the conversion rate of polymerization exceeds 50 %.

Description

METHODS FOR PREPARING AND COAGULATING GRAFT RUBBER LATEX HAVING HIGH THERMAL STABILITY

The present invention relates to a method for producing graft rubber latex, and more particularly, to increase the efficiency when applied to the compression dehydrator, and to a method for producing graft rubber latex having excellent thermal stability without adding an additional heat stabilizer and agglomeration thereof. It is about.

In general, rubber-reinforced resins such as acrylonitrile-butadiene-styrene (ABS), methacrylate-butadiene-styrene (MBS), acrylonitrile-styrene-acrylate (ASA), and the like, are generally prepared by emulsification polymerization. It is prepared, and then agglomerated and dried to prepare a powder, which is then added to an extruder together with resins such as styrene-acrylonitrile copolymer (SAN), polyvinyl chloride (PVC), and polycarbonate (PC). Primary processing in the form, and is produced through the secondary processing to inject it into the desired shape. At this time, it is common to inject the rubber-reinforced resin powder having a moisture content of less than 1% during the primary processing in the extruder.

In some cases, the rubber-reinforced resin aggregates the rubber-reinforced latex without drying in the post-process and directly enters the extruder in the form of a powder containing water, removes the water from the extruder, and the styrene-acrylonitrile copolymer (SAN). ), In the form of pellets in a continuous process, which is kneaded with resins such as polyvinyl chloride (PVC) and polycarbonate (PC). At this time, the rubber-reinforced resin in a powder state containing water has a water content of about 30%, and when the water content is increased, the water removal process in the dehydrator becomes long, which causes problems in quality variation and productivity. .

Therefore, when added to the extruder in a powder state containing water, it can be said that minimizing the moisture content for the improvement of productivity, the conventional centrifugal dehydration type water removal method has a limitation in solving this.

In order to solve this problem, there is a method of reducing the moisture content by using a compression dehydrator. However, when the compression type dehydrator is used, the thermal stability of the resin is lowered and the resin may be deformed because the processing of relatively high temperature and high pressure is further performed.

On the other hand, what is important in the industry in the manufacture of rubber-reinforced resins is to focus on the product quality as well as the productivity of these rubber-reinforced resins by maximizing the productivity of these rubber-reinforced resins.

As a method of improving the productivity of the rubber-reinforced resin, there is a method of improving the extrusion productivity. It is a common method to increase the amount of raw material introduced into the extruder and to increase the amount of resin discharged by increasing the screw ALPM and the temperature in the extruder accordingly, and in some cases, a special screw to enhance the kneading process of the raw material Sometimes used in combination.

This method for improving extrusion productivity is advantageous in improving physical properties such as impact strength by improving productivity and improving dispersibility of rubber particles, but in terms of resin, thermal stability is improved by increasing friction of resin due to high shear force. Of course, there is a problem that the degradation is accelerated by the temperature rise caused by the degradation. The deterioration of the thermal stability due to the deterioration of the resin discolors the final product, and even if the discoloration is slight, the user may cause a heat discoloration and gloss deterioration in the secondary processing such as injection, which may adversely affect the product.

In order to solve the above problems and maximize the productivity, it is necessary to devise a method for improving the thermal stability of the resin produced by emulsion polymerization as well as improving the thermal stability during processing.

In general, in order to improve the thermal stability of a resin produced by emulsion polymerization, in the case of having core-cell type particles such as resins, particularly rubber-reinforced resins, the graft polymerization for forming cells is of great importance. There may be a soybean, and secondly, there is a method of selecting an antioxidant to prevent oxidation of the resin and a method of adding the same to the thermal history that can be received in a flocculation and drying process. In addition, as a method for securing thermal stability during extrusion, there is a method of minimizing friction between the barrel and resin during processing through the addition of an additional heat stabilizer or an external lubricant to minimize friction between the extruder barrels.

However, the above methods have different effects upon application depending on the required extrusion productivity, and in particular, in order to obtain the same quality as before improving productivity, the amount of the antioxidant is increased, the type of the lubricant is increased, or the amount is increased, thereby increasing the mechanical effect. It may be accompanied by a change in physical properties and appearance properties, and at the same time there is a problem that can lose the advantage of price competitiveness to obtain through improved productivity.

In order to solve the problems of the prior art as described above, an object of the present invention is to increase the efficiency when applied to the compression type dehydrator and to provide a method and a method of producing a graft rubber latex excellent thermal stability without the addition of an additional heat stabilizer. do.

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

In order to achieve the above object, the present invention is a method for producing a graft rubber latex by polymerizing at least one monomer mixture selected from the group consisting of rubber latex, aromatic vinyl compound, vinyl cyan compound and acrylate compound. Provided is a method for producing graft rubber latex, characterized in that the primary fat-soluble peroxide-based polymerization initiator is applied within a time when the polymerization conversion rate of the mixture is 50%, and the second fat-soluble peroxide-based polymerization initiator is applied after the time. do.

In addition, the present invention is the initial aggregation step of aggregating the metal salt to the graft rubber latex prepared by the manufacturing method of claim 1; And a late agglomeration step of aggregating and aging by adding acid to the initial agglomerated latex to provide the agglomeration method of the graft rubber latex.

In addition, the present invention comprises the steps of aggregating the graft rubber latex prepared by the method of claim 1 according to the coagulation method of claim 8; Preparing a water-containing rubber resin by removing the water content of the aggregated graft rubber latex with a compression dehydrator to 2 to 10% or less; And mixing, melting, and kneading at least one resin selected from the group consisting of styrene-acrylonitrile copolymers, polyvinyl chlorides, and polycarbonates, and lubricants to water-containing rubber resins. It provides a method for producing a graft rubber resin composition.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention, in the production of thermoplastic graft rubber latex for application to the compression dehydrator, by using a rubber latex with a high gel content at the same time to increase the graft efficiency by applying a fat-soluble polymerization initiator to produce a latex by emulsion polymerization In order to solidify this, by selecting one or more types of flocculants and applying them stepwise, it was confirmed that a resin having excellent thermal stability under high temperature and high shear force was produced without additional input of a thermal stabilizer, and completed the present invention.

(A) Preparation of Graft Rubber Latex

The graft rubber latex of the present invention is selected from the group consisting of 50 to 70 parts by weight of rubber latex having an average particle diameter of 2,500 to 5,000 mm 3 and a gel content of 80 to 99%, and an aromatic vinyl compound, a vinyl cyanide compound and an acrylate compound. 30 to 50 parts by weight of one or more monomer mixtures are prepared by graft polymerization.

(a) Preparation of Rubber Latex

Rubber latex is a large diameter polybutadiene rubber latex prepared by producing a small diameter polybutadiene rubber latex and enlarging it.

The small-diameter polybutadiene rubber latex is 100 parts by weight of 1,3-butadiene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1.0 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator and ion exchanged water. 90-130 parts by weight of the batch is reacted at 50 to 65 ℃ for 7 to 12 hours, and then 0.05 to 1.2 parts by weight of a further molecular weight adjuster is prepared by reacting at 55 to 70 ℃ for 5 to 15 hours.

The small-diameter rubber latex preferably has an average particle diameter of 600 to 1500 mm 3 and a gel content of 80 to 99%.

The large-diameter rubber latex is prepared by gradually administering 1.0 to 4.0 parts by weight of an aqueous acetic acid solution to 100 parts by weight of the small-diameter rubber latex for 1 hour to enlarge the particles.

The large diameter rubber latex preferably has an average particle diameter of 2500 to 5000 mm 3 and a gel content of 80 to 99%. In the range of the gel content, graft copolymerization is effectively formed on the outside of the rubber particles, so that the impact strength and thermal stability are excellent, and in particular, it is possible to prevent a decrease in physical properties and thermal discoloration during extrusion under high temperature and high shear force to improve productivity.

(b) Preparation of Graft Rubber Latex

Graft rubber latex is graft copolymerized 30 to 50 parts by weight of the monomer mixture (50) to 50 to 70 parts by weight of the polybutadiene rubber latex, the polymerization initiator is differently applied within and after the polymerization conversion rate of the monomer mixture is 50% To prepare.

As said monomer mixture, an aromatic vinyl compound, a vinyl cyanide compound, an acrylate compound, etc. can be used individually or in mixture of 2 or more types.

With the above components, 0.1 to 2 parts by weight of an emulsifier, 0.05 to 2.0 parts by weight of a polymerization initiator, 0.1 to 0.5 parts by weight of an electrolyte, and 0.2 to 1.0 parts by weight of a molecular weight modifier may be used.

As said aromatic vinyl compound, styrene, (alpha) -methylstyrene, p-methylstyrene, vinyl toluene, t-butyl styrene, chloro styrene, these substituents, etc. can be used individually or in mixture of 2 or more types.

As said vinyl cyanide compound, acrylonitrile, methacrylonitrile, these substituents, etc. can be used individually or in mixture of 2 or more types.

As the acrylate compound, ethyl acrylate, methyl acrylate, butyl acrylate or ethyl hexyl acrylate may be used alone or in combination of two or more thereof.

As the emulsifier, a general adsorbent emulsifier such as alkyl aryl sulfonate, alkali methyl alkyl sulfate, sulfonated alkyl ester, alkali salt of fatty acid soap or rosin acid may be used alone or in combination of two or more thereof. In order to more effectively secure the stability of the latex, the reactive emulsifier and the polymer type reactive emulsifier may be used alone or in combination with the adsorptive emulsifier.

Examples of the polymerization initiator include fat-soluble peroxide-based polymerization initiators such as cumene hydroperoxide, diisopropyl benzenehydro peroxide, tertiary butylhydro peroxide, paramethane hydroperoxide or benzoyl peroxide and redox-based polymerization initiators. Can be used together

The fat-soluble peroxide-based polymerization initiator is applied to the primary fat-soluble peroxide-based polymerization initiator within the time point of the polymerization conversion rate of the initial monomer mixture is 50%, and after the reaction time the secondary fat-soluble peroxide-based polymerization initiator Applicable In addition, the fat-soluble peroxide-based polymerization initiator and the oxidation-reduction polymerization initiator may be used together to remove the unreacted monomer after the reaction is completed.

As the primary fat-soluble peroxide-based polymerization initiator, a polymerization initiator with strong fat-soluble properties such as cumene hydroperoxide or diisopropyl benzenehydro peroxide may be used.

As the secondary fat-soluble peroxide-based polymerization initiator, a relatively low fat-soluble polymerization initiator such as tertiary butyl hydroperoxide may be used.

The redox-based polymerization initiator is a metal salt such as iron (II), iron (III), cobalt (II) or cerium (IV), and as a reducing agent, polysaccharides such as dextrose, glucose, and flotose, Doxy acetone, polyamines, etc. can be used. Further, in order to maintain the activity of the metal catalyst under various basic conditions, it is possible to use tartaric acid, citric acid, phyllphosphoric acid or ethylene diamine tetraacetic acid salt.

As the electrolyte, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ or Na ₂ HPO ₄ or the like may be used alone or in combination of two or more thereof.

As the molecular weight regulator, mercaptans are preferable, and n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and the like can be used alone or in combination of two or more thereof.

In general, the monomer mixture in the graft polymerization may be used in a continuous input, batch or a continuous mixing and a batch input may be used in combination, there is no particular limitation on this, but preferably continuous input is effective for the cell graft reaction . In some cases, 5-30% of the total monomer mixture may be initially charged in a batch and the remaining monomer mixture may be continuously added. In this case, the monomer mixture to be initially added to the reaction batch is preferably added alone, and the monomer mixture to be continuously added is preferably added in an emulsified state including an emulsifier, ion-exchanged water and a polymerization initiator.

Preferably, the graft polymerization has a reaction time of 3 hours or less, a polymerization conversion rate after the reaction is 98.5% or more, and a molecular weight of 50,000 to 150,000.

The graft rubber latex prepared as described above may further include an antioxidant to prevent oxidation during processing.

As the antioxidant, phenol-based antioxidants, phosphorus-based, or sulfur-based antioxidants that are commonly used may be used, and 0.2 to 2 parts by weight based on 100 parts by weight of the graft rubber latex while the particle size is emulsified to 0.5 to 2 μm. It is desirable to be. When included in the content is effective to secure thermal stability during post-processing, it does not bring a change in mechanical properties and color is effective.

The antioxidant is typically added slowly to the graft rubber latex of 40 to 80 ℃ it is preferable to continuously stir until the aggregation process.

(B) Agglomeration of Graft Rubber Latex

Agglomeration method of the graft rubber latex of the present invention comprises the initial coagulation step of aggregating by adding a metal salt to the graft rubber latex prepared by the method of claim 1; And a late flocculation step of coagulation and maturation by adding acid to the initial flocculated latex.

As the metal salt, MgSO ₄ , CaCl ₂ or Al ₂ (SO ₄ ) ₃ may be used, and MgSO ₄ , CaCl ₂ is preferable.

Sulfuric acid, phosphoric acid or hydrochloric acid may be used as the acid, and sulfuric acid is preferable.

In general, in the flocculation process, either acid or metal salt is used, but the method of initial agglomeration with metal salt, followed by late agglomeration and aging with acid effectively ensures the oxidative stability and the color of the final product. Whiteness).

The pH of the graft rubber latex in the late coagulation step is preferably 3 to 7. In the above pH range, the whiteness of the resin does not tend to be lowered due to proper acid treatment, and thermal degradation due to the metal content remaining on the resin is not induced, which is effective.

The agglomerated graft rubber latex as described above may be separated into solids having a water content of 20 to 40% by removing water with a dehydrator, and then manufactured in a dry powder form using a hot air drying method and then introduced into an extruder. In addition, it may be introduced into the extruder as a solid content in the water-containing state, after the dehydration and water evaporation process in the extruder, and kneaded with a resin and a lubricant added as a matrix may be prepared into pellets.

(C) Graft Rubber Resin Composition Preparation

The method for producing a graft rubber resin composition of the present invention comprises the steps of: aggregating the graft rubber latex prepared by the above (A) production method by (B) agglomeration method; Preparing a water-containing rubber resin by removing the water content of the aggregated graft rubber latex with a compression dehydrator to 2 to 10% or less; And mixing, melting, and kneading the rubber resin containing water with at least one resin selected from the group consisting of styrene-acrylonitrile copolymer, polyvinyl chloride and polycarbonate, and a lubricant. .

In the step of dewatering the aggregated graft rubber latex with a compression type dehydrator, the water content may be removed to 2 to 10% or less, and preferably to 5% or less. In the case of the water content, it is possible to omit the extrusion step for dehydration and drying of the water, and at the same time there is an advantage to improve the extrusion productivity.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Example 1

Preparation of Graft Rubber Latex

60 parts by weight of polybutadiene rubber latex having a rubber particle diameter of 3,200 Å and a gel content of 98% (based on solids), 92 parts by weight of ion-exchanged water, and 0.2 parts by weight of fatty acid soap were added to a nitrogen-substituted polymerization reactor, and the temperature in the reactor was 50 ° C. 0.1 parts by weight of cumene hydroperoxide, 0.09 parts by weight of sodium pyrophosphate, 0.12 parts by weight of dextrose, 0.003 parts by weight of ferrous sulfide, and 28.8 parts by weight of styrene at a polymerization conversion rate of 55%. An emulsion of 11.2 parts by weight of acrylonitrile, 15 parts by weight of ion-exchanged water, 0.3 part by weight of tertiary dodecyl mercaptan, 0.6 part by weight of fatty acid soap, and 0.2 part by weight of tertiary butylhydroperoxide was heated to 70 ° C. for 2 hours. Continuous injection.

After the continuous administration, 0.05 parts by weight of cumene hydroperoxide, 0.043 parts by weight of sodium pyrophosphate, 0.055 parts by weight of dextrose and 0.001 parts by weight of ferrous sulfide were collectively administered at a temperature of 80 ° C. and maintained for 60 minutes. The reaction was terminated after removing the reaction monomer.

Agglomeration of Graft Rubber Latex

0.5 parts by weight of an antioxidant (Wingstay-L) emulsion having an average particle diameter of 1.0 μm was added to the finished graft rubber latex, and then primary aggregated in the presence of 1.5 parts by weight of MgSO ₄ at 78 ° C., and additional 0.5 parts by weight of an aqueous sulfuric acid solution. After the second agglomeration and aged at 90 ℃ and washed it to obtain a powdery graft polymer having a water content of 25% level.

Preparation of Graft Rubber Resin Composition

The water-containing graft copolymer having a water content of 25% was added to a compression dehydrator to remove water so that the water content was 5%. A sample was prepared so that the final rubber content was 14% by adding a styrene-acrylonitrile (SAN) copolymer having a weight average molecular weight of about 100,000 and an acrylonitrile content of about 28% and a lubricant, and extruding and injection molding. And the physical property was measured.

Example 2

In Example 1, 60 parts by weight of polybutadiene rubber latex having a rubber particle diameter of 3200 mm and a gel content of 98% (based on solids), 92 parts by weight of ion-exchanged water, 7.2 parts by weight of styrene, and acrylonitrile in a nitrogen-substituted polymerization reactor 2.8 parts by weight, 0.4 parts by weight of fatty acid soap, the temperature in the reactor was maintained at 50 ℃, 0.1 parts by weight cumene hydro peroxide, 0.09 parts by weight sodium pyrophosphate, 0.12 parts by weight dextrose, 0.003 parts by weight ferrous sulfide The batch was injected and the temperature was raised to 70 ° C. for 20 minutes.

After the temperature increase, the emulsion consisting of 21.6 parts by weight of styrene, 8.4 parts by weight of acrylonitrile, 15 parts by weight of ion-exchanged water, 0.3 parts by weight of tertiary dodecyl mercaptan, 0.6 parts by weight of fatty acid soap, and 0.2 parts by weight of tertiary butylhydroperoxide It was carried out in the same manner as in Example 1 except that the continuous injection while maintaining at 70 ℃ for 1 hour 40 minutes.

Example 3

Except that in Example 1 using 60 parts by weight of polybutadiene rubber latex having a rubber particle diameter of 3200 mm 3 and a gel content of 70 parts by weight, and using 2 parts by weight of MgSO ₄ alone with respect to the obtained graft rubber latex, It carried out by the same method as Example 1.

Example 4

In Example 3, 0.1 parts by weight of tertiary butylhydroperoxide instead of 0.1 parts by weight of cumene hydroperoxide was initially used as the polymerization initiator, and after the monomer emulsion was added, tertiary butyl instead of 0.05 parts by weight of the polymerization initiator cumene hydroperoxide. Except that 0.05 parts by weight of hydroperoxide was used in the same manner as in Example 3.

Example 5

Except for the use of a mixture of 30 parts by weight of polybutadiene rubber latex having a rubber particle diameter of 3200 mm 3 and a gel content of 98% and 30 parts by weight of polybutadiene rubber latex having a gel content of 70% at the same rubber particle size, It carried out by the same method as Example 4.

[Test Example]

The physical properties of the specimens prepared in Example were measured by the following method, and the results are shown in Table 1 below.

* Izod impact strength: Measured according to ASTM D256 method with 1/4 "thickness of specimen.

* Scotch: Moisture 25% or more of powder obtained from graft rubber latex is placed in aluminum foil in contact with oxygen in the air, then placed in a 190 ℃ hot air oven and sampled by time zone to observe the discoloration of each sample. It was. The relative thermal stability was determined by measuring the time, usually in the carbonized state.

* Maximum oxidation time: The sample was left in 190 ℃, oxygen atmosphere using a TGA measuring device and the value was measured by measuring the time at which the maximum weight change occurs.

* Retention gloss: The pellet obtained from the extruder was put in the injection molding machine and held for 15 minutes at 250 ° C., and then the gloss specimen was obtained. The gloss was measured at 45 ° and the deviation was measured. . Smaller measured values indicate better retention gloss.

* Retention Discoloration (△ E): For the gloss specimen obtained by the same method as the method of measuring the retention gloss, using the Suga color computer, calculate the L, a, b values for the specimens before and after the dwelling, The degree of retention discoloration was determined.

[Equation 1]

division Example 1 Example 2 Example 3 Example 4 Example 5 Rubber Latex Gel content (%) 98 98 70 70 98/70 Content (parts by weight) 60 60 60 60 30/30 Input of monomer mixture Batch / continuous 0/40 10/30 0/40 0/40 0/40 Polymerization initiator Within 50% of polymerization conversion rate CHP / TBHP CHP / TBHP CHP / TBHP TBHP / TBHP TBHP / TBHP Antioxidant Content (parts by weight) 0.5 0.5 0.5 0.5 0.5 Flocculant MgSO ₄ / H ₂ SO ₄ 1.5 / 0.5 1.5 / 0.5 2.0 / 0 2.0 / 0 2.0 / 0 Impact Strength (1/4 ") (kgcm / cm) 27 28 15 16 20 liquidity 19 18 19 18 19 Whiteness 56 55 48 45 49 Scorch (min) 50 45 15 10 13 Retention heat discoloration 1.9 2.3 4.0 6.2 5.2 Staying gloss △ 2 △ 5 △ 10 △ 15 △ 7

Through Table 1, the primary fat-soluble peroxide-based polymerization initiator is applied within 50% of the polymerization conversion rate according to the present invention, and the second fat-soluble peroxide-based polymerization initiator is applied to the graft rubber latex after the time point. The graft rubber resin composition specimens of Examples 1 to 2, which were prepared through a two-step flocculation process, were prepared by applying primary and secondary fat-soluble peroxide-based polymerization initiators. Example 3, without applying the primary and secondary fat-soluble peroxide-based polymerization initiator, it was confirmed that the physical properties and thermal stability is excellent compared to Examples 4 to 5 prepared through a single step flocculation process.

As described above, according to the present invention, there is an effect of increasing the efficiency when applied to the compression dehydrator and providing a method of producing graft rubber latex having excellent thermal stability and agglomeration thereof without the addition of an additional heat stabilizer.

Claims (11)

A method for producing graft rubber latex by polymerizing at least one monomer mixture selected from the group consisting of rubber latex, aromatic vinyl compound, vinyl cyan compound and acrylate compound, A primary fat-soluble peroxide-based polymerization initiator is applied within a time point at which the polymerization conversion rate of the monomer mixture is 50%, and a second fat-soluble peroxide-based polymerization initiator is applied after the time point. Method for producing graft rubber latex. The method of claim 1, The method for producing the graft rubber latex is selected from the group consisting of 50 to 70 parts by weight of rubber latex having an average particle diameter of 2,500 to 5,000 mm 3 and a gel content of 80 to 99%, an aromatic vinyl compound, a vinyl cyanide compound and an acrylate compound. 30 to 50 parts by weight of at least one monomer mixture, characterized in that the polymerization Method for producing graft rubber latex. The method of claim 1, The primary fat-soluble peroxide-based polymerization initiator is characterized in that at least one selected from the group consisting of cumene hydro peroxide and diisopropyl benzenehydro peroxide. Method for producing graft rubber latex. The method of claim 1, The secondary fat-soluble peroxide-based polymerization initiator is characterized in that using the tertiary butyl hydroperoxide Method for producing graft rubber latex. The method of claim 1, The primary and secondary fat-soluble peroxide-based polymerization initiator is characterized in that it is used in conjunction with the redox polymerization initiator Method for producing graft rubber latex. The method of claim 1, Method for producing the graft rubber latex is characterized in that it further adds at least one antioxidant selected from the group consisting of phenolic, phosphorus and sulfur-based antioxidants Method for producing graft rubber latex. The method of claim 6, The antioxidant is added in an amount of 0.2 to 2 parts by weight based on 100 parts by weight of the graft rubber latex while the particle size is emulsified to 0.5 to 2 ㎛ Method for producing graft rubber latex. The method of claim 6, The antioxidant is slowly added to the graft rubber latex of 40 to 80 ℃ characterized in that the stirring is continued until the flocculation process Method for producing graft rubber latex. An initial agglomeration step of aggregating by adding a metal salt to the graft rubber latex prepared by the method of claim 1; And Characterized in that it comprises a ;; agglomeration and maturation by adding an acid to the initial flocculated latex; Agglomeration method of graft rubber latex. The method of claim 9, The late coagulation step is characterized in that the pH of the graft rubber latex is 3 to 7 Agglomeration method of graft rubber latex. Agglomeration of the graft rubber latex produced by the manufacturing method of claim 1 by the coagulation method of claim 8; Preparing a water-containing rubber resin by removing the water content of the aggregated graft rubber latex with a compression dehydrator to 2 to 10% or less; And Mixing, melting, and kneading a rubber resin containing water with at least one resin selected from the group consisting of styrene-acrylonitrile copolymers, polyvinyl chlorides, and polycarbonates, and a lubricant. Method for producing a graft rubber resin composition.