KR20180047752A - Method for preparing abs graft copolymer and method for preparing abs molding product - Google Patents

Abstract

The present invention relates to a method for producing an acrylonitrile-butadiene-styrene (ABS)-based graft copolymer, and a method for producing an ABS-based injection-molded article including the same. More specifically, provided are a method for producing an ABS-based graft copolymer, and a method for producing an ABS-based injection-molded article including the same. When copolymerizing a vinyl cyan monomer and an aromatic vinyl monomer on a large-diameter diene-based rubbery latex, an amount of gas produced on a surface of a resin during a high temperature injection process can be reduced through introduction of polymer acid of unsaturated fatty acid or a metal salt thereof as an emulsifier, thereby improving definition and surface gloss of finally injected articles.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a process for producing an ABS-based graft copolymer and an ABS-based injection-

The present invention relates to a process for producing an ABS-based graft copolymer and a process for producing an ABS-based injection-molded article containing the same, and more particularly, to a process for producing an ABS-based graft copolymer by graft-polymerizing an aromatic vinyl monomer and a vinyl cyan monomer onto a large- , A process for producing an ABS-based graft copolymer capable of improving the surface gloss and sharpness of a final product by reducing the amount of gas generated in a high-temperature injection process by introducing a polymerizable unsaturated fatty acid or its metal salt as an emulsifier, and The present invention relates to a method of producing an ABS injection molded article.

Acrylonitrile-butadiene-styrene (ABS) copolymer resin has relatively good physical properties such as moldability and gloss as well as mechanical strength such as impact resistance and the like, Parts and the like.

Generally, when an aromatic vinyl compound and a vinyl cyan compound monomer are grafted by a emulsion polymerization method to a conjugated diene rubbery latex, an ABS copolymer resin is produced. The ABS copolymer resin exhibits a good balance of physical properties as compared with that prepared by the bulk polymerization method, And the ABS-based copolymer resin is usually produced by the emulsion polymerization method.

The ABS-based copolymer resin prepared as described above may also be blended with a styrene-acrylonitrile copolymer (SAN) to form an ABS-based thermoplastic resin composition. The ABS-based thermoplastic resin composition prepared by the above- Impact strength, processability, and chemical resistance. However, the use of an emulsifier and a coagulant in the production of the graft copolymer has physical limitations such as gloss and sharpness.

Korean Patent No. 1530150

In order to solve the problems of the prior art as described above, the present invention has introduced an emulsifier which can not easily vaporize in a high-temperature injection process, effectively reducing the amount of gas generated, and ultimately improving the surface gloss and sharpness of ABS- The present invention also provides a method for producing an ABS-based graft copolymer.

It is another object of the present invention to provide a process for producing an ABS injection molded article comprising the ABS-based graft copolymer according to the above production method.

These 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 relates to a composition comprising 100 parts by weight of a monomer mixture comprising 40 to 70% by weight (based on solids) of a large-diameter diene rubbery latex, 15 to 35% by weight of an aromatic vinyl monomer, and 5 to 25% by weight of a vinyl cyan monomer 0.01 to 3 parts by weight of an emulsifier, 0.01 to 3 parts by weight of an initiator, and 0.001 to 1 part by weight of an oxidation-reduction catalyst, wherein the emulsifier is a multimer acid of an unsaturated fatty acid or And a metal salt thereof. The present invention also provides a process for producing the ABS-based graft copolymer.

The present invention also relates to a process for producing a rubber composition, comprising the steps of: a) mixing 100 parts by weight of a monomer mixture comprising 40 to 70% by weight (based on solids) of a large diameter diene rubbery latex, 15 to 35% by weight of an aromatic vinyl monomer and 5 to 25% by weight of a vinyl cyan monomer, 0.01 to 3 parts by weight of an initiator, 0.01 to 2 parts by weight of an initiator, and 0.001 to 0.4 part by weight of an oxidation-reduction catalyst are subjected to primary graft polymerization; And b) 0.01 to 1 part by weight of an initiator and 0.001 to 0.6 part by weight of an oxidation-reduction catalyst are subjected to second graft polymerization after the step a), wherein the emulsifier is a polyvalent acid of an unsaturated fatty acid the present invention provides a method for producing an ABS-based graft copolymer, which is a multimer acid or a metal salt thereof.

The present invention also relates to a process for producing a rubber composition, which comprises mixing 10 to 50% by weight of an ABS-based graft copolymer and 50 to 90% by weight of an aromatic vinyl monomer-vinyl cyan monomer copolymer according to the above production method, A method of manufacturing an ABS injection molded article is provided.

According to the present invention, when the ABS-based graft copolymer is prepared, the polymerization reaction stability is ensured by introducing the polymerized acid or its salt of an unsaturated fatty acid as an emulsifier, and the amount of gas generated on the resin surface in the high- There is an advantage that the surface gloss and sharpness of the final product can be improved.

In addition, the ABS-based graft copolymer latex produced according to the present invention can contribute to the improvement of the productivity of the ABS resin by reducing the coagulated content.

The present inventors confirmed that the gas generated on the surface of the resin affects the roughness of the surface of the resin in a high temperature extrusion or injection process and analyzed the substances generating gas. As a result, it was found that the remaining emulsifier, unreacted monomer, And so on.

Accordingly, the present inventors have succeeded in securing the stability of the polymerization reaction by using a macromolecule of an unsaturated fatty acid having a high molecular weight and a high molecular weight in a high temperature extrusion or injection process as an emulsifier or a metal salt thereof, It was confirmed that the quality such as glossiness and clarity of the final molded product was improved, and based on this, the product was further sold out, thereby completing the present invention.

In the present invention, the polycarboxylic acid of the unsaturated fatty acid is a polyvalent carboxylic acid obtained by polymerization reaction of an unsaturated fatty acid having two or more molecules, and the unsaturated fatty acid includes a linear or branched type, a cyclic or a cyclic unsaturated fatty acid or a derivative thereof .

In the present description, a derivative means a compound in which one or two or more of the hydrogen atoms of the original compound are independently substituted with an alkyl group, a halogen group or a hydroxy group.

In the present description, the compound cyclic type means that at least two or more saturated or unsaturated cycloalkyl groups having 5 to 15 carbon atoms are contained.

Hereinafter, the method for producing the ABS-based graft copolymer of the present invention will be described in detail.

The method for producing an ABS-based graft copolymer according to the present invention is a method for producing an ABS-based graft copolymer comprising a monomer mixture 100 comprising 40 to 70% by weight (based on solids) of a large-diameter diene rubbery latex, 15 to 35% by weight of an aromatic vinyl monomer and 5 to 25% by weight of a vinyl cyan monomer 0.01 to 3 parts by weight of an emulsifier, 0.01 to 3 parts by weight of an initiator, and 0.001 to 1 part by weight of an oxidation-reduction catalyst are graft-polymerized with an emulsifier and a polymerizable unsaturated fatty acid or a metal salt thereof .

The large diameter diene rubbery latex may comprise a polymer polymerized from at least one monomer selected from the group consisting of conjugated diene monomers, for example, 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene and chloroprene have.

The large diameter diene rubbery latex preferably has an average particle diameter of 2800 to 3500 angstroms, 2900 to 3500 angstroms or 2900 to 3200 angstroms, because the physical properties of the ABS resin depend on the average particle size of the diene rubbery latex , And the ABS resin produced from a large-diameter diene rubbery latex having an average particle diameter in the above-mentioned range has an excellent impact strength and mechanical properties.

In the present invention, the average particle diameter of the latex can be measured by mixing 1 g of latex with 100 g of distilled water and then using a Nicol 370HPL in a dynamic laser light skating method.

The large diameter diene rubbery latex may have a solid content of 40 to 65% by weight or 50 to 65% by weight, and the ABS resin produced from a diene rubbery latex having a solid content within this range may have mechanical properties such as impact strength There is an excellent advantage.

The large-diameter diene rubbery latex may be mixed with the monomer mixture in an amount of 40 to 70% by weight, 50 to 70% by weight or 55 to 65% by weight based on the solid content.

When the above-mentioned large-diameter diene rubbery latex is used within the above-mentioned range, the ABS resin produced therefrom has an excellent balance of mechanical properties and physical properties.

Wherein the aromatic vinyl monomer is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Ethylstyrene, p-methylstyrene, ot-butylstyrene, bromostyrene, chlorostyrene, trichlorostyrene, But is not limited to,

The aromatic vinyl monomer may be mixed in the monomer mixture in an amount of 15 to 35% by weight, 20 to 35% by weight, or 25 to 35% by weight. Within this range, excellent balance of mechanical properties and physical properties There is an advantage to doing.

The vinyl cyan monomer may include at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and derivatives thereof, but is not limited thereto.

It is preferable that the vinyl cyan monomer is mixed with the remaining balance or 5 to 25% by weight, 5 to 20% by weight or 5 to 15% by weight in the monomer mixture. Within this range, the mechanical properties of the ABS- There is an effect that the physical property balance is excellent.

The emulsifier may contain a polymerizable unsaturated fatty acid or a metal salt thereof, which is not easily vaporized in a high temperature injection process, effectively reducing the amount of gas generated, and ultimately improving the surface gloss and sharpness of the ABS- .

The emulsifier may include, for example, a polycondensate of a linear or branched, cyclic or cyclic unsaturated fatty acid having 8 to 22 carbon atoms, or a metal salt thereof, which is not easily vaporized in a high temperature injection process, Thereby effectively reducing the surface gloss and sharpness of ABS resin articles.

The emulsifier may include, for example, a dimer acid of an unsaturated fatty acid or a metal salt thereof, which has the effect of improving surface gloss and sharpness of an ABS injection molded article.

Specific examples of the unsaturated fatty acids include 3-octenoic acid, 10-undecenoic acid, oleic acid, linoleic acid, elaidic acid, palmitoleic acid, linolenic acid or a mixture of two or more thereof or tallow fatty acid, soybean oil fatty acid, palm oil fatty acid, Fatty acids, peanut fatty acids, rice bran fatty acids, flaxseed oil fatty acids, and the like.

The emulsifier may include at least one dimer acid or a metal salt thereof selected from the group consisting of compounds represented by the following formulas (1) to (6) to improve the surface gloss and sharpness of the ABS injection molded article have.

[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The emulsifier may be, for example, an alkali metal salt or an alkaline earth metal salt of a polyunsaturated fatty acid. This reduces the amount of gas generated during a high-temperature extrusion or injection process, thereby improving surface gloss and sharpness of the final product.

The alkali metal salt may be, for example, a sodium salt or a potassium salt. When the sodium salt or potassium salt of the unsaturated fatty acid polymeric acid is used as an emulsifier, the surface gloss and sharpness of the ABS injection molded article may be improved.

The alkaline earth metal salt may be, for example, a magnesium salt or a calcium salt. When the magnesium salt or calcium salt of the unsaturated fatty acid polymeric acid is used as an emulsifier, surface gloss and sharpness of an ABS injection molded article are improved.

For example, the metal salt of the unsaturated fatty acid multimer may be a compound in which a hydrogen atom of a carboxylic acid is substituted with an alkali metal by adding a hydroxide of an alkali metal such as NaOH or KOH to the unsaturated fatty acid dimer acid, Or not.

As another example, the metal salt of the unsaturated fatty acid polymeric acid may be a compound prepared by adding a metal salt such as a calcium salt or a magnesium salt to the unsaturated fatty acid polymeric acid or the compound substituted with the alkali metal, but not limited thereto .

In the present invention, the emulsifier may be used in an amount of 0.01 to 3 parts by weight, 0.05 to 2 parts by weight, 0.1 to 1.5 parts by weight or 0.3 to 1.0 part by weight based on 100 parts by weight of the monomer mixture, The stability of the reaction can be secured.

In addition, the emulsifier may be used by mixing one or more auxiliary emulsifiers selected from the group consisting of alkylaryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters and metal salts of unsaturated fatty acids.

When the auxiliary emulsifier is used in combination, the content of the auxiliary emulsifier may be preferably 1 to 60% by weight, 5 to 40% by weight or 10 to 30% by weight based on 100% by weight of the emulsifier, The preferred amount is 10 to 30% by weight. When the auxiliary emulsifier is used in combination within the above-mentioned range, the amount of solidification of the ABS-based graft copolymer latex is reduced and the amount of gas generated during injection molding is reduced to improve the impact resistance, gloss and sharpness of the resin .

The initiator may be a water-soluble initiator or a water-soluble initiator. Examples of the water-soluble initiator include sodium persulfate, potassium persulfate, ammonium persulfate and the like. The oil-soluble initiator includes cumene hydroperoxide, diisopropylbenzene hydroperoxide Oxides, tertiary butyl hydroperoxide, para-methane hydroperoxide, benzoyl peroxide, and the like, and it may be possible to use them in combination as required.

The initiator may be added in an amount of, for example, 0.01 to 3 parts by weight, 0.05 to 2 parts by weight, or 0.1 to 2 parts by weight, and a polymer having a desired particle size and size distribution may be produced within the above range without causing excessive reaction .

The initiator may be added before the start of the graft polymerization and during the graft polymerization, for example. When the initiator is added in this manner, the unreacted monomer content is reduced and a resin having a high graft rate within a short period of time can be produced.

The oxidation-reduction catalyst may include at least one member selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, pyrrole sodium phosphate and sodium sulfite But is not limited thereto.

The oxidation-reduction catalyst may be used in an amount of, for example, 0.001 to 0.4 parts by weight, 0.005 to 0.2 parts by weight, or 0.01 to 0.2 parts by weight, and the polymerization reaction may be accelerated within the above range to produce an ABS-based graft copolymer in a short time .

The oxidation-reduction catalyst may be added before the initiation of the graft polymerization and during the graft polymerization, for example. When the oxidation-reduction catalyst is added in this manner, the unreacted monomer content is decreased and the polymerization degree is increased within a short period of time Can be achieved.

In the case where the initiator and the oxidation-reduction catalyst are separately introduced as described above in the present invention, for example, the following steps may be carried out including:

(a) 0.01 to 3 parts by weight of an emulsifier is added to 100 parts by weight of a monomer mixture comprising 40 to 70% by weight (based on solids) of a large-diameter diene rubbery latex, 15 to 35% by weight of an aromatic vinyl monomer and 5 to 25% by weight of a vinyl cyan monomer 0.01 to 2 parts by weight of an initiator, and 0.001 to 0.4 part by weight of a redox-based catalyst are subjected to primary graft polymerization; And

b) After the step a), the second graft polymerization is carried out by adding 0.01 to 1 part by weight of an initiator and 0.001 to 0.6 part by weight of an oxidation-reduction catalyst.

In the step a), 0.01 to 2 parts by weight, 0.05 to 1 part by weight or 0.05 to 0.5 part by weight of an initiator is added, and 0.001 to 0.4 parts by weight, 0.005 to 0.2 parts by weight or 0.01 to 0.2 parts by weight of an oxidation- The amount of the unreacted monomer in the product is reduced, so that a graft polymer having excellent physical properties can be prepared.

The step a) may be carried out at a temperature of, for example, 50 to 90 ° C or 60 to 80 ° C. Within the above range, the polymerization reaction is initiated by the activation of the initiator, Polymers can be prepared.

0.01 to 1 part by weight, 0.01 to 0.5 part by weight, or 0.01 to 0.1 part by weight of an initiator in the step b), 0.001 to 0.6 part by weight, 0.01 to 0.3 part by weight or 0.01 to 0.1 part by weight of an oxidation- And the content of the unreacted monomers in the product may be reduced within the above range, so that the physical properties of the polymer may be improved.

In step b), for example, it may be preferable to raise the reaction temperature to 60 to 100 ° C or 70 to 90 ° C (higher than the reaction temperature in step a), and the reaction may be carried out within this range. The physical properties of the polymer can be improved.

The molecular weight modifier may be added in an amount of 0.1 to 1 part by weight, 0.2 to 0.6 part by weight, or 0.3 to 0.5 part by weight, for example. In the above-mentioned range, , And the polymer has the effect of making the size uniform.

As the molecular weight modifier, for example, a mercaptan compound such as tertiary dodecyl mercaptan may be used, but it is not limited thereto.

In the present invention, it may be preferable to terminate the reaction at a conversion rate of 90 to 99%, 92 to 99%, or 95 to 99% of the graft polymerization reaction to obtain a graft copolymer, The unreacted monomer content is low and the physical properties can be further improved.

In the present invention, the conversion rate of the polymerization reaction can be calculated by calculating the total solid content (TSC) by measuring 1.5 g of the prepared latex in a 150 ° C hot air drier for 15 minutes and measuring the weight.

[Equation 1]

Polymerization Conversion (%) = Total Solid Content (TSC) X (Weight of Added Monomers and Substrates) / 100 -

The ABS-based graft copolymer latex prepared according to the present invention may preferably have a coagulated content of 0.15 wt% or less, or 0.01 to 0.1 wt% or less. The ABS-based resin latex exhibits excellent productivity of the ABS resin within the above range, The physical properties such as strength can be improved.

Other reaction conditions such as graft rate, reaction pressure, etc., in addition to the above-mentioned description are not particularly limited when they are within the range usually practiced in the technical field of the present invention, and it is specified that they can be appropriately selected and carried out if necessary.

The ABS-based graft copolymer latex prepared according to the present invention is prepared in powder form through conventional processes such as coagulation, washing and drying. The powder is mixed with a SAN resin or the like, extruded and injected to form an ABS injection molded article .

The ABS-based injection molded article manufacturing method of the present invention comprises mixing 10 to 50% by weight of the ABS-based graft copolymer and 50 to 90% by weight of an aromatic vinyl monomer-vinyl cyan monomer copolymer and extruding the mixture When the ABS injection molded product is manufactured by mixing within the above-mentioned range, it is possible to manufacture an ABS injection molded article having excellent mechanical properties, surface gloss and sharpness.

In another example, the ABS-based injection molded article manufacturing method of the present invention comprises extruding 20 to 40% by weight of an ABS-based graft copolymer and 60 to 80% by weight of an aromatic vinyl monomer-vinyl cyan monomer copolymer, And the mechanical properties, surface gloss and sharpness of the ABS injection molded article are excellent within the above range.

In another example, the ABS-based injection molded article manufacturing method of the present invention comprises mixing 25 to 30% by weight of an ABS-based graft copolymer and 70 to 75% by weight of an aromatic vinyl monomer-vinyl cyan monomer copolymer, And there is an effect of excellent mechanical properties and optical properties within this range.

The aromatic vinyl monomer-vinyl cyan monomer copolymer may be, for example, a copolymer of vinyl aromatic monomers such as styrene and? -Methyl styrene, and vinyl cyan monomers such as acrylonitrile, methacrylonitrile, and ethacrylonitrile.

The aromatic vinyl monomer-vinyl cyan monomer copolymer may be, for example, a copolymer of 50 to 80% by weight of an aromatic vinyl monomer and 20 to 50% by weight of a vinyl cyan monomer. In another example, an aromatic vinyl monomer may be contained in an amount of 65 to 80% 20 to 35% by weight of a cyan monomer, and it is possible to produce an ABS injection molded article having the desired mechanical properties within the above range.

The extrusion can be carried out under conditions of, for example, 200 to 400 ° C and 140 to 190 rpm, or 200 to 220 ° C and 150 to 180 rpm, and it is possible to produce an ABS resin having the desired mechanical properties within this range .

The injection may be carried out under conditions of, for example, 200 to 230 DEG C and 70 to 90 bar, or 200 to 220 DEG C and 70 to 80 bar, and the production of ABS injection molded articles having the desired mechanical properties within this range It can be possible.

In the injection, the gas generation amount may be preferably 4,500 ppm or less, 3,500 ppm or less, 3,000 ppm or less, 2,500 ppm or 10 to 4,500 ppm, and the surface gloss and sharpness of the injection- There is an effect to be improved.

In the present invention, the amount of gas generated can be measured by gas chromatography using 1 g of VOC generated at 200 to 300 DEG C for 1 hour with respect to 1 g of the resin composition.

The ABS injection molded product manufactured by the manufacturing method of the present invention may have a reflection haze of 2.5 or less, 2.0 or 1.9 or less, and a glossiness (45) of 90 or more or 93 or more , The reflective haze and gloss values can be measured according to standard measurements ASTM E430 and ASTM D528, respectively.

Other conditions not explicitly described in the above-mentioned production method of an ABS injection molded article are not particularly limited if they are within the range usually practiced in the technical field of the present invention, and can be appropriately selected as needed.

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 spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

[Example]

Example  One

1. Preparation of ABS Graft Copolymer

10 parts by weight of acrylonitrile mixed in a separate mixing apparatus in 60 parts by weight of a large diameter diene rubbery latex (average particle diameter of 3000 Å, solid content of 50% by weight) and 100 parts by weight of ion-exchanged water were added to a nitrogen- 25 parts by weight of ion exchanged water, 0.12 part by weight of t-butyl hydroperoxide, 0.7 part by weight of potassium dimetate (Cas No. 67701-19-3) and 0.35 part by weight of tertiary dodecyl mercaptan 0.054 part by weight of dextrose, 0.004 part by weight of sodium pyrrolephosphate and 0.002 part by weight of ferrous sulfate were added together at 70 DEG C for 3 hours.

After the addition, 0.05 part by weight of dextrose, 0.03 part by weight of sodium pyrrolephosphate, 0.001 part by weight of ferrous sulfate and 0.05 part by weight of t-butylhydroperoxide were fed into the polymerization reactor, And the reaction was terminated to prepare an ABS latex. The polymerization conversion was 97%.

2. Manufacture of ABS injection molding

27.5 parts by weight of this powder and 72.5 parts by weight of SAN (product name: 92HR, manufactured by LG Chemical Co., Ltd.) were mixed in a mixer, followed by mixing and kneading (Injection temperature: 210 ° C, injection pressure: 80 bar, Engel ES200 / 45 HL-Pro Series), and the specimens for measuring the properties were obtained.

Example  2

The procedure of Example 1 was repeated, except that 0.5 part by weight of potassium dimetate and 0.2 part by weight of rosin acid saponite were used in place of 0.7 part by weight of potassium dimyrate in Example 1.

Example  3

Example 1 was repeated except that 0.5 part by weight of potassium dimetate and 0.2 part by weight of fatty acid saponification C16 to C18 were used in place of 0.7 part by weight of potassium dimyrate .

Example  4

Except that 0.3 part by weight of potassium dimetate, 0.2 part by weight of rosin acid saponite and 0.2 part by weight of fatty acid saponified C16 to C18 were used in place of 0.7 part by weight of potassium dimyrate salt in Example 1 The procedure of Example 1 was repeated.

Comparative Example  One

The procedure of Example 1 was repeated, except that C16 to C18 fatty acid saponification was used instead of dimer acid potassium salt.

[Test Example]

The properties of the samples prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

Amount of gas generated (ppm)

The total amount of volatile organic compounds (VOC) generated at 250 ° C for 1 hour was analyzed for 1 g of the composition including the ABS resin prepared in the above Examples and Comparative Examples using HS-GC / MSD.

Reflection haze

Gloss specimens were used to measure sharpness by adding gloss values between 17-19 and 21-23 according to standard measurement ASTM E430.

Gloss (45 °)

The gloss of the specimen was measured according to ASTM D528 at 45 °.

Solidification product  Content (Coagulum, g / 100g)

The weight of the solidified product, the weight of the total rubber and the weight of the monomer produced in the reaction tank were measured and the solid solid content of the small-diameter rubbery polymer latex was calculated using the following equation (2).

&Quot; (2) "

(G) / total rubber weight and the weight of the monomer (100 g)

Example 1
Example 2
Example 3
Example 4
Comparative Example 1 Gas production [ppm] 2,100 2,400 2,900 3,100 4,800 definition 1.6 1.8 1.9 2.7 2.7 Glossiness 94.7 93.8 93.2 93.7 89.1 Of ABS latex
Solidification water content [g / 100 g]
0.14
0.11
0.09
0.07
0.19

As shown in Table 1, in Examples 1 to 4 using potassium dimyrate as an emulsifier at the time of preparing the ABS-based graft copolymer, it was confirmed that the amount of gas generated at the time of injection was considerably smaller than that of Comparative Example 1 , Which can be attributed to the property that the potassium salt of dimer acid is not well vaporized due to the high molecular weight of the emulsifier for the production of the ABS-based copolymer.

Further, it was confirmed that the gas generation amount affects the roughness of the surface of the resin, and in Examples 1 to 4 in which the amount of gas generation was small, the reflection haze (sharpness) value was low and the glossiness was high compared with Comparative Example 1, I could.

As a result of the measurement of the coagulated content of the ABS polymer latex, it was confirmed that the values of Examples 1 to 4 were lower than those of Comparative Example 1, and it was found through this that the macromolecule metal salt also contributed to the improvement of the stability of the latex .

Claims (15)

To 100 parts by weight of a monomer mixture comprising 40 to 70% by weight (based on solid content) of a large-diameter diene rubbery latex, 15 to 35% by weight of an aromatic vinyl monomer and 5 to 25% by weight of a vinyl cyan monomer, 0.01 to 3 parts by weight of an emulsifier, 0.01 to 3 parts by weight, and 0.001 to 1 part by weight of an oxidation-reduction catalyst,
Wherein the emulsifier is a multimer acid of an unsaturated fatty acid or a metal salt thereof. The method according to claim 1,
Wherein the unsaturated fatty acid is a linear, branched or cyclic unsaturated fatty acid having 8 to 22 carbon atoms. The method according to claim 1,
Wherein the multimeric acid is a dimer acid. ≪ RTI ID = 0.0 > 11. < / RTI > The method of claim 3,
Wherein the dimer acid is at least one compound selected from the group consisting of compounds represented by the following formulas (1) to (6).
[Chemical Formula 1]

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The method according to claim 1,
Wherein the metal salt is an alkali metal salt or an alkaline earth metal salt. 6. The method of claim 5,
Wherein the alkali metal salt is a sodium salt or a potassium salt. 6. The method of claim 5,
Wherein the alkaline earth metal salt is a magnesium salt or a calcium salt. The method according to claim 1,
Wherein the large-diameter diene-based rubbery latex has an average particle diameter of 2800 to 3500 Å and a solid content of 40 to 65% by weight. The method according to claim 1,
Wherein the emulsifier further comprises at least one auxiliary emulsifier selected from the group consisting of alkylaryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters and metal salts of unsaturated fatty acids. Way. 10. The method of claim 9,
Wherein the auxiliary emulsifier is contained in an amount of 1 to 60% by weight based on 100% by weight of the total amount of the emulsifier. The method according to claim 1,
Wherein the ABS-based graft copolymer latex prepared by the graft polymerization has a coagulated content of 0.15% by weight or less. (a) 0.01 to 3 parts by weight of an emulsifier is added to 100 parts by weight of a monomer mixture comprising 40 to 70% by weight (based on solids) of a large-diameter diene rubbery latex, 15 to 35% by weight of an aromatic vinyl monomer and 5 to 25% by weight of a vinyl cyan monomer 0.01 to 2 parts by weight of an initiator, and 0.001 to 0.4 part by weight of an oxidation-reduction catalyst are subjected to primary graft polymerization; And b) 0.01 to 1 part by weight of an initiator and 0.001 to 0.6 part by weight of an oxidation-reduction catalyst are subjected to second graft polymerization after the step a)
Wherein the emulsifier is a multimer acid of an unsaturated fatty acid or a metal salt thereof. 10 to 50% by weight of an ABS-based graft copolymer according to the production method of any one of claims 1 to 12 and 50 to 90% by weight of an aromatic vinyl monomer-vinyl cyan monomer copolymer are mixed and extruded, Based on the total weight of the injection-molded article. 14. The method of claim 13,
Wherein the gas generation amount at the time of injection is 4,500 ppm or less. 14. The method of claim 13,
Wherein the ABS injection molded article has a reflection haze of 2.5 or less and a glossiness (45) of 90 or more.