KR101288752B1 - Rubber polymer latex, method of preparing the same, and ABS graft copolymer comprising the same - Google Patents

Abstract

The present invention relates to a large-diameter rubbery polymer latex, a method for preparing the same, and an ABS graft copolymer including the same. More specifically, the conjugated diene-based compound may be prepared by controlling the point of introduction of a crosslinking agent when preparing a rubbery polymer latex applied to an ABS resin. The gel content of the rubbery polymer latex can be controlled by controlling the distance between the crosslinking points. Applying the latex gel content control technology of the present invention can maximize the conversion rate of the large diameter rubbery polymer latex applied to the ABS resin in a short time to provide an ABS thermoplastic resin excellent in impact strength, gloss and processability, surface sharpness. .

ABS resin, rubbery polymer, crosslinking agent, polymerization conversion rate, conjugated diene compound, impact resistance, tensile property

Description

Rubbery polymer latex, a method for preparing the same, and an ABS graft copolymer comprising the same {Rubber polymer latex, method of preparing the same, and ABS graft copolymer comprising the same}

The present invention relates to a rubbery polymer latex and a method for manufacturing the same, and more particularly, by controlling the distance of the crosslinking point between the double bonds in the butadiene by appropriately adjusting the injection time of the crosslinking agent in the production of the rubbery polymer latex applied to the ABS resin The large-diameter rubbery polymer latex having a controlled gel content can be effectively produced and applied to provide an ABS thermoplastic resin having excellent gloss, impact strength, processability, surface sharpness and thermal stability.

The conjugated diene rubber polymers represented by polybutadiene are widely used as impact modifiers of various thermoplastic resins such as ABS (Acrylonirtile-Butadiene-Styrene, ABS) and MBS (Methacrylate-Butadiene-Styrene, MBS) resins due to their excellent rubber properties.

However, since the impact strength and mechanical properties of these thermoplastic resins have properties that depend on the particle size and gel content of the rubbery polymer latex, the production of large diameter rubbery polymer latex generally terminates the reaction at a particle diameter of 3000Å and a polymerization conversion rate of about 90%. The remaining 10% of the monomer is stripped and used in the grafting process.

The reason for terminating the reaction at about 90% of the polymerization conversion rate is that the gel content of the rubbery polymer latex is rapidly increased at 90% or more because such a sudden increase in the gel content causes the problem of lowering the impact strength of the ABS resin.

The rubbery polymer latex usually produced by emulsion polymerization contains ion exchanged water, monomers, emulsifiers, initiators, molecular weight regulators, electrolytes and the like. These components remain in the final ABS resin and affect the thermal stability during melt processing of the ABS resin.

In addition, the particle size and gel content in the preparation of rubbery polymer latex by emulsion polymerization method are closely related to the polymerization time, and a long polymerization time is required to obtain a rubbery polymer latex having a large particle size.

As a method of obtaining a rubbery latex having a large particle diameter in a relatively short time, a method using a small amount of an emulsifier and a vinyl cyanide monomer before the start of polymerization; A method of using a small amount of an emulsifier and an organic solvent such as acetonitrile, propionitrile, butyronitrile at a polymerization conversion of 20% or less; Or a method of continuously adding an emulsifier at a polymerization conversion rate of 10 to 70% to obtain a rubbery latex having a large particle size (JP 1993-17508, 1996-27227).

The above methods are a method of controlling the particle size enlargement by a phenomenon in which the coverage of the particle surface by the emulsifier is lowered and the rubber polymer latex destabilizes, thereby causing the fusion coalescence between the particles and the continuous addition of the emulsifier. However, such a production method also has a problem of low productivity because a reaction time is required for 30 hours or more to obtain a rubbery polymer latex having a large particle size.

In the present invention, it takes a long polymerization time to prepare a large-diameter rubbery polymer latex applied to the ABS graft copolymer resin, thereby increasing the gel content, the problem of the prior art such as poor physical properties such as impact strength To solve them.

Accordingly, it is an object of the present invention to provide a large diameter rubbery polymer latex having a low gel content with a shorter polymerization time compared to the prior art and a method for producing the same.

Another object of the present invention is to provide an ABS graft copolymer having excellent physical properties such as impact strength, thermal stability, and workability by including a large diameter rubbery polymer latex having the above characteristics.

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

In the present invention, the crosslinking point of butadiene constituting the rubbery polymer latex by adding a crosslinking agent at the beginning of the reaction, the polymerization conversion rate of 30-40%, or both the initial reaction and the polymerization conversion rate of 30-40% in the production of large diameter rubbery polymer latex Crosslinking agent penetrates between the (double bonds) to increase the distance between the crosslinking points, thereby increasing the flexibility of the rubbery polymer so that the gel content does not increase even if the polymerization conversion rate is increased, and thus the ABS graft It is possible to play a role of improving the impact strength of the copolymer.

According to the present invention, when preparing a large diameter rubbery polymer having a conjugated diene-based compound as a base, a cross-linking agent is added to prepare a large-diameter rubbery latex having a low gel content compared to the conversion rate by controlling the distance between the crosslinking points. Through this, a large-diameter rubbery latex having a high conversion rate (95% or more) obtained in a short time (more than 2600 Pa) can be applied to the ABS graft reaction to obtain an ABS resin having excellent mechanical properties, processability, and thermal stability.

   Large diameter rubbery polymer latex for achieving the object of the present invention has an average particle diameter of 2600 ~ 5000Å, it uses a reactive material having two or more vinyl functional groups at the end as a crosslinking agent, the crosslinking agent at the beginning of the reaction, polymerization conversion rate 30 to 40% of the time, or may be prepared by adding to both the initial reaction and 30 to 40% of the polymerization conversion rate.

Hereinafter, the present invention will be described in more detail.

In the present invention, a large-diameter rubbery polymer latex is prepared and included in the ABS graft copolymer resin to provide a copolymer resin having excellent physical properties such as impact strength.

One. Large Diameter Rubber Polymer Latex

The rubbery polymer latex according to the present invention is a large diameter rubbery polymer latex having an average particle diameter of 2600 to 5000 mm 3. This is because rubber polymer latex having a large particle size is required to improve mechanical properties such as impact strength of ABS graft copolymer resin.

The rubbery polymer latex of the present invention is prepared by an emulsion polymerization method, and the rubber component constituting the rubbery polymer is a conjugated diene-based compound, and includes ion-exchanged water, an emulsifier, a polymerization initiator, a molecular weight regulator, an electrolyte, and the like. In the present invention, a crosslinking agent is used in particular, and the gel content may be controlled even if the polymerization conversion is increased by adjusting the point of introduction thereof.

The crosslinking agent according to the present invention is a reactive substance having two or more vinyl-based functional groups at its terminals, and specific examples thereof include polyethylene glycol dimethacrylate (n = 1 to 60) and polyethylene glycol diacrylate (n = 1 to 60). ), Propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,4-butylene glycol dimethacrylate, aryl methacrylate , Diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polybisphenol A-ethylene oxide diacrylate (n = 1-40), tetraethylene glycol dimethacrylate, triethylene glycol dimethacrylate At least one selected from the group consisting of, and divinylbenzene, but any reactive material having two or more vinyl functional groups at the end thereof can be used. The.

The crosslinking agent according to the present invention is characterized by being able to be added at different times of injecting. Specifically, the crosslinking agent is added at the beginning of the reaction before the actual polymerization is started, or the polymerization is started and the polymerization conversion rate is 30 to 40%. Or at both the initial stage of the reaction and at the time of 30-40% polymerization conversion. That is, in the present invention, the crosslinking agent may be collectively added at the beginning of the reaction, divided into both the initial reaction and 30 to 40% of the polymerization conversion rate, or continuously added at the 30 to 40% polymerization conversion rate.

The crosslinking agent according to the present invention is used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the rubber component constituting the rubbery polymer, that is, the conjugated diene-based compound monomer, to control the distance between the crosslinking points of the rubbery polymer latex, thereby reducing gel even at a high conversion rate. Induced content shows excellent impact strength and mechanical properties when applied to ABS resin. However, if the content is used less than 0.01 parts by weight, the effect is insignificant, and when used in excess of 5 parts by weight may inhibit the polymerization stability is not preferable.

When the crosslinking agent is added at the beginning of the reaction or at the time of 30 to 40% of the polymerization conversion rate, the crosslinking agent in the above range may be added at once. In addition, when the crosslinking agent is added at both the initial reaction time and the polymerization conversion time of 30 to 40%, 30 to 70% by weight of the total crosslinking agent is added at the initial reaction, and the remaining amount of the crosslinking agent is added to the polymerization conversion rate of 30 to 40%. It can be put in.

In the present invention, when a crosslinking agent is added to prepare a large diameter rubbery polymer latex, the crosslinking agent penetrates between the crosslinking points which are double bonds in the conjugated diene-based compound used as the monomer of the rubbery polymer, thereby increasing the distance between the crosslinking points. Accordingly, as the distance between the crosslinking points increases, the flexibility of the conjugated diene compound increases, and the crosslinking density between the double bonds of the conjugated diene compound decreases. Therefore, even if the reaction continues to increase the polymerization conversion rate, the gel content of the rubbery polymer latex can be controlled so as not to increase in proportion to the polymerization conversion rate.

Accordingly, in the prior art, the reaction was stopped at about 90% of the polymerization conversion rate for controlling the gel content. In the case of using the method of the present invention, the polymerization can be performed up to a high conversion rate of 95% or more, and the polymerization time is 25 ~ It can be shortened compared to 30 hours, it is possible to produce a large diameter rubbery polymer latex having an average particle diameter of 2600 mm 3 or more, preferably 2,600 to 5,000 mm 3.

The rubber component constituting the rubbery polymer latex of the present invention is a conjugated diene-based compound, specifically selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, pipeperylene and comonomers thereof, 1,3-butadiene is particularly preferred.

The conjugated diene compound monomers may be used alone, or may be used in combination with an aromatic vinyl compound such as styrene and α-methylstyrene copolymerizable therewith and a vinyl cyan compound such as acrylonitrile.

The copolymerizable monomer may be used in up to 20 parts by weight of the total monomer content.

The conjugated diene-based compound may also be collectively added at the beginning of the reaction, or introduced at the time of the polymerization reaction rate of 30 to 40%, or dividedly added at the time of the initial reaction and the polymerization reaction rate of 30 to 40%. When the conjugated diene compound is separately added at the time of the initial reaction and the polymerization reaction rate of 30 to 40%, 50 to 85 parts by weight of 100 parts by weight of the total conjugated diene compound is added at the initial reaction, and the polymerization reaction rate is 30 to 40%. The remaining amount can be added at this point.

The emulsifier included in the rubbery polymer latex of the present invention uses an emulsifier having a low critical micelle concentration (CMC), which forms a large number of micelles to promote the formation of rubbery polymer base particles. It is desirable to reduce the amount of emulsifier and electrolyte used. However, when only the emulsifier CMC is too low, the number of particles to be produced increases, so in order to prepare a rubber latex having an appropriate particle size, the electrolyte content must be increased, which results in deterioration of thermal stability.

Therefore, the emulsifier according to the present invention preferably has a critical micelle concentration (CMC) in the range of 10 ⁻⁴ to 10 ⁻³ mol / L.

The emulsifier according to the present invention is an alkyl aryl sulfonate, alkali methyl alkyl sulfate, fatty acid soap, oleic acid alkali salt and the like 40 to 60% of the total weight of the emulsifier and the residual rosin acid alkali salt, lauric acid alkali salt or a mixture thereof It is preferable to use.

In addition, the content of the emulsifier is preferably 1 to 3 parts by weight based on 100 parts by weight of the conjugated diene compound.

As a polymerization initiator contained in the large diameter rubbery polymer latex of this invention, Water-soluble persulfate type polymerization initiators, such as potassium persulfate, sodium persulfate, or ammonium persulfate; Redox-based polymerization initiators containing peroxides such as hydrogen peroxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, tertiary butyl hydroperoxide and paramethane hydroperoxide can be used. In the case of adding at a conversion rate of 30 to 40%, a water-soluble persulfate-based polymerization initiator is preferable.

In addition, as the electrolyte, potassium chloride, sodium chloride, potassium bicarbonate (KHCO ₃ ), sodium carbonate (NaHCO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), potassium hydrogen sulfite (KHSO ₃ ), sodium hydrogen sulfite (NaHSO ₃ ), Potassium Pyrophosphate (K ₄ P ₂ O ₇ ), Sodium Pyrophosphate (Na ₄ P ₂ O ₇ ), Tripotassium Phosphate (K ₃ PO ₄ ), Trisodium Phosphate (Na ₃ PO ₄ ) And at least one selected from the group consisting of dipotassium hydrogen phosphate (K ₂ HPO ₄ ) and disodium hydrogen phosphate (Na ₂ HPO ₄ ).

As a molecular weight regulator, mercaptans can be mainly used.

Large-diameter rubbery polymer latex according to an embodiment of the present invention is prepared using emulsion polymerization, the reaction temperature is polymerized at 55 ~ 75 ℃.

Method for producing a large diameter rubbery polymer latex according to a preferred embodiment of the present invention comprises the steps of a) 50 to 85 parts by weight of a conjugated diene compound monomer, a crosslinking agent, an emulsifier, and other additives in a batch; b) polymerizing by administering a residual amount of the conjugated diene compound monomer, a crosslinking agent, a polymerization initiator, and other additives when the polymerization conversion rate of step a) is 30 to 40%.

The step a) is polymerized at 55-75 ° C., and the step b) is polymerized at 65-85 ° C. by adding the respective constituents at the time when the polymerization conversion rate of a) is 30-40%.

2. ABS Graft Copolymer

The ABS graft copolymer according to the present invention includes the large diameter rubbery polymer latex prepared above, and is prepared by adding an aromatic vinyl compound and a vinyl cyan compound.

The large-diameter rubbery polymer latex included in the ABS graft copolymer is preferably contained in 50 to 80% by weight of the monomer mixture constituting the graft copolymer.

Specifically, 100 parts by weight of a monomer mixture consisting of 50 to 80% by weight of a large diameter rubbery polymer latex, 20 to 50% by weight of a monomer selected from the group consisting of aromatic vinyl compounds and vinyl cyan compounds is added to a nitrogen-substituted polymerization reactor. To prepare a graft copolymer, the monomer mixture is graft copolymerized by continuous administration in an emulsified state. At this time, the emulsifier 0.2 ~ 2 parts by weight, the molecular weight regulator 0.1 ~ 0.5 parts by weight, the polymerization initiator 0.1 ~ 0.5 parts by weight based on 100 parts by weight of the monomer mixture, the polymerization temperature is 45 ~ 80 ℃ suitable, polymerization time 3-6 hours is suitable.

Monomers constituting the ABS graft copolymer may be initially added in the form of a single or a mixture, or may be continuously added in an emulsified state.

As the emulsifier used in the polymerization reaction, alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like are used, either alone or as a mixture of two or more thereof. It is possible. It is very important to select an emulsifier in order to secure latex stability in the production of graft copolymer having high rubber content.

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

Polymerization initiators include peroxides such as cumenehydro peroxide, diisopropylbenzenehydroperoxide, persulfate, and the like, sodium formaldehyde succilate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and Oxidation-reduction catalyst systems in admixture with one or more reducing agents selected from the group consisting of sodium sulfate can be used.

The polymerization conversion rate of the ABS graft copolymer latex obtained after the end of the polymerization is 98% or more. The stability of the prepared ABS graft copolymer latex was determined by measuring the solidification percentage (%) as shown in the following equation (1).

(G) / total rubber (large-diameter rubbery polymer) and weight (g) of the monomer} x 100

When the solidified solid content is 0.7% or more, latex stability is extremely low and a large amount of coagulated material makes it difficult to obtain a graft polymer suitable for the present invention.

In addition, the graft ratio of the ABS graft polymer is measured as follows. The graft polymer latex is coagulated, washed, and dried to obtain a powder form, and 2 g of this powder is placed in 300 ml of acetone and stirred for 24 hours. The solution is separated using an ultracentrifuge, and then the separated acetone solution is dropped in methanol to obtain an grafted portion, which is dried and weighed. From these weights, the graft ratio is calculated according to the following equation.

Graft Rate (%) = Weight of Grafted Monomer (g) / Rubber Weight (g) x 100

At this time, if the graft ratio is 25% or less, the glossiness is lowered, which is not preferable.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and various changes and modifications within the scope and spirit of the invention are apparent to those skilled in the art. It is natural that such variations and modifications fall within the scope of the appended claims.

≪ Preparation of rubber polymer latex >

Example 1

60 parts by weight of ion-exchanged water, 75 parts by weight of 1,3-butadiene as monomer, 1 part by weight of polyethylene glycol dimethacrylate (n = 6) as crosslinking agent, potassium rosin as emulsifier in a nitrogen-substituted polymerization reactor (autoclave) 1 part by weight of salt, 0.8 parts by weight of fatty acid soap, 1.5 parts by weight of potassium carbonate as an electrolyte, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight regulator, and 0.3 parts by weight of potassium persulfate (K2S2O8) as an initiator It was made to react at the temperature of 70 degreeC to the time point which is 30 to 40% of a polymerization conversion rate. Then, at a time of 30-40% polymerization conversion, 25 parts by weight of 1,3-butadiene and 0.15 parts by weight of potassium persulfate were collectively administered, followed by reaction at 70 ° C to a time of 60% polymerization conversion, and the temperature was raised to 80 ° C. The reaction was terminated when the polymerization conversion rate was 97%.

Example 2

A rubbery polymer latex was prepared in the same manner as in Example 1, except that 1 part by weight of the crosslinking agent polyethylene glycol dimethacrylate (n = 6) was added at a polymerization conversion rate of 30 to 40%.

Example 3

A rubbery polymer latex was prepared in the same manner as in Example 1 except that 1 part by weight of polyethylene glycol diacrylate (n = 6) was added instead of polyethylene glycol dimethacrylate as a crosslinking agent.

Example 4

A rubbery polymer latex was prepared in the same manner as in Example 3, except that 1 part by weight of the crosslinking agent polyethylene glycol diacrylate (n = 6) was added at a polymerization conversion rate of 30 to 40%.

Comparative Example 1

65 parts by weight of ion-exchanged water, 73 parts by weight of 1,3-butadiene as monomer, 1 part by weight of potassium rosin salt as emulsifier, 0.8 parts by weight of fatty acid soap, 1.2 parts by weight of potassium carbonate as electrolyte in a nitrogen-substituted polymerization reactor (autoclave) In addition, 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as the molecular weight regulator and 0.3 parts by weight of potassium persulfate (K2S2O8) as the initiator were collectively administered and reacted at a reaction temperature of 72 ° C. up to a point of 30 to 40% polymerization conversion. Then, 27 parts by weight of 1,3-butadiene and 0.15 parts by weight of potassium persulfate were collectively administered at a time of 30-40% polymerization conversion, and then reacted at a temperature of 60% polymerization conversion at 70 ° C, and then heated up to 80 ° C. The reaction was terminated when the polymerization conversion rate was 97.5%. And the obtained rubbery polymer latex was analyzed.

The gel content and average particle diameter of the rubbery polymer latex prepared according to the Examples and Comparative Examples were measured as follows, and the results are shown in Table 1 below.

(1) gel content

   The rubber latex was coagulated with dilute acid or metal salt and washed, dried in a vacuum oven at 60 ° C. for 24 hours, and the resulting rubber mass was chopped with scissors, and then 1 g of rubber fragments were put in 100 g of toluene for 48 hours. After storage in the dark, it is separated into sol and gel and the gel content is measured by the following equation (3).

Gel content (%) = weight of insolubles (gel) / weight of sample * 100

(2) particle size and particle size distribution

Measurements were performed using a Nicomp 370HPL instrument (Nicomp, USA) by the dynamic laser light scattering method.

Content (parts by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Ion-exchange water 60 60 60 60 65 1,3-butadiene
(Initial reaction) 75 75 75 75 73 Cross-linking agent content One One One One - Input time Initial polymerization 30-40% conversion rate Initial polymerization 30-40% conversion rate - 1,3-butadiene
(30-40% conversion) 25 25 25 25 27 Polymerization time (hr) 20 20 21 21 20 Polymerization Conversion (%) 97 97.5 96 97.5 97.5 Gel content (%) 85 85.5 84 85 90 Particle size 2900 2880 2950 2920 2880

As shown in the results of Table 1, when manufacturing a large diameter rubber latex as in the present invention, it is possible to produce a large diameter rubber latex having a low gel content compared to the conversion rate by controlling the distance between crosslinking points. Particularly, Examples 2 and 4 and Comparative Example 1 had the same polymerization conversion rate as 97.5%, but the gel content was as low as 85.5%, 85% and 90%, respectively. In addition, Comparative Example 1 does not add a crosslinking agent, the reaction time can be shortened to the level of the present invention, but there is a problem that the physical properties (gel content) of the rubbery polymer latex is not secured.

<ABS graft copolymer production>

Example 5

60 parts by weight of the rubbery polymer latex obtained in Example 1, 10 parts by weight of styrene, and 0.2 parts by weight of fatty acid soap were added to the reactor and mixed. 10 parts by weight of acrylonitrile, 20 parts by weight of styrene, 10 parts by weight of ion-exchanged water, 0.12 parts by weight of cumene hydroperoxide, 0.3 parts by weight of fatty acid soap, and 0.3 parts by weight of tertiary dodecyl mercaptan in a separate mixing device. A monomer emulsion was prepared, which was continuously charged at 70 ° C. for 2 hours in a reactor containing the rubbery polymer latex. At this time, 0.054 parts by weight of dextrose, 0.004 parts by weight of sodium pyrolate, and 0.002 parts by weight of ferrous sulfate were continuously added together.

After the addition of the monomer emulsion, 0.05 parts by weight of dextrose, 0.03 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of t-butyl hydroperoxide were added to the reactor in a batch. The reaction was terminated after raising the temperature to 80 ° C. over 1 hour.

Example 6

70 parts by weight of the rubbery polymer latex obtained in Example 1, 5 parts by weight of styrene, and 0.2 parts by weight of fatty acid soap were added to the reactor and mixed. Separately, 7.5 parts by weight of acrylonitrile, 17.5 parts by weight of styrene, 10 parts by weight of ion-exchanged water, 0.10 parts by weight of cumene hydroperoxide, 0.3 parts by weight of fatty acid soap, and 0.3 parts by weight of tertiary dodecyl mercaptan were mixed. A monomer emulsion was prepared, which was continuously charged at 70 ° C. for 2 hours in a reactor containing the rubbery polymer latex. The following manufacturing process was prepared in the same manner as in Example 5 ABS graft copolymer.

Example 7

An ABS graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the rubbery polymer latex obtained in Example 2 was used.

Example 8

An ABS graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the rubbery polymer latex obtained in Example 3 was used.

Example 9

An ABS graft copolymer was prepared in the same manner as in Example 5, except that 60 parts by weight of the rubbery polymer latex obtained in Example 4 was used.

Comparative Example 2

An ABS graft copolymer was manufactured in the same manner as in Example 5, except that 60 parts by weight of the rubbery polymer latex obtained in Comparative Example 1 was used.

<ABS resin powder>

Examples 10-14, Comparative Example 3

The graft copolymer latex obtained in Examples 5 to 9 and Comparative Example 2 was coagulated by washing with an aqueous sulfuric acid solution, washed, and then made into a powder, and 27.5 parts by weight of the powder prepared to have a rubber content of 16.5% and SAN (LG Chem.) Product, product name: 92HR) After mixing 72.5 parts by weight, the amount of red pigment is adjusted to have similar L, a, b values in order to determine the degree of coloring improvement, and then mixed into pellets using an extruder. The specimen was obtained using the next injection machine, and the physical properties thereof were measured as shown in Table 4 below.

1) Izod impact strength-The thickness of the specimen was measured by ASTM 256 method with 1 / 4˝.

2) Melt Flow Index (MI) -Measured by ASTM D1238 under the condition of 220 ° C./10 kg.

3) Tensile strength-measured by ASTM D638 method.

4) Surface gloss-measured by ASTM D528 method at 45˚ angle.

5) retention gloss: Pellet obtained from the extruder is placed in the injection machine and held for 15 minutes at 250 ℃ conditions to obtain a gloss specimen, measured 45 ° gloss like the specimen injected without stay at 200 ℃ and measure the deviation value It was. The smaller the measured value, the better the staying gloss.

6) Residual discoloration (△ E): For the gloss specimen obtained by the same method as the method of measuring the retention gloss, using the Suga color computer to obtain the L, a, b value for the specimen before and after the stay in the equation (4) The degree of retention discoloration was determined based on this. The smaller the measured value, the smaller the retention discoloration, indicating excellent.

division Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 3 ABS graft latex Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 2 Conversion Rate (%) 98.0 98.5 98.3 98.8 98 .9 98.5 Coagulation content (%) 0.02 0.015 0.025 0.025 0.03 0.3 Graft Rate (%) 38 42 37.5 37 36 31 Izod impact strength
1/4 ”(kgcm / cm) 29 28.5 29.5 30 27.8 23 Fluidity (g / 10 min) 20 20.5 21 20.5 19 17 Tensile Strength (㎏ / ㎠) 450 445 452 455 455 440 Surface gloss (%) 102 103 101.5 101 102 98 Retention discoloration 2.0 1.5 1.9 2.1 2 5 Staying gloss 5 4.5 4.9 5.2 5 8

Through Table 2, it can be confirmed that the ABS resin of Examples 10 to 14 prepared according to the present invention has excellent mechanical properties, processability and thermal stability. In particular, the ABS resin prepared according to the present invention can be seen that the coagulant content is significantly superior to the comparative example, it can be seen that the resin of the present invention is excellent in terms of safety.

Claims (13)

In the rubbery polymer latex prepared by emulsion polymerization of a conjugated diene compound monomer selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, piperylene and combinations thereof A rubbery polymer latex having an average particle diameter of 2600 to 5000 kPa comprising a crosslinking agent, which is a reactive substance having two or more vinyl functional groups at its terminals, at the beginning of the reaction and the polymerization conversion rate of 30 to 40%. delete The method of claim 1, wherein the crosslinking agent is polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol diol Methacrylate, 1.4-butylene glycol dimethacrylate, aryl methacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polybisphenol A-ethylene oxide diacrylate, tetraethylene glycol dimethacrylate A rubbery polymer latex characterized in that it is selected from the group consisting of acrylate, triethylene glycol dimethacrylate, and divinylbenzene. The rubbery polymer latex according to claim 1, wherein the crosslinking agent is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the conjugated diene compound monomer. delete The rubbery polymer latex according to claim 1, wherein the latex comprises at least one additive selected from the group consisting of an emulsifier, a polymerization initiator, a molecular weight regulator, an electrolyte, and ion-exchanged water. In the method for producing a rubbery polymer latex prepared by emulsion polymerization of a conjugated diene compound monomer selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, piperylene and combinations thereof A method for producing a rubbery polymer latex comprising the step of adding a crosslinking agent which is a reactive substance having two or more vinyl-based functional groups at the terminal at a time selected from the initial reaction and the polymerization conversion rate of 30 to 40% when the reaction starts. delete delete The method of claim 7, wherein the crosslinking agent is polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol diol Methacrylate, 1.4-butylene glycol dimethacrylate, aryl methacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polybisphenol A-ethylene oxide diacrylate, tetraethylene glycol dimethacrylate A process for producing a rubbery polymer latex characterized in that it is selected from the group consisting of acrylate, triethylene glycol dimethacrylate, and divinylbenzene. ABS graft copolymer comprising a rubbery polymer latex according to claim 1. The method according to claim 11, wherein the ABS graft copolymer is characterized in that it comprises 20 to 50% by weight of the monomer selected from the group consisting of 50 to 80% by weight of the rubbery polymer latex, aromatic vinyl compound and vinyl cyan compound. ABS graft copolymer. The ABS graft copolymer according to claim 11, wherein the monomers constituting the ABS graft copolymer are initially added in the form of a single or a mixture, or continuously administered in an emulsified state.