KR20030049927A - Rubber-modified thermoplastic resin composition and method for preparing the same - Google Patents

Abstract

PURPOSE: Provided are a thermoplastic ABS(acrylonitrile butadiene styrene) resin composition which has excellent impact strength and elongation and high gloss, and a method for producing the same. CONSTITUTION: The ABS resin composition is produced the method comprising the steps of (a) introducing 5-12 parts by weight of rubber mixture containing (i) a high viscosity butadiene rubber having solution viscosity of 70-150 cps in 5 parts by weight of styrene solution having mixing ratio(by weight) of 9:1-1:9, in which the solution viscosity is 1 to 4 times as high as Mooney viscosity, and a low viscosity butadiene rubber having solution viscosity of 10-70 cps in 5 parts by weight of the styrene solution, in which the solution viscosity is 0.2-1 time as low as Mooney viscosity, or (ii) a butadiene rubber having solution viscosity of 20-150 cps in 5 parts by weight of styrene solution having mixing ratio(by weight) of 9:1-1:9, and a styrene-butadiene rubber having solution viscosity of 10-70 cps in 5 parts by weight of the styrene solution, to a mixed solution containing 40-60 parts by weight of styrene or styrene derivative monomer, 10-30 parts by weight of acrylonitrile or acrylonitrile derivative monomer, and 5-38 parts by weight of reaction medium, so as to primarily bulk-polymerizing them; and (b) secondarily bulk-polymerizing the primarily polymerized product by introducing 60-100 parts by weight of reaction medium to 100 parts by weight of the product.

Description

Rubber-modified thermoplastic resin composition and its manufacturing method {RUBBER-MODIFIED THERMOPLASTIC RESIN COMPOSITION AND METHOD FOR PREPARING THE SAME}

[Industrial use]

The present invention relates to a rubber-modified thermoplastic resin composition and a method for manufacturing the same, and more particularly, a high viscosity butadiene rubber and a low viscosity butadiene rubber, or a mixture of butadiene rubber and styrene-butadiene rubber in a monomer mixture solution in the production of ABS thermoplastic resin It relates to a rubber-modified thermoplastic ABS resin composition comprising the step of bulk polymerization by administering in a ratio.

[Prior art]

Common methods for producing ABS resin, which is a rubber-modified thermoplastic resin, include emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and bulk polymerization, suspension polymerization, or bulk polymerization and emulsion polymerization. At present, the emulsion polymerization method and the bulk polymerization method are widely used at the production site, and among them, the emulsion polymerization method is most used. The ABS resin prepared by the emulsion polymerization method exhibits excellent mechanical properties and gloss with an average size of 0.2 to 1.5 μm of rubber particles present in the dispersed phase in the continuous SAN copolymer. However, the emulsion polymerization method has a problem in that the emulsifier and flocculant, which must be used in the nature of the process, are not removed in the flocculation and dehydration process and remain in the final squeeze, causing deterioration of physical properties. There is a serious problem. In addition, the emulsion polymerization requires a separate process of coagulation and dehydration after polymerization, and thus, additional energy consumption and productivity may be lower than that of the bulk polymerization, which is a continuous process.

In addition, when the ABS resin is prepared by the bulk polymerization method, it is difficult to control the process because the viscosity of the reaction solution is higher than that of the emulsion polymerization method, and the size of the rubber particles is larger than that of the ABS resin produced by the emulsion polymerization method, resulting in poor glossiness. There is. For this reason, studies are currently underway to manufacture ABS resins by the bulk polymerization method.

In general, the gloss and mechanical properties of ABS resin depend on the size of the dispersed rubber particles.

In particular, Souheng Wu describes the rubber reinforcing effect of rubber modified thermoplastic resins in Polymer engineering and science, Vol. 30, No. 13, 1990, and the average size of rubber particles effective for ABS resin is 0.75. claimed to be about um.

When the ABS resin is manufactured by the bulk polymerization method, a method of controlling the size of rubber particles may be performed by stirring a non-uniform polymerization solution with a high shear force to crush the rubber phase and increasing the amount of the grafted SAN copolymer. There is a method of making the particle size smaller by making the particles well dispersed.

Another way to effectively control particle size is to use specific rubber.

Generally used butadiene rubbers have high molecular weight and linear chain structure, and have high viscosity butadiene rubber having very high solution viscosity in 5 parts by weight styrene solution and 1 to 3 times the Mooney viscosity, and low molecular weight and branched chain structure. There are many low viscosity butadiene rubbers which have a very low solution viscosity in the 5 parts by weight styrene solution and are 0.1 to 1 times the Mooney viscosity.

When the ABS resin is manufactured by the bulk polymerization method using the high viscosity butadiene rubber, the size of the resulting rubber particles is relatively large and has an excellent impact strength. However, in order to prepare ABS resins having low gloss and small size particles, the graft reaction should be promoted by stirring with high shear force during polymerization or by using a specific initiator or reactant. In addition, when the low viscosity butadiene rubber is used, it is possible to easily make small particles, so that an excellent ABS resin can be produced. However, the impact strength is low to increase the rubber content in order to increase the impact strength.

Therefore, in order to manufacture the ABS resin which has the outstanding mechanical strength and glossiness by the mass polymerization method, the technique which can appropriately control the size of a rubber particle is absolutely necessary.

As a manufacturing method of ABS resin for this purpose, US Patent Nos. 5,414,045, 5,569,709, 4,640,959, and 5,506,304, European Patent 277,687, European Patent 103,657, Japanese Patent No. 9-176214, And International Publication No. 148043.

In the above methods, peroxide initiators are commonly used to increase the efficiency of the graft reaction or to apply high shear force to reduce the size of the rubber particles. In addition, in order to control the molecular weight of the copolymer affecting the viscosity and particle size of the reaction solution and the mechanical properties of the ABS resin produced, a mass polymerization agent was controlled by various methods. However, a method for producing an ABS resin having excellent glossiness and mechanical properties simultaneously by effectively using rubbers having different properties is not known.

The U.S. Patent Nos. 5,414,045 and 5,569,709 disclose a method of preparing ABS resins having easy phase inversion control and small rubber particles by continuous bulk polymerization using a tubular polymerization reactor and a continuous stirred tank polymerization reactor. However, the above method has a disadvantage in that the concentration of the grafted side chain groups can be increased by using a specific reactor, and there is a disadvantage that the flowability of the produced ABS resin is bad.

U.S. Patent Nos. 4,640,959, and European Patent No. 103,657 use high viscosity butadiene rubber having a solution viscosity of 120 cp in a 5 parts by weight styrene solution to provide monomer composition, reaction initiator and molecular weight regulators, and timing and stirring. Disclosed is a method for producing an ABS resin having a relatively large particle having an average particle diameter of 1.5 um by controlling the speed by a bulk polymerization method. However, the resin thus prepared has a problem that the particles are large and excellent in impact strength but relatively low in fluidity and low in glossiness measured at 15 ° C.

In addition, the U.S. Patent No. 5,506,304 discloses a method for producing an ABS resin having excellent surface gloss with relatively small rubber particles having a size of 0.6 um or less by bulk polymerization using styrene-butadiene rubber, but has a low impact strength. Has a problem.

In addition, European Patent No. 277,687 discloses a method for producing an ABS resin having excellent impact strength and elongation and relatively high gloss by using one kind of butadiene rubber having a specific value ratio between solution viscosity and Mooney viscosity. Since the acrylonitrile content in the prepared resin is 25 parts by weight or less, there is a problem of poor chemical resistance.

Japanese Patent Laid-Open No. 9-176214 discloses a method for producing an ABS resin having a very low amount of residual monomer using a low viscosity styrene-butadiene rubber, but has a problem of very low gloss.

International Publication No. 148043 discloses a method for producing an ABS resin having rubber particles having a size of 0.3 to 0.7 um using butadiene rubber, but the content of gloss is not mentioned.

In view of the problems of the prior art as described above, an object of the present invention is to provide a method for producing an ABS thermoplastic resin composition having excellent gloss strength and high impact strength and elongation characteristics.

Another object of the present invention is to provide a method for preparing a rubber-modified ABS resin composition that is easy to control the phase inversion and the size and graft reaction of the rubber particles.

In order to achieve the above object, the present invention is a method for producing a rubber-modified ABS thermoplastic resin composition,

a) 40 to 60 parts by weight of styrene or styrene derivative monomers; 10 to 30 parts by weight of acrylonitrile or acrylonitrile derivative monomers; And 5 to 38 parts by weight of the reaction medium.

Viii) the mixing weight ratio is from 9: 1 to 1: 9

High viscosity butadiene rubber having a solution viscosity of 70 to 150 cps and a solution viscosity of 1 to 4 times the Mooney viscosity in a 5 parts by weight styrene solution, and a solution viscosity of 10 to 70 cps and a solution viscosity of the Mooney viscosity to a 5 parts by weight styrene solution. Low viscosity butadiene rubber that is 0.2 to 1 times; or

Ii) the mixing weight ratio is from 9: 1 to 1: 9

Butadiene rubber with a solution viscosity of 20 to 150 cps in 5 parts by weight of styrene solution, and styrene-butadiene rubber with a solution viscosity of 10 to 70 cps in 5 parts by weight of styrene solution

5 to 12 parts by weight of the rubber mixture containing the first step of mass polymerization; And

b) 100 parts by weight of the first bulk polymer obtained above

Second mass polymerization by adding 60 to 100 parts by weight of reaction medium

It provides a method for producing a rubber-modified ABS thermoplastic resin composition comprising a.

Hereinafter, the present invention will be described in detail.

The present invention provides a rubber-modified ABS thermoplastic resin composition and a method for producing the same, which are bulk polymerized using a high and low viscosity butadiene-based rubber mixture or a mixture of butadiene rubber and styrene-butadiene rubber mixed at a constant ratio. According to the present invention, it is possible to produce an ABS thermoplastic resin having excellent impact strength and elongation characteristics and high gloss.

Such ABS thermoplastic resin compositions of the present invention include styrene or styrene derivative monomers, acrylonitrile or acrylonitrile derivative monomers, and high viscosity butadiene rubbers and low viscosity butadiene rubbers mixed in a proportion, or butadiene rubbers and styrene-butadiene rubbers. do.

In particular, the present invention is characterized by using a butadiene rubber mixture having a different viscosity to facilitate phase inversion and control of the size and graft reaction of the rubber particles. Butadiene mixtures having different viscosities preferably use a mixture of high viscosity butadiene rubber and low viscosity butadiene rubber, or a mixture of butadiene rubber or styrene-butadiene rubber having another viscosity. The mixing ratio of the high viscosity butadiene rubber and low viscosity butadiene rubber, or butadiene rubber or styrene-butadiene rubber is preferably mixed in a weight ratio of 9: 1 to 1: 9. When the mixing weight ratio is less than the above range, the viscosity of the polymerization solution is too high, so that it is difficult to control the polymerization reaction and the size of the rubber particles is too large, resulting in poor physical properties. There is.

The high viscosity butadiene-based rubber is preferably used in the 5 parts by weight of the styrene solution, the solution viscosity is 70 to 150 cps and the solution viscosity is 1 to 4 times the Mooney viscosity. The low viscosity butadiene-based rubber is preferably used in a 5 parts by weight of the styrene solution of a solution viscosity of 10 to 70 cps and a solution viscosity of 0.2 to 1 times the Mooney viscosity.

The butadiene rubber mixed with the styrene-butadiene rubber is preferably used having a solution viscosity of 20 to 150 cps in 5 parts by weight of a styrene solution. The styrene-butadiene rubber is preferably used to have a solution viscosity of 10 to 70 cps in 5 parts by weight of styrene solution.

The content of the high-viscosity butadiene-based rubber and the low-viscosity-butadiene-based rubber mixture, or the rubber mixture of butadiene rubber and styrene-butadiene is preferably 5 to 12 parts by weight, and if the content of the rubber mixture is less than 5 parts by weight, the polymerized resin There is a problem that the rubber reinforcing effect is lowered because the rubber content is low, and if more than 12 parts by weight, the total rubber content is too high, difficult to control the polymerization process and difficult to control the size of the rubber particles.

The styrene or styrene derivative monomers include styrene, α-methylstyrene, derivatives thereof, and derivatives having one or more addition substituents in the benzene nucleus. Derivatives having one or more addition substituents in the benzene nucleus include p-bromostyrene, p-methylstyrene, p-chlorostyrene, o-bromostyrene, and derivatives thereof. The content of the styrene or styrene derivative is preferably used in 40 to 60 parts by weight in the first block polymerization step, and 0.1 to 25 parts by weight in the secondary block polymerization step.

In addition, the acrylonitrile or acrylonitrile derivative monomers include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. The content of the acrylonitrile or acrylonitrile derivative is preferably used in 10 to 30 parts by weight in the first block polymerization step, and 0.1 to 15 parts by weight in the second block polymerization step.

The reaction medium is preferably ethylbenzene or toluene, the content of the reaction medium is preferably used in 5 to 38 parts by weight in the first block polymerization step, 60 to 99 parts by weight in the second block polymerization step.

The polymerization initiator may be 1,1, -bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t It is preferable to use an organic peroxide having a bifunctional group such as -butylperoxy) 2-methylcyclohexane. The content of the polymerization initiator is preferably 0.005 to 0.05 parts by weight.

The molecular weight modifier is a thiol-based compound, for example t-dodecyl mercaptan, n-octyl mercaptan and the like. The content of the molecular weight modifier is preferably 0.005 to 0.05 parts by weight.

In addition, the method of manufacturing the ABS resin of the present invention by bulk polymerization will be briefly described as follows. First, a predetermined amount of butadiene rubber mixtures having different viscosities or a mixture of butadiene rubbers and styrene-butadiene rubbers is dissolved in a solution in which monomers styrene or styrene derivatives, acrylonitrile or acrylonitrile derivatives, and a reaction medium are mixed at a predetermined ratio. Reaction initiators, molecular weight regulators and other additives are mixed and heated and polymerized. As the polymerization proceeds, a copolymer (SAN) of the monomer styrene or styrene derivative and acrylonitrile or acrylonitrile derivative is produced. In this case, the newly polymerized SAN copolymer and the rubber dissolved in the reaction medium from the beginning of the reaction do not mix with each other, but are separated into two phases by dissolving the reaction solvent and the monomer solution into two phases, resulting in an uneven phase of the entire polymerization solution. In this non-uniform state, at the initial stage of the polymerization reaction with low conversion rate, the rubber phase dissolved in the polymerization solution forms a continuous phase. However, as the reaction proceeds, the volume of the copolymer phase of the styrene or styrene derivative and the acrylonitrile or acrylonitrile derivative increased as the volume of the rubber phase in the polymerization solution increases, thereby forming the copolymer in a continuous phase. This phenomenon is called "phase inversion" and the point at which the volume of the copolymer phase and the rubber phase become equal is a phase inversion point. Unlike the SAN copolymer which forms a continuous phase as the polymerization proceeds separately from the phase inversion, the rubber and monomers react to grow the SAN copolymer in the side chain in the rubber chain. This reaction is called the "graft reaction" and this side chain is called the "grafted SAN copolymer", and the resulting grafted SAN copolymer is commercialized to mix them well between a rubber phase and a SAN copolymer phase that do not mix well with each other. It's my job.

Referring to the manufacturing method of the ABS thermoplastic resin composition of the present invention in more detail as follows.

First, the present invention is added by mixing the reaction medium to the monomer mixture of styrene or styrene derivative and acrylonitrile or acrylonitrile derivative. Thereafter, the rubber mixture having different viscosities is dissolved in the mixed solution, and then a bulk polymerization is first performed by adding a bifunctional peroxide catalyst. At this time, a molecular weight modifier may be added.

Then, by varying the amount of the reaction medium used in the first bulk polymerization is mixed and the thiol compound-based molecular weight regulator is diluted therein. Subsequently, the solution in which the molecular weight modifier is diluted is separately added to the first bulk polymer, and then bulk polymerized in a second step to prepare an ABS thermoplastic resin composition. The content of the reaction medium is preferably used in an amount of 60 to 100 parts by weight based on 100 parts by weight of the first bulk polymer. In addition, the secondary bulk polymerization may be performed by further including 0.1 to 25 parts by weight of styrene derivatives and 0.1 to 15 parts by weight of acrylonitrile or acrylonitrile derivative monomer together with the reaction medium. In this case, the content of the mixture of the monomers and the reaction medium is preferably used to 5 to 30 parts by weight of the reaction solution.

In the first block polymerization, the polymerization initiator and the molecular weight regulator are mixed at a constant ratio, and then polymerized for 2 to 6 hours while heating to 90 to 120 ° C., followed by polymerization to 2 to 6 hours by raising the temperature to 100 to 160 ° C. It is desirable to. The secondary bulk polymerization is preferably carried out for 2 to 6 hours under a temperature condition of 140 to 180 ℃ while diluting the molecular weight regulator in the monomer and reaction medium mixed solution. The polymerization solution thus polymerized is pulverized to remove unreacted monomer and reaction medium and then pulverized into pellets.

The present invention will be described in more detail with reference to the following examples. However, the examples are only for illustrating the present invention and not for limiting the present invention.

EXAMPLE

Example 1

50.6 parts by weight of monomer styrene and 16.9 parts by weight of acrylonitrile were mixed with 24.5 parts by weight of ethylbenzene as a reaction medium, and the mixed solution was 91 cps in solution of 5 parts by weight of styrene solution, 8 parts by weight of a rubber mixture of 2.4 times butadiene rubber and 5 parts by weight of a styrene solution with a solution viscosity of 25 cps and a solution viscosity of 0.6 times the Mooney viscosity with a weight ratio of 5: 5 was added to dissolve for 7 hours. 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane was added to 150 ppm as a peroxide polymerization initiator, and the polymerization was carried out while heating to 110 ° C. Then, 0.5 part by weight of the molecular weight regulator t-dodecylmercaptan was dissolved in a mixed solution of 10 parts by weight of styrene, 10 parts by weight of acrylonitrile, and 75 parts by weight of ethylbenzene as a reaction medium, and the solution was adjusted to 5 parts by weight of the reaction solution. The polymerization was carried out at 145 ° C while charging to prepare an ABS thermoplastic resin composition. The total polymerization time was 8 hours, and the physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 1 below.

Example 2

Butadiene rubber and solution in 5 parts by weight of styrene solution with a solution viscosity of 91 cps and a solution viscosity of 2.4 times the Mooney viscosity by varying the proportion of butadiene rubber mixture in the same manner as in Example 1. An ABS thermoplastic resin composition was prepared using a mixture of butadiene rubber having a viscosity of 25 cps and a solution viscosity of 0.6 times the Mooney viscosity at a weight ratio of 7: 3. Physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 1 below.

Example 3

In the same manner as in Example 1, butadiene rubber mixture of 5 parts by weight of butadiene rubber and 5 parts by weight of a styrene solution with a solution viscosity of 91 cps and a solution viscosity of 2.4 times the Mooney viscosity by varying the proportion of butadiene rubber mixture An ABS thermoplastic resin composition was prepared using a mixture of butadiene rubber having a viscosity of 25 cps and a solution viscosity of 0.6 times the Mooney viscosity at a weight ratio of 3: 7. Physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 1 below.

Example 4

In the same manner as in Example 1, butadiene rubber mixture was dissolved in the monomer mixture solution, and then the peroxide initiator was changed to a concentration of 200 ppm to prepare an ABS thermoplastic resin composition. Physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 1 below.

Comparative Example 1

In the same manner as in Example 1, butadiene rubber was used to prepare an ABS thermoplastic resin composition using only butadiene rubber having a solution viscosity of 91 cps and a solution viscosity of 2.4 times the Mooney viscosity of 5 parts by weight of a styrene solution. Physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 1 below.

Comparative Example 2

It was carried out in the same manner as in Example 1, but using a butadiene rubber, the ABS resin composition was prepared using only butadiene rubber having a solution viscosity of 25 cps and a solution viscosity of 0.6 times the Mooney viscosity of 5 parts by weight of a styrene solution. The physical property analysis results of the ABS resin composition thus prepared are shown in Table 1 below.

division Example Comparative example One 2 3 4 One 2 Particle size (um) Average 1.2 1.3 0.7 0.6 1.6 0.5 Distribution 1.9 2.1 2 1.7 2.5 2.3 Glossiness (%) 90 89 90 91 81 93 Izod impact strength kgcm / cm (1/4 ") 13.3 14.3 12.1 14.6 14.8 8.5 kgcm / cm (1/8 ") 14.4 15.8 13.7 16.2 16.5 9.3 Tensile Strength (kg / ㎠) 440 451 422 455 423 398 Elongation at Break,% 33.6 42.7 31.2 33.1 36.3 40.1 Fluidity (g / min) 220 ℃ / 10 kg) 22.3 20.8 21.5 27.3 24.9 23.3

As shown in Table 1, in the case of Examples 1 to 5 of the present invention, it is possible to control the size of the rubber particles in comparison with Comparative Examples 1 and 2, ABS resin excellent in gloss, elongation, flow, impact strength and tensile strength Could get

Example 5

In the same manner as in Example 1, butadiene rubber mixture was changed to prepare butadiene rubber having a solution viscosity of 91 cps in 5 parts by weight of styrene solution and styrene-butadiene rubber having a solution viscosity of 10 cps in 5 parts by weight of styrene solution. ABS thermoplastic resin composition was manufactured using the thing mix | blended in the weight ratio of 5: 5. The physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 2 below.

Example 6

Butadiene rubber having a solution viscosity of 91 cps in a 5 parts by weight of styrene solution and a styrene-butadiene rubber having a solution viscosity of 10 cps in a 5 parts by weight of styrene solution were prepared in the same manner as in Example 1. The ABS thermoplastic resin composition was manufactured using the thing mixed by the weight ratio of 8: 2. The physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 2 below.

Example 7

Butadiene rubber having a solution viscosity of 91 cps in a 5 parts by weight of styrene solution and a styrene-butadiene rubber having a solution viscosity of 10 cps in a 5 parts by weight of styrene solution were prepared in the same manner as in Example 1. An ABS thermoplastic resin composition was prepared using the mixture of 2: 8 by weight. The physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 2 below.

Example 8

In the same manner as in Example 1, butadiene rubber mixture was dissolved in the monomer mixture solution, and then the peroxide initiator was changed to a concentration of 200 ppm to prepare an ABS thermoplastic resin composition. The physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 2 below.

Comparative Example 3

ABS thermoplastic resin composition was prepared in the same manner as in Example 1, using butadiene rubber having a solution viscosity of 91 cps in a 5 parts by weight styrene solution using butadiene rubber. The physical property analysis results of the ABS thermoplastic resin composition thus prepared are shown in Table 2 below.

Comparative Example 4

ABS resin composition was prepared in the same manner as in Example 1, but using only styrene-butadiene rubber having a solution viscosity of 10 cps in a 5 parts by weight of styrene solution with butadiene rubber. The physical property analysis results of the ABS resin composition thus prepared are shown in Table 2 below.

division Example Comparative example 5 6 7 8 3 4 Particle size (um) Average 0.7 1.1 0.9 0.5 1.6 0.4 Distribution 1.6 2 2.1 1.7 2.5 1.6 Glossiness (%) 91 90 90 91 81 92 Izod impact strength kgcm / cm (1/4 ") 10.3 13.3 10.1 9.6 14.8 6.6 kgcm / cm (1/8 ") 12.4 15.2 12.7 11.2 16.5 8.0 Tensile Strength (kg / ㎠) 440 433 410 405 423 384 Elongation at Break,% 30.5 37.8 30.8 23.1 36.3 25.1 Fluidity (g / min) 220 ℃ / 10 kg) 22.3 22.8 22.5 22.3 24.9 20.3

As shown in Table 2, in the case of Examples 6 to 9 of the present invention, it is possible to control the size of the rubber particles compared to Comparative Examples 3 and 4, so that the ABS resin excellent in gloss, elongation, flowability, impact strength and tensile strength Could get

As described above, according to the production method of the present invention, butadiene rubber mixtures having different viscosities can be easily phase-shifted by bulk polymerization, the size of rubber particles and graft reaction can be easily controlled, and thus the impact strength and elongation characteristics are excellent, and the gloss is excellent. A high ABS thermoplastic resin composition can be obtained.

Claims (6)

In the method for producing a rubber-modified ABS thermoplastic resin composition, a) 40 to 60 parts by weight of styrene or styrene derivative monomers; 10 to 30 parts by weight of acrylonitrile or acrylonitrile derivative monomers; And 5 to 38 parts by weight of the reaction medium. Viii) the mixing weight ratio is from 9: 1 to 1: 9 High viscosity butadiene rubber having a solution viscosity of 70 to 150 cps and a solution viscosity of 1 to 4 times the Mooney viscosity in a 5 parts by weight styrene solution, and a solution viscosity of 10 to 70 cps and a solution viscosity of the Mooney viscosity to a 5 parts by weight styrene solution. Low viscosity butadiene rubber that is 0.2 to 1 times; or Ii) the mixing weight ratio is from 9: 1 to 1: 9 Butadiene rubber with a solution viscosity of 20 to 150 cps in 5 parts by weight of styrene solution, and styrene-butadiene rubber with a solution viscosity of 10 to 70 cps in 5 parts by weight of styrene solution 5 to 12 parts by weight of the rubber mixture containing the first step of mass polymerization; And b) 100 parts by weight of the first bulk polymer obtained above Second mass polymerization by adding 60 to 100 parts by weight of reaction medium Method of producing a rubber-modified ABS thermoplastic resin composition comprising a. The method of claim 1, Process for producing a rubber-modified ABS thermoplastic resin composition of step a) and b) step iii) the reaction medium is ethylbenzene or toluene. The method of claim 1, The bulk polymerization of step b) further comprises 0.1 to 25 parts by weight of styrene derivatives, and 0.1 to 15 parts by weight of acrylonitrile or acrylonitrile derivative monomers. The method of claim 1, The bulk polymerization is a method of producing a rubber-modified ABS thermoplastic resin composition further comprises 0.005 to 0.05 parts by weight of a polymerization initiator and 0.005 to 0.05 parts by weight of a molecular weight regulator. The method of claim 4, wherein The polymerization initiator is selected from the group consisting of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, and 1,1-bis (t-butylperoxy) cyclohexane Method for producing a rubber-modified ABS thermoplastic resin composition. The method of claim 4, wherein A method for producing a rubber-modified ABS thermoplastic resin composition wherein the molecular weight modifier is t-dodecyl mercaptan or n-octyl mercaptan.