KR20020035711A - Thermoplastic resin composition having superior coloring properties - Google Patents

Abstract

The present invention relates to a thermoplastic resin composition, and more particularly, to a styrene resin composition having excellent impact resistance, glossiness, and colorability.

To this end, in the styrene-based thermoplastic resin composition, a) i) the average particle diameter is 2800 to 3300 mm 3, the particle size distribution range is average particle diameter ± 25 to average particle diameter ± 75 mm 3, and the gel content is 70 to 95% by weight Phosphorus large diameter polybutadiene rubber latex 30 to 60 parts by weight; Ii) 15 to 30 parts by weight of an aromatic vinyl compound; Iii) 10 to 25 parts by weight of a vinylcyan compound; V) 0.6 to 2.0 parts by weight of emulsifier; V) 0.2 to 1.0 parts by weight of molecular weight modifier; And iv) 20 to 40 parts by weight of an ABS copolymer resin prepared by graft copolymerization of 0.05 to 0.5 parts by weight of a polymerization initiator; And b) 60 to 80 parts by weight of a styrene-acrylonitrile copolymer.

The composition of the present invention has the effect of providing a thermoplastic resin composition excellent in colorability while maintaining impact resistance.

Description

Thermoplastic resin composition excellent in colorability {THERMOPLASTIC RESIN COMPOSITION HAVING SUPERIOR COLORING PROPERTIES}

[Industrial use]

The present invention relates to a thermoplastic resin composition, and more particularly, to a styrene resin composition having excellent impact resistance, glossiness, and colorability.

[Private Technology]

Generally, acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) copolymer resin is obtained by adding a rubber component to the styrene-acrylonitrile copolymer, and has excellent quality such as impact resistance, chemical resistance, processability, and surface glossiness. Do. Taking advantage of these properties, ABS copolymer resins are widely used in monitor housings, game machine housings, home appliances, office equipment, and the like. However, as the impact, chemical resistance, processability, and surface glossiness are important factors in the selection of the product, the design and color of the exterior are important factors, and the necessity of a resin having the property of easily coloring various colors is increasing. Several methods have been proposed to improve this.

In order to improve the colorability, a method of reducing the refractive index little by little by manufacturing the rubber particles in a multilayer structure is known, but there is a problem in terms of economics by greatly increasing the manufacturing cost of ABS used as a general-purpose resin. Another method for improving the colorability is to increase the refractive index of the rubber particles by using a styrene-butadiene copolymer or the like by using the property that the colorability is improved by increasing the refractive index of the rubber particles themselves. Has the disadvantage of falling. The method of lowering the refractive index by copolymerizing another monomer having a low refractive index is also known as a method of improving colorability. However, when the amount of the monomer having a low refractive index is low, the effect is insignificant.

An object of the present invention is to provide a thermoplastic resin composition excellent in colorability while maintaining impact resistance in consideration of the problems of the prior art.

[Means for solving the problem]

The present invention, in order to achieve the above object, in the styrene-based thermoplastic resin composition,

a) i) Average particle size ranges from 2800 to 3300 mm 3 and particle size distribution ranges to average particle size

± 25 to average particle diameter ± 75 mm 3, and gel content of 70 to 95 weight percent

30 to 60 parts by weight of large-diameter polybutadiene rubber latex;

Ii) 15 to 30 parts by weight of an aromatic vinyl compound;

Iii) 10 to 25 parts by weight of a vinylcyan compound;

V) 0.6 to 2.0 parts by weight of emulsifier;

V) 0.2 to 1.0 parts by weight of molecular weight modifier; And

Iii) 0.05 to 0.5 parts by weight of polymerization initiator

20 to 40 parts by weight of an ABS copolymer resin prepared by graft copolymerization;

And

b) 60 to 80 parts by weight of styrene-acrylonitrile copolymer

It provides a thermoplastic resin composition excellent in colorability comprising a.

Hereinafter, the present invention will be described in detail.

[Action]

The thermoplastic resin composition excellent in colorability of the present invention is prepared by kneading a) 20 to 40 parts by weight of ABS copolymer resin and b) 60 to 80 parts by weight of styrene-acrylonitrile (SAN) copolymer.

Experimental results show that the colorability is improved by reducing the cross-sectional area of the rubber particles in the ABS copolymer resin of a). In order to reduce the cross-sectional area of the rubber particles, a method of reducing the total cross-sectional area of the rubber particles or when mixing with a SAN copolymer A method of reducing the content of can be used.

In order to reduce the total cross-sectional area of the particles, if the particle size of the rubber particles is the same, narrowing the particle size distribution decreases the total cross-sectional area, and if the particle size distribution range is the same, increasing the size of the particle increases the cross-sectional area of each particle but decreases the number of particles. This results in a smaller total cross section. In addition, when the amount of the rubber powder when kneaded with SAN, there is a problem that the impact strength is reduced. Therefore, it is necessary to use large-diameter rubber latex having a narrow particle size distribution range and a large particle size.

The ABS copolymer resin of a) is iii) a large diameter polybutadiene rubber latex having a high gel content and a narrow particle size distribution range; Ii) aromatic vinyl compounds; Iii) a vinylcyan compound; Iii) emulsifiers; Iii) a molecular weight modifier; And iii) graft copolymerization of the polymerization initiator.

The large diameter polybutadiene rubber latex of a) i) specifically has an average particle diameter of 2800 to 3300 mm 3, a particle size distribution range of average particle diameter ± 25 to average particle diameter ± 75 mm 3, and a gel content of 70 to 95 wt%, an average particle diameter Was added to 100 parts by weight of a small diameter rubber latex having a swelling index of 12 to 30 and a gel content of 70 to 95% by weight, and 1.0 to 4.0 parts by weight of an aqueous acetic acid solution was slowly stirred for 1 hour to enlarge the particles. It is then prepared by stopping the stirring.

The small-diameter rubber latex is 50 to 100 parts by weight of the total 100 parts by weight of the conjugated diene compound monomer, 1 to 4 parts by weight of the non-reacting emulsifier, 0.01 to 1.0 parts by weight of the reactive emulsifier, 0.1 to 0.6 parts by weight of the polymerization initiator, electrolyte 0.2 To 1.0 part by weight, 0.1 to 0.5 parts by weight of a molecular weight modifier, 90 to 130 parts by weight of ion-exchanged water, and reacted at 50 to 70 ° C. for 5 to 15 hours, followed by the rest of the conjugated diene compound monomer and 0.5 parts by weight or less of the reactive emulsifier. , 0.01 to 1.0 parts by weight of the non-reacting emulsifier, 0.05 to 1.2 parts by weight of the molecular weight regulator are administered in a batch or sequentially to react for 3 to 10 hours at 55 to 70 ℃ to minimize the coagulum, while having a large particle size and narrow particle size distribution range Prepare rubber latex.

The conjugated diene compound may be used alone as a monomer used in the preparation of the small-diameter rubber latex, and 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. However, when used in combination, it is preferable to use within 20% by weight of the total monomer mixture. As the conjugated diene compound, 1,3-butadiene, isoprene, chloroprene, pyrrylene, and comonomers thereof can be used.

The non-reactive emulsifier is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acid.

The reactive emulsifier is an anionic emulsifier having an allyl group, an anionic emulsifier having acryloyl group or a methacryloyl group, an anionic emulsifier having a propenyl group, a neutral emulsifier having an allyl group, acryloyl group or a methacryloyl group The branch is selected from two or more kinds from the group consisting of a neutral emulsifier and a neutral emulsifier having a propenyl group. Anionic emulsifiers having an allyl group may be representative of sulfate salts of polyoxyethylene allylglycidyl nonylphenyl ether and specifically exemplify the Adecaria SOAP SE series (manufactured by Asahi Denka). Can be. Neutral emulsifiers having an allyl group include polyoxyethylene allylglycidyl nonylphenyl ether series, and specifically, there are Adecaria SOAP (ADEKARIA SOAP) NE series (manufactured by Asahi Denka). Specifically, the anionic emulsifier having a methacryloyl group or acryloyl group has an ELEMINOL RS series (manufactured by Sanyo Kasei) and the neutral emulsifier is an RMA-560 series (Nippon Surfactant Company) may be used. As an anionic emulsifier having a propene group, ammonium sulfate salt of polyoxyethylene allylglycidyl nonyl propenyl phenyl ether is typically used. Specifically, the AQUARON HS series (Daiichi Kogyo Seiyaku) Co., Ltd.), and the neutral emulsifier may be used, such as AQUARON BC series (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). It may be used as a mixture of the above, and may be used in combination with a non-reactive emulsifier, in which the total amount of the reactive emulsifier used is preferably not more than 1.0 parts by weight, and when the amount is exceeded, small-diameter rubber latex may be used as an acidic substance. It is difficult to produce large-diameter rubber latex by fusion.

As the polymerization initiator, a water-soluble persulfate or a peroxy compound can be used, and an oxidation-reduction system can also be used. The most suitable water soluble persulfates are sodium persulfate or potassium persulfate and the fat soluble polymerization initiators are cumenehydro peroxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, And benzoyl peroxide and the like.

The electrolyte is KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , And Na ₂ HPO ₄ is used. Mercaptans are mainly used for molecular weight regulators.

The ABS copolymer resin of a) may be prepared by further comprising a large-diameter rubber latex having a low gel content. Specifically, the large-diameter rubber latex having a low gel content has an average particle diameter of 3300 to 4500 mm 3 and a gel content of 60 to 85 weight. %, And is prepared according to conventionally known methods. Specifically, the low-recrystallized rubber latex can be made by adjusting the amount of the emulsifier and the reaction temperature, and the low gel content can be controlled by lowering the polymerization conversion rate and the reaction temperature and adding a molecular weight regulator during the reaction. .

The ABS copolymer resin of a) is iii) 30 to 60 parts by weight of a large diameter polybutadiene rubber latex having a high gel content and a narrow particle size distribution range; Ii) 30 parts by weight or less of rubber latex having a low gel content; Iii) 15 to 30 parts by weight of an aromatic vinyl compound; Iii) 10 to 25 parts by weight of a vinylcyan compound; V) 0.6 to 2.0 parts by weight of emulsifier; V) 0.2 to 1.0 parts by weight of molecular weight modifier; And iii) 0.05 to 0.5 parts by weight of a polymerization initiator is prepared by graft copolymerization. 0 to 80 parts by weight of the monomers used in the production of the ABS copolymer resin are reacted after the batch administration in the initial reaction, and when the conversion rate of the monomer added after 30 to 90 minutes is 40 to 90% by weight, the remaining monomers are collectively administered or Alternatively, the reaction is performed sequentially and the reaction is further proceeded for 1 hour after the administration is completed, and then the polymerization reaction is terminated. At this time, the polymerization temperature is 40 to 80 ℃, the total polymerization time is preferably 2 to 7 hours.

The emulsifier used in the polymerization reaction may be the emulsifier used to prepare the small-diameter latex. As the molecular weight regulator, tertiary dodecyl mercaptan is mainly used, and polymerization initiators include peroxides such as tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzenehydro peroxide, and peroxide, sodium formaldehyde succilate, sodium Mixtures with reducing agents such as ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite and the like can be used. The polymerized latex is agglomerated by using a well-known coagulant sulfuric acid or MgSO ₄ , CaCl ₂ , Al ₂ (SO ₄ ) ₃ and the like to obtain a powder and the solid coagulum produced during the reaction is represented by the following equation (1). It was.

[Equation 1]

20 to 40 parts by weight of the ABS copolymer resin prepared above and 60 to 80 parts by weight of the styrene-acrylonitrile (SAN) copolymer are kneaded to prepare a thermoplastic resin composition having excellent colorability while maintaining impact resistance.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Example 1

(Manufacture of Small Diameter Rubber Latex a)

110 parts by weight of ion-exchanged water, 85 parts by weight of 1,3-butadiene, 1.2 parts by weight of potassium rosin salt, 1.0 parts by weight of potassium oleate salt, and Aquaron HS-10 (AQUARON HS-10) 0.35 part by weight of Daiichi Kogyo Seiyaku (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 0.5 part by weight of potassium carbonate, 0.3 part by weight of tertiary dodecyl mercaptan (TDDM), and 0.3 part by weight of potassium persulfate at once After reacting for 15 hours, 1 part by weight of 1,3-butadiene and 0.05 part by weight of tertiary dodecyl mercaptan were added in a batch and reacted for 6 hours at 65 ° C. After the completion of the reaction, the rubber polymer latex gel was prepared. The content and swelling index were measured.

The gel content and swelling index of the rubber latex were solidified by diluting the prepared rubber latex with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and then chopped into pieces of rubber and then 1 g of The rubber sections were placed in 100 g of toluene, stored in a dark room at room temperature for 48 hours, separated into sol and gel, and calculated according to the following equations (2) and (3), and the average particle size was measured using Nicomp 370 HPL by dynamic laser light scattering. It was.

[Equation 2]

[Equation 3]

The average particle diameter of the small-diameter rubber latex a measured by the above method was 1000 GP, the gel content was 85% by weight, and the swelling index was 18.

(Manufacture of large diameter rubber latex A)

100 parts by weight of the small-diameter rubber latex a prepared above was added to the reactor, and the stirring speed was adjusted to 10 rpm, and the temperature was adjusted to 30 ° C., followed by gradually adding 2 parts by weight of 6% by weight of acetic acid aqueous solution for 1 hour, followed by stirring. Was stopped and left for 30 minutes to prepare large diameter rubber latex A. 10 wt% of potassium hydroxide was added to the prepared large-diameter rubber latex A at a weight part as shown in Table 1, followed by stabilization, and the physical properties thereof were measured. The results are shown in Table 1 below.

(Production of ABS Copolymer Resin I)

60 parts by weight of large diameter rubber latex A, 145 parts by weight of ion-exchanged water, 0.09 parts by weight of dextrose, 0.08 parts by weight of sodium pyrrolate, 0.002 parts by weight of ferrous sulfate, and cumene, as shown in Table 2 below. 0.05 parts by weight of hydroperoxide was added. 1.2 parts by weight of potassium rosin acid, 25 parts by weight of ion-exchanged water, 28 parts by weight of styrene monomer, 12 parts by weight of acrylonitrile, 0.3 parts by weight of t-dodecyl mercaptan, and 0.16 parts by weight of cumene hydroperoxide The emulsion was added sequentially while maintaining the reaction temperature of 70 ℃ for 3 hours. After the addition, 0.083 parts by weight of dextrose, 0.05 parts by weight of sodium pyrolate, 0.001 parts by weight of ferrous sulfate, and 0.05 parts by weight of cumene hydroperoxide were added to the reactor at once, and the temperature was raised to 80 ° C. over 1 hour, followed by reaction. To terminate the ABS copolymer resin I was prepared. The reaction conversion rate at this time was 99 weight%. After the completion of the reaction, an antioxidant was added to the ABS copolymer resin I, and then coagulated with 25 wt% magnesium sulfate aqueous solution, followed by washing and drying to prepare a powder of the ABS copolymer resin I.

(Production of the thermoplastic resin composition)

A thermoplastic resin composition was prepared by adding 74 parts by weight of a SAN and 28 g of an acrylonitrile content and a lubricant to 26 parts by weight of the powder of the ABS copolymer resin I prepared in the above step. Injection molding the prepared thermoplastic resin composition to prepare a specimen with a final rubber content of 15% by weight and measured the physical properties are shown in Table 2 below.

Izod impact strength is ASTM D256 method with 1/4 "thickness of specimen, tensile strength is ASTM D638 method, and Melt Flow Index (MI) is ASTM D1238 method under conditions of 220 ℃ and 10 Kg. Surface gloss was measured by ASTM D528 method at an angle of 45 °, and colorability is expressed by L, a and b values by measuring the degree of coloring based on green color sensitive to human eyes using a SUGA Color Computer. It was assumed that the lower the L value and the higher the a value, the better the red value was.

Example 2

(Manufacture of large diameter rubber latex B)

100 parts by weight of the small-diameter rubber latex a prepared in Example 1 was carried out in the same manner as in the preparation of the large-diameter rubber latex A of Example 1, but the amount of acetic acid aqueous solution and potassium hydroxide was used as the weight parts shown in Table 1 to the gel content. This high diameter and narrow particle size distribution range was prepared large diameter rubber latex B, the physical properties of the prepared large diameter rubber latex B was measured in the same manner as in Example 1 and the results are shown in Table 1.

(Production of ABS Copolymer Resin II)

ABS copolymer resin II was carried out in the same manner as in the ABS copolymer resin preparation of Example 1, but using the large-diameter rubber latex B prepared above as shown in Table 2 instead of the large-diameter rubber latex A used in Example 1. Was prepared.

(Production of the thermoplastic resin composition)

The same procedure as in the preparation of the thermoplastic resin composition of Example 1 was carried out, except for using ABS copolymer resin II prepared in Example 1 and using ABS copolymer resin II and acrylonitrile. The amount of SAN having a content of 28% by weight was prepared as shown in Table 3 to prepare a thermoplastic resin composition. The prepared thermoplastic resin composition was injection molded to prepare a specimen, and the physical properties thereof were measured in the same manner as in Example 1, and are shown in Table 3 below.

Example 3

(Production of ABS Copolymer Resin III)

The same procedure as in the ABS copolymer resin manufacturing method of Example 1 was carried out, but the large-diameter rubber latex B prepared in Example 2 together with the large-diameter rubber latex A used in Example 1 was used by weight as shown in Table 2. Copolymer Resin III was prepared.

(Production of the thermoplastic resin composition)

The same procedure as in the preparation of the thermoplastic resin composition of Example 1 was carried out, except that the ABS copolymer resin III prepared above was used instead of the ABS copolymer resin I used in Example 1, and the ABS copolymer resin III and acrylonitrile The amount of SAN having a content of 28% by weight was prepared as shown in Table 3 to prepare a thermoplastic resin composition. The prepared thermoplastic resin composition was injection molded to prepare a specimen, and the physical properties thereof were measured in the same manner as in Example 1, and are shown in Table 3 below.

Example 4

(Preparation of large diameter rubber latex C with low gel content)

100 parts by weight of 1,3-butadiene, 65 parts by weight of ion-exchanged water, 1.5 parts by weight of potassium rosin salt, 0.2 parts by weight of potassium oleate salt, 2.0 parts by weight of potassium carbonate, tertiary dodecyl mercaptan ( 0.3 parts by weight of TDDM) and 0.2 parts by weight of potassium persulfate were collectively administered and reacted at a reaction temperature of 70 ° C. for 10 hours. When the conversion rate was measured and the polymerization conversion rate was 50% by weight, 0.3 parts by weight of AQUARON HS-10, a reactive emulsifier, was added at 75 ° C for 20 hours, and then reacted when the polymerization conversion rate was 85% by weight. Terminated. The prepared rubbery polymer latex was analyzed in the same manner as in Example 1, and the average particle diameter was 3500 mm 3, the particle size distribution range was ± 190 mm 3, and the gel content was 65 wt%.

(Production of ABS Copolymer Resin IV)

The ABS copolymer was prepared in the same manner as in the ABS copolymer resin preparation of Example 1, but using the large-diameter rubber latex C prepared in Example 1 by weight as shown in Table 2, together with the large-diameter rubber latex A prepared in Example 1. Resin IV was prepared.

(Production of the thermoplastic resin composition)

The same procedure as in the preparation of the thermoplastic resin composition of Example 1 was carried out, except that ABS copolymer resin IV prepared above was used instead of ABS copolymer resin I used in Example 1, and ABS copolymer resin IV and acrylonitrile were used. The amount of SAN having a content of 28% by weight was prepared as shown in Table 3 to prepare a thermoplastic resin composition. The prepared thermoplastic resin composition was injection molded to prepare a specimen, and the physical properties thereof were measured in the same manner as in Example 1, and are shown in Table 3 below.

Comparative Examples 1 and 2

(Manufacture of small-diameter rubber latex b)

A small-diameter rubber latex b was prepared in the same manner as in the method of preparing the small-diameter rubber latex a of Example 1, but without adding the reactive emulsifier AQUARON HS-10.

The physical properties of the prepared small-diameter rubber latex b were measured in the same manner as in Example 1, and the average particle diameter was 1000 mm 3, the gel content was 83 wt%, and the swelling index was 17.

(Manufacture of large diameter rubber latex D, E)

The same procedure as in the preparation of the large-diameter rubber latex A of Example 1 was carried out. Instead of the small-diameter rubber latex a, the small-diameter rubber latex b prepared above was used, and the amounts of sodium dodecyl sulfonate, an aqueous solution of acetic acid, and potassium hydroxide were Using large parts by weight shown in 1 to prepare large diameter rubber latex D, E, the physical properties of the prepared large diameter rubber latex D, E was measured in the same manner as in Example 1 and the results are shown in Table 1.

(Preparation of ABS Copolymer Resins V and VI)

The same procedure as in the preparation of the ABS copolymer resin of Example 1 was carried out, but instead of the large-diameter rubber latex A used in Example 1, the large-diameter rubber latex D and E prepared above were used by weight as shown in Table 2. ABS copolymer resins V and VI were prepared.

(Production of the thermoplastic resin composition)

The same procedure as in the preparation of the thermoplastic resin composition of Example 1 was carried out, except that the ABS copolymer resins V and VI prepared above were used instead of the ABS copolymer resin I used in Example 1, and the ABS copolymer resins V and VI The amount of SAN having an acrylonitrile content of 28% by weight was prepared as shown in Table 3. The prepared thermoplastic resin composition was injection molded to prepare a specimen, and the physical properties thereof were measured in the same manner as in Example 1, and are shown in Table 3 below.

TABLE 1

division Large Diameter Rubber Latex A Large Diameter Rubber Latex B Large Diameter Rubber Latex D Large Diameter Rubber Latex E Small Diameter Rubber Latex a (parts by weight) 100 100 - - Small-diameter rubber latex b (part by weight) - - 100 100 Sodium dodecyl sulfonate (parts by weight) - - 0.4 0.4 Acetic acid (parts by weight) 2 2.5 2 2.5 Potassium hydroxide (parts by weight) 1.9 2.4 1.9 2.4 Gel content (% by weight) 81 82 83 80 Swelling index 18 19 15 19 Average particle size 3000 3500 2900 3400 Drop size distribution range Average particle size ± 50 Average particle size ± 75 Average particle size ± 200 Average particle size ± 250 Product coagulated product (% by weight) 0.01 0.015 0.05 0.075

TABLE 2

division ABS copolymer resin I ABS copolymer resin II ABS copolymer resin III ABS copolymer resin IV ABS copolymer resin V ABS copolymer resin VI Large Diameter Rubber Latex A (parts by weight) 60 - 30 30 - - Large Diameter Rubber Latex B (Weight) - 60 30 - - - Large Diameter Rubber Latex C (Weight) - - - 30 - - Large Diameter Rubber Latex D (parts by weight) - - - - 60 - Large Diameter Rubber Latex E (Weight) - - - - - 60

TABLE 3

division Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Type and amount of powder (parts by weight) ABS copolymer resin I, 26 ABS copolymer resin II, 24 ABS copolymer resin III, 24 ABS copolymer resin IV, 24 ABS copolymer resin V, 26 ABS copolymer resin VI, 24 SAN (part by weight) 74 76 76 76 74 76 Izod impact strength (㎏㎝ / ㎝) 22.3 21.7 20.9 21.5 22.2 21.4 Liquidity Index (g / 10 min) 22.4 23.9 23.0 22.9 22.1 23.4 Tensile Strength (kg / cm 3) 502 505 509 501 498 510 Surface gloss (%) 101 93 100 99 101 94 Colorant Usage 0.16 0.14 0.14 0.14 0.16 0.14 Coloring L 30.7 30.4 30.6 30.5 30.7 30.8 Coloring a 53.2 53.1 53.0 53.0 51.4 52.4

As shown in Table 3, the compositions of Examples 1 to 4 using the large-diameter rubber latex satisfying the conditions mentioned in the detailed description of the invention are excellent in colorability while maintaining impact resistance compared to the compositions of Comparative Examples 1 and 2. I could see that.

The composition of the present invention has the effect of providing a thermoplastic resin composition excellent in colorability while maintaining impact resistance.

Claims (15)

a) i) Average particle size ranges from 2800 to 3300 mm 3 and particle size distribution ranges to average particle size ± 25 to average particle diameter ± 75 mm 3, and gel content of 70 to 95 weight percent 30 to 60 parts by weight of large-diameter polybutadiene rubber latex; Ii) 15 to 30 parts by weight of an aromatic vinyl compound; Iii) 10 to 25 parts by weight of a vinylcyan compound; V) 0.6 to 2.0 parts by weight of emulsifier; V) 0.2 to 1.0 parts by weight of molecular weight modifier; And Iii) 0.05 to 0.5 parts by weight of polymerization initiator 20 to 40 parts by weight of an ABS copolymer resin prepared by graft copolymerization; And b) 60 to 80 parts by weight of styrene-acrylonitrile copolymer Excellent thermoplastic resin composition comprising a. The method of claim 1, The thermoplastic resin composition of claim 1, wherein the ABS copolymer resin further comprises 30 parts by weight or less of rubber latex having an average particle diameter of 3300 to 4500 mm 3 and a gel content of 60 to 85 wt%. The method of claim 1, The large diameter polybutadiene rubber latex of a) i) A) 100 parts by weight of the conjugated diene compound monomer; B) 1.01 to 5 parts by weight of a non-reactive emulsifier; C) 0.01 to 1.5 parts by weight of a reactive emulsifier; D) 0.1 to 0.6 parts by weight of a polymerization initiator; M) 0.2 to 1.0 parts by weight of electrolyte; Iii) 0.1 to 0.5 parts by weight of a molecular weight modifier; And ㅅ) 90 to 130 parts by weight of ion-exchanged water A thermoplastic resin composition having excellent colorability prepared by stirring 100 parts by weight of a small-diameter rubber latex having an average particle diameter of 600 to 1500 mm 3 and a gel content of 70 to 95 wt% and 1.0 to 4.0 parts by weight of an acetic acid aqueous solution. The method of claim 3, wherein The small diameter rubber latex is an aromatic vinyl compound selected from the group consisting of styrene, α-methylstyrene, 0-etherstyrene, p-ethylstyrene, and vinyltoluene, and acrylonitrile, methacrylonitrile and ethacrylonitrile. A thermoplastic resin composition excellent in colorability prepared by further comprising a vinylcyan compound selected from the group consisting of: The method of claim 3, wherein The thermoplastic resin composition having excellent colorability, wherein the conjugated diene compound monomer of a) is selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, pyrrylene, and comonomers thereof. The method of claim 3, wherein The non-reactive emulsifier of b) is a thermoplastic resin having excellent colorability selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid. Composition. The method of claim 3, wherein The reactive emulsifier of c) is a group consisting of sulfate salts of polyoxyethylene allylglycidyl nonylphenyl ether, polyoxyethylene allylglycidyl nonylphenyl ether, and ammonium sulfate salts of polyoxyethylene allylglycidyl nonylpropenyl phenyl ether Thermoplastic resin composition excellent in the coloring property selected from two or more types. The method of claim 3, wherein The polymerization initiator of d) is sodium persulfate, potassium persulfate, cumene hydroperoxide, diisopropyl benzenehydroperoxide, azobis isobutylnitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl per A thermoplastic resin composition excellent in colorability selected from the group consisting of oxides. The method of claim 3, wherein ㅁ) the electrolyte of KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P2O7, K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ And a thermoplastic resin composition excellent in colorability selected from at least one member selected from the group consisting of Na ₂ HPO ₄ . The method of claim 3, wherein The thermoplastic resin composition excellent in the coloring property whose molecular weight modifier of said i) is a tertiary dodecyl mercaptan. The method of claim 1, A thermoplastic resin composition having excellent colorability, wherein the aromatic vinyl compound of a) ii) is selected from the group consisting of styrene, α-methylstyrene, 0-ethylstyrene, p-ethylstyrene, and vinyltoluene. The method of claim 1, The thermoplastic resin composition having excellent colorability, wherein the vinyl cyan compound of a) iii) is selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. The method of claim 1, The thermoplastic resin composition excellent in colorability in which the emulsifier of a) iii) is selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, and alkali salts of rosin acid. . The method of claim 1, The thermoplastic resin composition excellent in the coloring property whose said molecular weight modifier of (a) i) is tertiary dodecyl mercaptan. The method of claim 1, The polymerization initiator of a) iii) is a peroxide selected from the group consisting of tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and peranthate, sodium formaldehyde succilate, sodium ethylenediamine A thermoplastic resin composition excellent in colorability, which is a mixture of a reducing agent selected from the group consisting of tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium sulfite.