KR100508145B1 - Low Gloss Thermoplastic Resin Composition Having Heat Resistance and High Impact Strength - Google Patents

Abstract

The present invention relates to a matte thermoplastic resin composition excellent in impact resistance and heat resistance, graft ABS polymer 10 to 40 parts by weight; 60 to 90 parts by weight of the heat resistant copolymer; 0.1 to 10 parts by weight of acrylonitrile polymer for matte filler; And 5 to 20 parts by weight of a styrene acrylonitrile polymer for a matte filler, and the matte thermoplastic resin composition of the present invention does not deteriorate impact resistance, heat resistance, and other physical properties even when a matte filler is added to the impact and heat resistant ABS resin. It does not work.

Description

Low Gloss Thermoplastic Resin Composition Having Heat Resistance and High Impact Strength

The present invention relates to a matte thermoplastic resin composition having excellent impact resistance and heat resistance, and more particularly, to a kraft acrylonitrile-butadiene-styrene polymer having excellent impact resistance and heat resistance, even when kneaded by adding a filler for a matte filler. The present invention relates to a matte thermoplastic resin composition excellent in impact resistance and heat resistance that does not deteriorate impact resistance and heat resistance.

Recently, many researches have been made to use a car interior material by providing heat resistance to acrylonitrile-butadiene-styrene resin having excellent impact resistance, chemical resistance, and workability due to the necessity of lightening the automobile. As a method for imparting heat resistance to acrylonitrile-butadiene-styrene (hereinafter referred to as ABS), a method of kneading a graft ABS polymer with a heat resistant copolymer excellent in heat resistance to produce a heat resistant ABS resin has been proposed. As a method of manufacturing the heat resistant ABS resin, a part or the entirety of the styrene used in the preparation of the kneading heat resistant copolymer disclosed in US Patent Nos. 3,010,936 and 4,659,790 is replaced with α-methylstyrene having excellent heat resistance. There is a method for producing a method, including a maleimide compound disclosed in Japanese Patent Application Laid-Open No. 58-206657, No. 63-162708, No. 63-235350 and US Patent No. 4,757,109 is a method for producing a heat resistant ABS resin In addition, there are known a method of kneading with other polycarbonate resin, a method of filling an inorganic material, and the like.

Also, in recent years, users have increased the demand for matte resins in order to create a more elegant atmosphere with higher levels of emotional quality.In addition, the use of matte resins has been omitted and the use of matte coatings or pads has been omitted as environmental problems arise. The trend is to try. US Pat. No. 5,162,419 discloses a method for producing a matte ABS resin by adding acrylonitrile resin to a polycarbonate resin and acrylonitrile butadiene blend as a matte filler and expressing a matte effect. A method of filling a nitrile butadiene blend with a mineral to give a matt effect is disclosed.

Such a technique of expressing the matte in the existing heat-resistant ABS resin is excellent in the matte effect, but causes a problem that the heat resistance and impact strength is lowered by using a matte filler. In addition, the heat-resistant ABS resin has a lot of post-processing process after injection molding, there is an effort to shorten the post-processing process. One such effort is the development of matte ABS resins.

Accordingly, the present inventors have kneaded by adding a styrene acrylonitrile polymer and an acrylonitrile polymer as a matte filler to the heat resistant ABS resin at a predetermined ratio to complete a matt thermoplastic resin composition having excellent impact resistance and heat resistance.

An object of the present invention is to provide a matte thermoplastic resin composition excellent in impact resistance and heat resistance that does not lower impact resistance and heat resistance even when a matte filler is added.

These and other objects can be achieved by the present invention described below.

Matte thermoplastic resin composition excellent in impact resistance and heat resistance according to the present invention is 10 to 40 parts by weight of the graft ABS polymer; 60 to 90 parts by weight of the heat resistant copolymer; 0.1 to 10 parts by weight of acrylonitrile polymer for matte filler; And 5 to 20 parts by weight of a styrene acrylonitrile polymer for a matte filler.

The matt thermoplastic resin is 0.5 to 5.0 parts by weight of inorganic materials for matte,

The lubricant may further comprise 0.2 to 1.5 parts by weight and 0.1 to 1.0 parts by weight of antioxidant.

The graft ABS polymer is 40 to 70 parts by weight of a conjugated diene rubber latex, 15 to 40 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyanide compound, 0.2 to 0.6 parts by weight of an emulsifier, and 0.2 to 0.6 parts by weight of a molecular weight regulator. And 0.1 to 0.5 parts by weight of the polymerization initiator.

The heat resistant copolymer comprises 50 to 80 parts by weight of α-methylstyrene (AMS), 20 to 50 parts by weight of acrylonitrile (AN), 26 to 30 parts by weight of toluene and a molecular weight modifier.

The styrene acrylonitrile polymer for the matte filler is 20 to 77 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyanide compound, 0.1 to 6 parts by weight of α, β-unsaturated carboxylic acid, 0.1 to 1 weight of a molecular weight regulator Part, 0.1 to 2 parts by weight of an emulsifier, 0.1 to 0.2 parts by weight of a polymerization initiator, and 0.1 to 0.5 parts by weight of an oxidation-reduction catalyst.

The matt inorganic material is zeolite. The lubricant is based on bis-steramide.

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

The thermoplastic resin composition having excellent heat resistance and impact resistance of the present invention is prepared by preparing a graft ABS polymer, a heat resistant copolymer, an acrylonitrile polymer for a matte filler and a styrene acrylonitrile for a matte filler, respectively, and then mixing them.

The thermoplastic resin composition excellent in heat resistance and impact resistance of the present invention is prepared by the following production method.

(A) Preparation of Graft ABS Polymer

The particle diameter and gel content of the conjugated diene rubber latex used in the manufacture of graft ABS polymer have a great influence on the impact strength and processability of the resin. In general, the smaller the particle diameter of the rubber latex, the better the glossiness, but the impact resistance and workability are lowered, and the larger the particle diameter, the better the impact resistance but the glossiness is lowered. The lower the gel content, the more polymerized in the state in which the monomer is swelled in the rubber latex and the larger the apparent particle size, the higher the impact strength and the lower the gloss.

In addition, when the graft ABS polymer is manufactured, the graft ratio greatly affects physical properties. When the graft ratio is lowered, a large number of ungrafted rubber latexes are present, thereby reducing thermal stability. In addition, the higher the content of the rubber latex and the larger the particle size, the lower the graft rate, which has a limit of improving thermal stability.

Therefore, a method for producing a conjugated diene rubber latex having an appropriate particle size and gel content is important, and a method of increasing the graft ratio when grafting an aromatic vinyl compound and a vinyl cyanide compound to a large diameter rubber latex is important.

In consideration of the above points, in the present invention, in order to prepare a graft ABS polymer, a conjugated diene-based polymer has a particle diameter of 600 to 1,500 mm 3, a gel content of 70 to 95%, and a swelling index of 12 to 30. After the caliber rubber latex is manufactured, the small-diameter rubber latex is fused to prepare a large-diameter rubber latex having a particle diameter of 2,500 to 5,000 mm 3, and grafting. Particularly, the gel content of the small-diameter rubber latex is 70 to 95% because the impact strength is lowered when the gel content is more than 95%, and the thermal stability is lowered when the gel content is less than 70%. The particle diameter is an important factor in imparting high impact properties to the thermoplastic resin, and the particle diameter satisfying the physical properties of the present invention is 2500 to 5000 mm 3.

1) Small Diameter Rubber Latex Manufacturing Process

100 parts by weight of conjugated diene, 1 to 4 parts by weight of emulsifier, 0.1 to 0.6 parts by weight of polymerization initiator, 0.1 to 1.0 parts by weight of electrolyte, 0.1 to 0.5 parts by weight of molecular weight regulator, and 90 to 130 parts by weight of ion-exchanged water After reacting at a temperature of 50 to 65 ° C. for 7 to 12 hours, 0.05 to 1.2 parts by weight of a molecular weight modifier was further added and reacted at a temperature of 55 to 70 ° C. for 5 to 15 hours, with an average particle size of 600 to 1500 kPa and a gel content. The small-diameter conjugated diene rubber latex having 70 to 95% and swelling index of 12 to 30 is prepared.

As the conjugated diene rubber latex, an aliphatic conjugated diene compound alone or a mixture of an aliphatic conjugated diene compound and an ethylenically unsaturated compound may be selected and used.

The emulsifier may be selected from one or more selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like.

The polymerization initiators include water-soluble persulfates such as sodium persulfate and potassium persulfate, peroxy compounds, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate and sodium sulfite Redox-based compounds or cumene hydroperoxides, diisopropyl benzenehydroperoxides, azobis isobutylnitriles, tertiary butyl hydroperoxides, paramethane hydroperoxides, benzoyl peroxides, At least one oil-soluble polymerization initiator selected from the group consisting of persulfates can be selected and used.

As the electrolyte, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ , and Na ₂ HPO ₄ It can be used by selecting one or more from the group consisting of.

As the molecular weight regulator, mercaptans such as t-dodecyl mercaptan or n-dodecyl mercaptan can be used.

The polymerization temperature is very important for adjusting the gel content and swelling index of the rubber latex, and the selection of the initiator should also be considered.

2) Large Diameter Rubber Latex Manufacturing Process (Small Diameter Rubber Latex Fusion Process)

In general, since the large-diameter rubber latex particle diameter imparts a high impact to the thermoplastic resin, its preparation is very important, and the particle size required to satisfy the physical properties in the present invention is about 2500 to 5000Å.

The particles were agitated by gradually adding 2.5 to 4.5 parts by weight of an aqueous acetic acid solution to 100 parts by weight of a small diameter rubber latex having a particle diameter of 600 to 1500 mm, a gel content of 70 to 95%, and a swelling index of 12 to 30, for 1 hour, and then agitating the particles. The large-diameter rubber latex was prepared by fusing a particle diameter of 500 to 5000Å, a gel content of 70 to 95%, and a swelling index of 12 to 30.

3) Grafting Process

40 to 70 parts by weight of the large diameter conjugated diene rubber latex prepared by the above method, 15 to 40 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyanide compound, 0.2 to 0.6 parts by weight of an emulsifier, and 0.2 to 0.6 parts by weight of a molecular weight regulator. And graft copolymerization using 0.1 to 0.5 parts by weight of a polymerization initiator and the like. At this time, the polymerization temperature is 45 to 80 ℃, the polymerization time is preferably 3 to 5 hours. Examples of the method of adding each component during graft polymerization include a method of collectively administering each component, a method of dividing the components into multiple stages, and a method of continuously administering the components, but in order to improve the graft rate and minimize the formation of coagulated products, The divided administration method or the continuous administration method is preferable.

As the aromatic vinyl compound, one or more selected from the group consisting of styrene, α-methylstyrene, o-ethylstyrene, p-ethylstyrene and vinyltoluene can be used.

As the vinyl cyan compound, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile can be used.

The emulsifier may be selected from one or more selected from the group consisting of alkylaryl sulfonates, alkali methylalkyl sulfates, sulfonated alkyl esters, fatty acid soaps, alkali salts of rosin acid, and the like.

As the molecular weight regulator, tertiary dodecyl mercaptan may be mainly used.

The polymerization initiators include water-soluble persulfates such as sodium persulfate and potassium persulfate, peroxy compounds, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate and sodium sulfite Redox-based compounds or cumene hydroperoxides, diisopropyl benzenehydroperoxides, azobis isobutylnitriles, tertiary butyl hydroperoxides, paramethane hydroperoxides, benzoyl peroxides, At least one oil-soluble polymerization initiator selected from the group consisting of persulfates can be selected and used.

The polymerization conversion rate of the latex obtained after the completion of the polymerization is 96% or more, and it is preferable to obtain an antioxidant and a stabilizer to the latex to coagulate with an aqueous sulfuric acid solution at a temperature of 80 ° C. or higher, and then dehydrate and dry.

The stability of the graft copolymer latex prepared above is determined by measuring the solid coagulation content (%) according to Equation 1 below. When the solid coagulation content is 0.7% or more, the latex stability is extremely lowered and a large amount of coagulum is determined. It is not suitable for the present invention.

[Equation 1]

Solid coagulation (%) = (weight of coagulant produced in the reactor (g) / weight of total rubber and monomers) * 100

The graft rate of the graft polymer solidifies the graft polymer latex. wash. Drying to obtain a powder form, 2g of this powder in 300ml of acetone and stirred for 24 hours to separate the solution obtained by ultracentrifuge and drop the separated acetone solution in methanol to obtain a non-grafted portion to dry the weight It measures and measured by following formula (2). At this time, if the graft ratio is 25% or less, the thermal stability is lowered and is not suitable for the present invention.

[Equation 2]

Graft Rate (%) = (weight of grafted monomer / rubber weight) * 100

(B) Preparation of heat resistant copolymer

To prepare a heat resistant copolymer suitable for the present invention, 50 to 80 parts by weight of α-methylstyrene as a monomer, 20 to 50 parts by weight of acrylonitrile as a monomer, 26 to 30 parts by weight of toluene as a solvent and tertiary dodecyl as a molecular weight regulator After the mercaptan is mixed, the mixture is reacted for 2 to 4 hours while continuously introducing the mixture into the reactor, and the reaction temperature at this time is preferably maintained at 140 to 170 ° C. The manufacturing process of the polymer is a continuous process consisting of a raw material input pump, a continuous stirring tank, a preheating tank, a volatilization tank, a polymer transfer pump and an extrusion process. Chain structure distribution of α-methylstyrene (hereinafter referred to as 'AMS' in structure) and acrylonitrile (hereinafter referred to as 'AN' in structure) copolymer prepared by the above process was ¹³ C NMR analyzer The identification method is determined by dissolving the polymer in pellet form with deuterated chloroform and using tetramethylsilane (TMS) as an internal standard. Among the peaks measured, the peaks in the range of 141 to 144 ppm were the {AMS-AN-AN} chains, and the peaks in the range of 144.5 to 147 ppm were the {AMS-AMS-AN} chains, and the peaks in the range of 147.5 to 150 ppm were { AMS-AMS-AMS} The molecular structure of the copolymer is confirmed by measuring the area of these peaks as the chain structure.

In the present invention, when the chain structure of {AMS-AMS-AMS} in the molecular chain structure of the copolymer is 15% or more of the entire structure, the chain structure of {AMS-AMS-AMS} is thermally decomposed to reduce thermal stability. In addition, if the chain structure of {AMS-AN-AN} is 40% or more of the whole structure, heat resistance is not good, which is not preferable.

(C) Preparation of Matte Filler Acrylonitrile Polymer

Preparation of matte filler acrylonitrile polymers suitable for the present invention is prepared by including diepoxide, an epoxide-based electrolyte in an acrylonitrile monomer, according to the method disclosed in US Pat. No. 5,536,780.

(D) Preparation of Matte Filler Styreneacrylonitrile Polymer

In order to prepare a matte filler styrene acrylonitrile polymer suitable for the present invention, 20 to 77 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyanide compound, 0.1 to 6 parts by weight of an α, β-unsaturated carboxylic acid, 0.1 to 1 parts by weight of the molecular weight regulator, 0.1 to 2 parts by weight of the emulsifier, 0.1 to 0.2 parts by weight of the polymerization initiator, 0.1 to 0.5 parts by weight of the oxidation-reduction catalyst, and then the mixture was continuously added to the reactor for reaction for 3 to 4 hours. At this time, the reaction temperature is preferably maintained at 60 to 80 ℃. After completion of the reaction, the prepared polymer is aggregated with calcium chloride, washed and dried to obtain styrene acrylonitrile in powder form.

As said aromatic vinyl compound, it is preferable that they are styrene, (alpha) -methylstyrene, or a mixture thereof.

The vinyl cyan compound is preferably acrylonitrile, methacrylonitrile or a mixture thereof.

As the α, β-unsaturated carboxylic acid compound, at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid and crotononic acid may be used.

As the emulsifier, it is preferable to use a sulfone-based, sulfate-based or sulfosuccinate-based compound, more preferably at most 2 parts by weight of alkylbenzenesulfonate.

Examples of the initiator include peroxides such as cumene hydroperoxide, diisopropylbenzenehydroperoxide, and peracid salt, sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrolate, and Preference is given to using an oxidation-reduction catalyst system in a mixture with a reducing agent such as sodium sulfate or the like.

The molecular weight modifier is preferably mercaptans such as t-dodecyl mercaptan or n-dodecyl mercaptan.

(E) kneading process

10 to 40 parts by weight of the graft ABS polymer prepared in (A), 60 to 90 parts by weight of the heat resistant copolymer prepared in (B), 0.1 to 10 parts by weight of the matte polymer prepared in (C), 5 to 20 parts by weight of the prepared matt polymer, 0.5 to 5 parts by weight of inorganic material, 0.2 to 1.5 parts by weight of lubricant and 0.1 to 1.0 part by weight of antioxidant are added and then kneaded at 200 to 250 ° C.

The matt inorganic material is intended to exert the matt effect of the resin, and alumino silicate metal hydroxide is preferably zeolite which is a crystalline anhydride.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to Examples.

Evaluation of the physical properties of the rubber latex and the final resin produced through the Examples and Comparative Examples was carried out by the following method.

◎ Gel content and swelling index: The rubber latex is solidified with dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C for 24 hours, chopped rubber mass with scissors, and then 1 g of rubber sections is added to 100 g of toluene. After storing for 48 hours at room temperature in the dark and separated into a sol and a gel to calculate the gel content by the following equation (3), the swelling index was calculated by the equation (4).

[Equation 3]

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

[Equation 4]

      Swelling index = weight of swollen gel / weight of gel

◎ Particle diameter: Measured using Nicomp 370 HPL by the dynamic laser light scattering method.

◎ Other Properties: Izod Impact is ASTM D256, Tensile Strength is ASTM D638, Fluidity is ASTM D1238, Heat Deflection Temperature (HDT) is ASTM D648, and Surface Glossiness is It was measured by ASTM D523 method.

EXAMPLE

(A) Preparation of Graft ABS Polymer

㉠ Preparation of small-diameter rubber latex: polymerization reactor in which nitrogen is injected to remove oxygen, 100 parts by weight of ion-exchanged water, 100 parts by weight of 1,3-butadiene, 1.2 parts by weight of potassium rosin salt as an emulsifier, potassium oleate 1.5 parts by weight of salt, 0.1 parts by weight of sodium carbonate (Na ₂ CO ₃ ) as an electrolyte, 0.5 parts by weight of potassium hydrogen carbonate (KHCO ₃ ), and 0.3 parts by weight of tertiary dodecyl mercaptan (TDDM) as a molecular weight modifier were added in a batch. After adjusting to 55 ° C, 0.3 parts by weight of potassium persulfate as an initiator was administered and reacted for 10 hours. After the reaction, 0.05 parts by weight of tertiary dodecyl mercaptan was further administered to increase the reaction temperature to 65 ° C., and then reacted for 8 hours to prepare a small diameter rubber latex. The rubber latex prepared had a particle diameter of 1000 mm, a gel content of 90%, and an swelling index of 18.

제조 Preparation of large-diameter rubber latex: 100 parts by weight of the small-diameter rubber latex prepared in ㉠ was added to the reaction tank, and 3.0 parts by weight of a 7% acetic acid aqueous solution was slowly added for 1 hour while stirring at 10 rpm at a temperature of 30 ° C., followed by stirring. A large diameter conjugated diene rubber latex was prepared by fusing the small diameter rubber latex by stopping and standing for 30 minutes. The particle diameter of the prepared large-diameter rubber latex was 3100 mm 3, the gel content was 90% and the swelling index was 17.

㉢ Grafting process: 50 parts by weight of large diameter rubber latex prepared by 기에, 65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosin emulsifier, and 0.1 parts by weight of ethylenediaminetetraacetate , 0.005 parts by weight of ferrous sulfate and 0.23 parts by weight of formaldehyde sodium sulfoxylate were collectively administered, and the temperature was raised to 70 ° C. And 50 parts by weight of ion-exchanged water, 0.65 parts by weight of potassium rosinate, 35 parts by weight of styrene, 15 parts by weight of acrylonitrile, 0.4 parts by weight of t-dodecyl mercaptan, and 0.4 parts by weight of diisopropylene hydroperoxide. After the continuous dosing for hours, the temperature was raised to 80 ℃ and aged for 1 hour again to terminate the reaction to prepare a graft ABS polymer. The polymerization conversion rate of the prepared graft ABS polymer was 97.5%, the solid coagulum was 0.2% and the graft rate was 37%. The graft ABS polymer was solidified with an aqueous sulfuric acid solution and washed to obtain a powder.

(B) Preparation of heat resistant copolymer

70 parts by weight of α-methylstyrene, 30 parts by weight of acrylonitrile, 15 parts by weight of ion-exchanged water, and 0.20 parts by weight of dietary dodecyl mercaptan, which is a molecular weight control agent, were added to the reactor, followed by reaction for 4 hours. At this time, the reaction temperature was maintained at 65 ° C. The polymer solution discharged after the reaction was heated in a preheating tank and the unreacted monomer was volatilized in a volatilization tank to maintain the temperature of the polymer at 210 ° C., thereby processing the copolymer resin into pellets using a polymer transfer pump extruder.

(C) Preparation of Matte Filler Acrylonitrile Polymer

Batt (B MAT, GE), an acrylonitrile resin containing no butadiene, was used as a matte filler acrylonitrile polymer. The product was yellow powder.

(D) Preparation of Matte Filler Styreneacrylonitrile Polymer

44 weight part of styrene which is aromatic vinyl type, 30 weight part of (alpha) -methylstyrene, 10 parts by weight of acrylonitrile, 10 parts by weight of methacrylonitrile, which is a vinyl cyan compound, 6 parts by weight of methacrylic acid as an α, β-unsaturated carboxylic acid, 0.1 part by weight of cumene hydroperoxide as an initiator, 0.1 part by weight of hydroperoxide and 0.2 part by weight of t-dodecyl mercaptan as a molecular weight regulator, alkylbenzenesulfonic acid as an emulsifier After mixing 2 parts by weight of salt and 0.1 part by weight of ferrous sulfate as an oxidation-reduction catalyst, the mixture was reacted for 4 hours while continuously introducing the mixture into the reactor, and the reaction temperature was maintained at 70 ° C. After completion of the reaction, the mixture was agglomerated with calcium chloride, washed and dried to prepare a styrene acrylonitrile polymer in powder form.

(E) kneading process

38 parts by weight of the graft ABS polymer prepared by (A), 52 parts by weight of the heat-resistant copolymer prepared by (B) (3) parts of the matte filler prepared by (C) matte 5 parts by weight of filler, 0.8 parts by weight of N'N-Ethylene bis Stearamide (LPEB, precursor chemical) which is a stearamide-based lubricant, and IAL 1076 (IR1076, CIBA GEIGY Co., Ltd.) as an antioxidant After mixing 0.3 parts by weight, pellets were prepared by a twin screw extruder at a temperature of 230 ° C., specimens were prepared from the prepared pellets, and physical properties thereof were measured. The results are shown in Table 2 below.

[Comparative Examples 1 to 3]

Except that the composition and the composition ratio as shown in Table 1 below to prepare a specimen in the same manner as in Example to measure the physical properties, the results are shown in Table 2.

Division (weight part) Example Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Graft ABS Polymer 38 30 38 30 (B) heat resistant polymer 62 70 62 70 (C) matte filler 3 - 6 3 (D) matte filler 5 - - - Matte mineral - - - 1.0 Lubricant 0.8 1.0 0.8 0.8 Antioxidant 0.3 0.3 0.3 0.3

division Example Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact strength 1/4 " 23.2 22.7 21.2 19.8 1/8 " 26.2 26.6 25.2 23.1 Tensile Strength (kg / cm ² ) 440 480 460 470 Fluidity (g / 10min) 5.2 7.6 6.2 6.8 Heat Deflection Temperature (1/4 ", ℃) 100.0 98.9 96.8 97.3 Glossiness (45 °) 10.5 90.0 21.5 37.5

As can be seen in Table 2, the heat resistance (heat deformation temperature) and glossiness of the examples according to the present invention were superior to the comparative examples. In addition, the tensile strength and inducibility show that the examples are slightly lower than those of the comparative examples, but the physical properties of the matte thermoplastic resin that can be used in general are maintained.

The matte thermoplastic resin composition according to the present invention is prepared by adding a matte filler to the impact resistance and heat resistant ABS resin and has excellent impact resistance, heat resistance, matteness, and other physical properties.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (7)

a) 10 to 40 parts by weight of the graft ABS copolymer; b) 60 to 90 parts by weight of the heat resistant copolymer; c) 0.1 to 10 parts by weight of acrylonitrile polymer for matte fillers; And d) 5 to 20 parts by weight of styrene acrylonitrile polymer for matte filler Matte thermoplastic resin composition comprising a. The method of claim 1, The matte thermoplastic resin is 0.5 to 5.0 parts by weight of the inorganic material for the matte, Matte thermoplastic resin composition, characterized in that it further comprises 0.2 to 1.5 parts by weight of lubricant and 0.1 to 1.0 part by weight of antioxidant. The method of claim 1, The graft ABS polymer is 40 to 70 parts by weight of a conjugated diene rubber latex, 15 to 40 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyanide compound, 0.2 to 0.6 parts by weight of an emulsifier, and 0.2 to 0.6 parts by weight of a molecular weight regulator. Part, and 0.1 to 0.5 parts by weight of the polymerization initiator comprises a matt thermoplastic resin composition. The method of claim 1, The heat-resistant copolymer is a matte thermoplastic resin comprising 50 to 80 parts by weight of α-methylstyrene (AMS), 20 to 50 parts by weight of acrylonitrile (AN), 26 to 30 parts by weight of toluene and a molecular weight modifier. Composition. The method of claim 1, The styrene acrylonitrile polymer for the matte filler is 20 to 77 parts by weight of an aromatic vinyl compound, 5 to 20 parts by weight of a vinyl cyanide compound, 0.1 to 6 parts by weight of α, β-unsaturated carboxylic acid, 0.1 to 1 weight of a molecular weight regulator Part, 0.1 to 2 parts by weight of an emulsifier, 0.1 to 0.2 parts by weight of a polymerization initiator, 0.1 to 0.5 parts by weight of an oxidation-reduction catalyst comprising a matte thermoplastic resin composition. The method of claim 2, Matte thermoplastic resin composition, characterized in that the inorganic material for the matte is zeolite. The method of claim 2, Matte thermoplastic resin composition, characterized in that the lubricant is a bis-steramide (bis-steramide).