KR20080036790A - Low-gloss thermoplastic resin composition having excellent impact resistance and heat resistance - Google Patents

Abstract

A low gloss thermoplastic resin composition is provided to improve impact resistance and heat resistance and to reduce gloss by using a maleimide-based copolymer as a heat resistant copolymer. A thermoplastic resin composition comprises 30-70 parts by weight of an ASA (acrylate/styrene/acrylonitrile) copolymer; 5-20 parts by weight of a heat resistant copolymer; 0.1-10 parts by weight of an acrylonitrile copolymer for a low gloss filler; and 10-35 parts by weight of a SAN copolymer. Preferably the heat resistant copolymer is prepared by copolymerizing 70 wt% or less of an aromatic vinyl compound, 20 wt% or less of a vinyl cyano compound, and 10-60 wt% of a maleimide-based compound.

Description

LOW-GLOSS THERMOPLASTIC RESIN COMPOSITION HAVING EXCELLENT IMPACT RESISTANCE AND HEAT RESISTANCE}

The present invention relates to a low gloss thermoplastic resin composition, and more particularly, to a thermoplastic resin composition excellent in impact resistance and heat resistance and at the same time excellent in low gloss.

ABS (acrylonitrile / butadiene / styrene), MBS (methyl methacrylate / butadiene / styrene), ASA (acrylate / styrene / acrylonitrile), AIM (acrylic impact modifier) resin produced through emulsion polymerization It has excellent physical properties such as impact resistance, rigidity and fluidity, and is widely used as a modifier of various plastics.

In particular, ABS resin has been widely used in materials such as monitor housings, game machine housings, home appliances, office equipment, automobile lamp housings, etc., because of excellent dimensional stability, processability, and chemical resistance. In addition, in recent years, a lot of researches have been conducted to provide heat resistance to ABS resin having excellent impact resistance, chemical resistance, and processability as the necessity of automobile weight reduction, and to use it as an automotive interior material.

However, ABS resin has excellent impact resistance at low temperatures, but has a problem of low weatherability and aging resistance.

Therefore, in order to manufacture a product having not only high impact strength but also weather resistance and aging resistance, there should be no ethylenically unsaturated polymer in the resin, and ASA resin using a crosslinked alkyl acrylate rubber polymer is suitable. In order to replace ASA resins, research is underway.

In addition, as users' emotional quality level increases in recent years, the demand for low gloss resins is increasing in order to create a more elegant atmosphere. Also, due to environmental problems, low gloss resins or padding processes are omitted and low gloss resins are used. The trend is to use it directly.

The main principle applied to produce such a low gloss resin is to adjust the smoothness of the surface of the resin to be larger than the visible light region to scatter incident light to exert a low light effect. As a specific method, there is a method of improving the ASA resin to produce and use 1 µm or more large-diameter rubber particles. However, the resin produced by this method is low in gloss effect and poor in impact strength and heat resistance. Another method is to add a matte filler having a particle size of 5 μm or more to the resin. The resin produced by this method shows excellent moldability, but low glossiness, and particularly, the impact strength is severely reduced.

Conventional low gloss resin manufacturing method has a method of embossing the resin surface or coating with a low gloss material, but increases the processing cost, there is a problem that the low gloss effect is lowered by abrasion during processing.

On the other hand, conventionally a method for imparting heat resistance to the resin is a method for preparing α-methylstyrene-acrylonitrile heat-resistant copolymer and kneading with the resin, US Patent Nos. 3,010,936 and 4,659,790 A method of partially or totally replacing styrene with α-methylstyrene in preparation is disclosed. However, the resin produced by this method has a problem that the heat resistance is excellent, the impact strength is severely lowered, and the colorability is lowered due to the color of the heat resistant copolymer itself. In addition, a low gloss filler is added in order to exhibit low glossiness, which is also required to add a large amount in order to exhibit low glossiness, resulting in a drop in impact strength and an increase in production cost.

Therefore, there is a demand for a resin that satisfies the existing impact resistance and heat resistance and imparts low gloss characteristics.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a thermoplastic resin composition which is excellent in impact resistance and heat resistance and at the same time excellent in low gloss.

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

In order to achieve the above object, the present invention

(a) 30 to 70 parts by weight of the ASA copolymer;

(b) 5 to 20 parts by weight of the heat resistant copolymer;

(c) 0.1 to 10 parts by weight of acrylonitrile copolymer for low gloss filler; And

It provides a low-gloss thermoplastic resin composition comprising (d) 10 to 35 parts by weight of the SAN copolymer.

Hereinafter, the present invention will be described in detail.

The inventors of the present invention, when using a maleimide-based copolymer as a heat-resistant copolymer with ASA resin, the maleimide-based heat-resistant copolymer is excellent in heat resistance can impart heat resistance even at a small amount during kneading, so the impact strength is not severely reduced In addition, according to the content of the maleimide, there is less degradation of the kneading property between the matrix and the maleimide-based resin, confirming that the maleimide-based resin can form a domain between the matrix to obtain a low gloss effect, based on this, to complete the present invention Was done.

The low gloss thermoplastic resin composition of the present invention comprises an ASA copolymer, a heat resistant copolymer, an acrylonitrile copolymer for a low gloss filler and a SAN copolymer.

(a) ASA copolymer

The ASA copolymer of the present invention comprises (i) a polymer seed, (ii) a crosslinked alkylacrylate core, and (iii) a graft shell.

(Iii) 5-25 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, an alkyl methacrylate compound, and an alkyl acrylate compound, 0.05 to 0.3 part by weight of an electrolyte, and 0.01 to 0.01 crosslinking agent. 0.5 parts by weight, a grafting agent 0.01 to 0.5 parts by weight, a surfactant 0.05 to 4 parts by weight, a polymerization initiator 0.01 to 0.3 parts by weight, and a seed prepared by polymerizing distilled water.

It is preferable to use a styrene derivative as the aromatic vinyl compound, and specifically, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, or a substituent thereof may be used.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile or ethacrylonitrile may be used.

As the alkyl methacrylate compound, alkyl methacrylate having 1 to 4 carbon atoms of the alkyl moiety may be used alone or in combination of two or more thereof. Preferably, methyl methacrylate having 1 to 2 carbon atoms of the alkyl moiety or Ethyl methacrylate etc. are used.

As the alkyl acrylate compound, alkyl acrylates having 1 to 4 carbon atoms of the alkyl moiety may be used alone or in combination of two or more thereof. Preferably, alkyl acrylates having 4 to 8 carbon atoms of the alkyl moiety are more preferred. Is using butyl acrylate or ethylhexyl acrylate.

As the electrolyte, NaHCO ₃ , Na ₂ S ₂ O ₇ or K ₂ CO ₃ may be used, and preferably NaHCO ₃ is used.

The crosslinking agent may be ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl Glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol methane triacrylate, and the like.

As the grafting agent, aryl methacrylate (AMA), triaryl isocyanurate (TAIC), triaryl amine (TAA) or diaryl amine (DAA) may be used.

The surfactant is not particularly limited, but the fatty acid soap system represented by oleic acid, stearic acid, lauric acid, sodium or potassium salts of mixed fatty acids, or the rosin acid soap system represented by abietin acid salts, etc. It can be used individually or in mixture of 2 or more types.

As the polymerization initiator, an inorganic or organic peroxide initiator may be used. Specifically, a water-soluble initiator such as potassium persulfate, sodium persulfate, ammonium persulfate, or an oil-soluble initiator such as cumene hydroperoxide or benzoyl peroxide may be used. have.

An activator may be used to promote the initiation reaction of the peroxide together with the polymerization initiator, and the activator may be sodium formaldehyde sulfoxylate, sodium ethylene diamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate or arbor. Sodium sulfate or the like may be used alone or in combination of two or more thereof. Preferably, 0.001 to 0.02 parts by weight of sodium formaldehyde, 0.001 to 0.02 parts by weight of sodium ethylenediamine tetraacetate, and 0.0001 to 0.002 parts by weight of ferrous sulfate .

Such components may be polymerized by emulsion polymerization alone, or by mixing emulsion polymerization and emulsion-free polymerization. In this case, the monomer injection method may be a single injection or a continuous injection.

The prepared polymer seed preferably has an average particle diameter of 150 to 400 nm.

(Ii) the crosslinked alkylacrylate core is 20 to 70 parts by weight of the alkylacrylate compound, 0.05 to 0.3 parts by weight of the electrolyte, 0.1 to 1 part by weight of the crosslinking agent, and 0.05 to 0.5 parts by weight of the grafting agent in the presence of the prepared (iii) polymer seed. It is a core prepared by polymerizing a surfactant, 0.05 to 4 parts by weight of surfactant, 0.01 to 0.3 parts by weight of polymerization initiator, and distilled water.

The alkyl acrylate compound, the electrolyte, the crosslinking agent, the grafting agent, and the surfactant may be the same as those used in the preparation of the (i) polymer seed.

In addition, the polymerization method can use the same method as used at the time of manufacture of said (iii) polymer seed.

The prepared alkyl acrylate core is a crosslinked alkyl acrylate rubber polymer having a free transition temperature of less than 0 ° C., more preferably a glass transition temperature of −20 to −70 ° C.

The crosslinked alkylacrylate core preferably has an average particle diameter of 400 to 800 nm, more preferably 600 to 800 nm. When the average particle diameter is 400 to 800 nm, there is an effect of improving the low glossiness of the thermoplastic resin composition.

(Iii) The graft shell comprises 10 to 50 parts by weight of aromatic vinyl compound, 5 to 25 parts by weight of vinyl cyan compound, and 0.05 to surfactant in the presence of 30 to 80 parts by weight (based on solids) of the prepared (ii) alkylacrylate core. 4 weight part, 0.01-0.3 weight part of polymerization initiators, and the shell manufactured by superposing | polymerizing distilled water.

As the third monomer together with the aromatic vinyl compound and the vinyl cyan compound, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-phenylmaleimide, methyl methacrylate, methyl acrylate In addition, a small amount of vinyl monomers such as butyl acrylate, acrylic acid, or maleic anhydride can be used.

The said aromatic vinyl compound, a vinyl cyan compound, and a polymerization initiator can use the same thing as what was used at the time of manufacture of said (iii) polymer seed.

As the surfactant, the same as those used in the preparation of the polymer seed (i) may be used, and derivatives of alkyl sulfo succinate metal salts having a pH of 3 to 9 with 12 to 18 carbon atoms and alkyl sulfates having 12 to 20 carbon atoms Esters, derivatives of sulfonic acid metal salts, and the like.

Examples of the derivative of the alkyl sulfo succinate metal salt having 12 to 18 carbon atoms include dicyclohexyl sulfo succinate, dihexyl sulfo succinate, di 2-ethyl hexyl sulfo succinate sodium salt and di 2-ethylhexyl sulfo succinate potassium salt. , Dioctyl sulfo succinate sodium salt or dioctyl sulfo succinate potassium salt and the like can be used.

In addition, examples of the alkyl sulfate ester or sulfonic acid metal salt having 12 to 20 carbon atoms include sodium lauryl sulfate, sodium dodecyl sulfate, sodium dodecyl benzene sulfate, sodium octadecyl sulfate, sodium oleic sulfate, and potassium dodecyl sulfate. Or potassium octadecyl sulfate and the like.

The polymerization method is preferably an emulsion polymerization method, and the monomer input method is preferably a continuous injection method. When the monomer mixture containing the surfactant is added at the same time during the manufacture of the graft shell, the pH of the polymerization system is raised temporarily, so that the grafting is difficult and the stability of the particles is lowered, so that the internal structure of the particles is not uniform. The method is preferred.

The ASA copolymer prepared as described above, comprising (i) a polymer seed, (ii) a crosslinked alkylacrylate core, and (iii) a graft shell, is in a latex state and has a total solid content of at least 35% by weight. Stable. The ASA copolymer latex preferably has a pH of 8 to 11, more preferably 9 to 10.5.

The latex ASA copolymer is prepared as a powder by flocculation, ripening, dehydration, washing, and drying with a well known flocculant. As the flocculant, sulfuric acid, MgSO ₄ , CaCl ₂ , Al ₂ (SO ₄ ) ₃ , and the like may be used, and CaCl ₂ is preferably used. The ASA copolymer latex is subjected to atmospheric aggregation at 80 ° C. using CaCl ₂ aqueous solution, then aged at 95 ° C., dehydrated and washed, and dried in hot air at 90 ° C. for 30 minutes to prepare a powder.

The ASA copolymer is preferably included in the low-gloss thermoplastic resin composition of the present invention in 30 to 70 parts by weight.

(b) heat resistant copolymer

The heat resistant copolymer of the present invention is a copolymer prepared by polymerizing up to 70 parts by weight of aromatic vinyl compounds, up to 20 parts by weight of vinyl cyan compounds, and 10 to 60 parts by weight of maleimide compounds based on 100 parts by weight of the total content.

As said aromatic vinyl compound, styrene, (alpha) -methylstyrene, p-methylstyrene, vinyl toluene, etc. can be used, Preferably styrene is used.

Acrylonitrile or methacrylonitrile may be used as the vinyl cyan compound.

Although the kind is not specifically limited as said maleimide type compound, It is preferable to use N-substituted maleimide defined by following General formula (1). Specifically, N-cyclohexyl maleimide, N-phenylmaleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, Nt-butyl maleimide, N-lauryl maleimide, N- It is preferable to use benzyl maleimide or N-tribromophenyl maleimide and the like, and more preferably N-cyclohexyl maleimide or N-phenyl in consideration of transparency, low colorability, heat resistance, etc. of the heat-resistant copolymer to be produced. This is to use maleimide.

In Formula 1, R is hydrogen or an alkyl group of 1 to 15 oxygen, cycloalkyl group, aryl group.

The maleimide compound is preferably used in 10 to 60 parts by weight based on 100 parts by weight of the heat resistant copolymer. When the content is 10 to 60 parts by weight, while ensuring the polymerization stability, there is an effect that easy color control and heat resistance increase.

Such components may be polymerized by suspension polymerization or bulk polymerization, and the suspension polymerization method is preferable in terms of color of the heat resistant copolymer.

It is preferable that the produced heat resistant copolymer has a weight average molecular weight of 60,000 to 300,000, and at this time, the molecular weight may be adjusted using a molecular weight regulator. When the weight average molecular weight is 60,000 to 300,000, the fluidity is good and the workability is improved, and the impact strength of the final thermoplastic resin is improved. As the molecular weight regulator, mercaptans such as n-octyl mercaptan, t-dodecyl mercaptan or n-dodecyl mercaptan can be used.

In addition, the heat resistant copolymer preferably has a glass transition temperature of 130 to 200 ℃.

The heat resistant copolymer is preferably contained in 5 to 20 parts by weight of the low-gloss thermoplastic resin composition of the present invention.

(c) Acrylonitrile Copolymers for Low Gloss Fillers

The acrylonitrile copolymer of the present invention is used as a low gloss filler and is a copolymer prepared by adding a diepoxide, which is an epoxide-based electrolyte, to the acrylonitrile monomer and polymerizing it.

The acrylonitrile copolymer may be one containing at least 5 parts by weight of an unsaturated nitrile monomer such as acrylonitrile, methacrylonitrile or fumaronitrile based on 100 parts by weight of the total content.

Such components may be polymerized by emulsion polymerization, block polymerization, suspension polymerization, block-suspension polymerization or solution polymerization.

The acrylonitrile copolymer is preferably included in the low-gloss thermoplastic resin composition of the present invention 0.1 to 10 parts by weight.

(d) SAN copolymer

The SAN copolymer of the present invention is composed of a hard polymer-forming monomer having a glass transition temperature of at least 60 ° C. or higher. A styrene-based monomer or an acrylonitrile-based monomer includes a vinyl cyan compound and a compound including units derived from methyl methacrylate. It is a copolymer manufactured by mixing single or 2 types or more of compounds which can form a carbonate polymer.

The SAN copolymer has an acrylonitrile content of 24 to 28 parts by weight, and preferably a weight average molecular weight of 80,000 to 120,000.

The SAN copolymer is preferably included in 10 to 35 parts by weight of the low-gloss thermoplastic resin composition of the present invention.

The low-gloss thermoplastic resin composition comprising the above components (a) to (d) is a dye, pigment, lubricant, antioxidant, ultraviolet stabilizer, thermal stabilizer, reinforcing agent, filler, flame retardant, foaming agent, It may further include additives such as a plasticizer or a low gloss agent.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

(a) Preparation of ASA Copolymer

(Iii) polymer seed

5 parts by weight of butyl acrylate, 0.15 parts by weight of NaHCO ₃ , 0.2 parts by weight of potassium rosin salt, ethylene glycol dimeth, based on 100 parts by weight of the total monomers used to prepare the ASA copolymer in a nitrogen-substituted polymerization reactor (autoclave). 0.05 weight part of acrylate, 0.025 weight part of aryl methacrylates, and 60 weight part of distilled water were collectively administered, and it heated up to 70 degreeC, and 0.05 weight part of potassium persulfate was thrown in, and reaction was started. After the reaction was maintained for 1 hour at 70 ℃ to prepare a polymer seed latex.

The average particle diameter of the prepared seed latex was 253 nm.

(Ii) Alkylacrylate Core Preparation

In the presence of the prepared seed latex, 45 parts by weight of butyl acrylate, 0.15 parts by weight of NaHCO ₃ , 0.5 parts by weight of potassium rosin acid salt and 0.5 parts by weight of potassium oleate salt, 0.3 parts by weight of ethylene glycol dimethacrylate, aryl methacrylate A mixture of 0.15 parts by weight, 40 parts by weight of distilled water and 0.05 parts by weight of potassium persulfate was continuously added at 70 ° C. for 3 hours, and further polymerized for 1 hour after the end of the charge to prepare an alkylacrylate core latex.

The average particle diameter of the prepared core latex was 623 nm.

(Iii) graft shell manufacturing

37.5 parts by weight of styrene, 12.5 parts by weight of acrylonitrile, 1.5 parts by weight of potassium rosin, potassium in the presence of 50 parts by weight of alkylacrylate core latex (based on solids), based on 100 parts by weight of the total monomers used to prepare the ASA copolymer. The polymerization reaction was carried out while continuously adding a mixture of 0.05 parts by weight of persulfate, 0.1 parts by weight of tertiary dodecyl mercaptan and 60 parts by weight of distilled water at 70 ° C. for 4 hours. In addition, in order to increase the polymerization conversion rate, the temperature was raised to 78 ° C. after completion of the addition, and further reacted for 1 hour, and cooled to 60 ° C. The total solid content in the final ASA copolymer latex obtained after completion of the reaction was 35%, the polymerization conversion was 99.5%.

The obtained ASA copolymer latex was subjected to atmospheric aggregation at 80 ° C. using CaCl ₂ aqueous solution, then aged at 95 ° C., dehydrated and washed, and dried for 30 minutes by hot air at 90 ° C. to obtain ASA copolymer powder particles. Obtained.

(b1) Preparation of heat resistant copolymer

49 parts by weight of styrene, 6 parts by weight of acrylonitrile, 0.1 part by weight of initiator 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 0.2 part by weight of t-butyl peroxybenzoate, 0.15 parts by weight of n-octyl mercaptan as a molecular weight regulator and 0.05 parts by weight of 2,6-di-t-butyl-p-cresol as an antioxidant were prepared. 30% of the mixed solution was added to a reactor containing 100 parts by weight of distilled water and 2 parts by weight of 10% sodium sulfate solution, followed by stirring for 20 minutes. Thereafter, the reactor was heated to 100 ° C. for 1 hour, maintained for 20 minutes, and 2.5 parts by weight of acrylic acid and 2% 2-ethylhexyl acrylate copolymer solution were added as a dispersant. From 25 minutes at 100 ℃ was dissolved 45 parts by weight of N- phenylmaleimide in 70% of the mixed solution prepared above was continuously added for 3 hours 30 minutes. After the continuous injection was completed, it was maintained for 30 minutes, the temperature was raised to 120 ℃ for 1 hour and maintained for 3 hours, and then cooled to 40 ℃ for 1 hour. The prepared product was dehydrated and dried to obtain a final heat resistant copolymer.

The prepared heat resistant copolymer had a weight average molecular weight of 150,000 and a glass transition temperature of 175 ° C.

(b2) Preparation of heat resistant copolymer

(B1) Heat resistance except that in the preparation of the heat resistant copolymer (35 parts by weight instead of 49 parts by weight of styrene, 5 parts by weight instead of 6 parts by weight of acrylonitrile, 60 parts by weight instead of 45 parts by weight of phenylmaleimide) It carried out by the same method as the preparation of a copolymer.

The prepared heat resistant copolymer had a weight average molecular weight of 160,000 and a glass transition temperature of 197 ° C.

(c) Acrylonitrile copolymer for low gloss filler

As the acrylonitrile copolymer for the low gloss filler, an acrylonitrile resin matrix (B MAT, manufactured by GE), which is a light yellow powder containing no butadiene, was used.

(d) SAN copolymer

As the SAN copolymer, a styrene-acrylonitrile copolymer (81HR, manufactured by LG Chemical) was used.

<Low gloss thermoplastic resin composition preparation>

Example 1

40 parts by weight of the prepared (a) ASA copolymer, (b1) 10 parts by weight of the heat resistant copolymer, (c) 5 parts by weight of the acrylonitrile copolymer, and (d) 50 parts by weight of the SAN copolymer were added thereto. After adding 1 part by weight of lubricant and 0.5 part by weight of antioxidant, the resultant was prepared in pellet form using a 40 pie extrusion kneader at a cylinder temperature of 220 ° C., and the pellet was injected to prepare a physical specimen.

Example 2, Comparative Examples 1 to 3

In Example 1, except that (a) to (d) component was added in the composition shown in Table 1 below was carried out in the same manner as in Example 1.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (a) ASA copolymer 40 40 40 40 40 (b) heat resistant copolymer b1 10 - - - 30 b2 - 7 - - - (c) acrylonitrile copolymer 5 5 5 10 5 (d) SAN copolymer 50 53 60 60 30 Lubricant One One One One One Antioxidant 0.5 0.5 0.5 0.5 0.5

[Test Example]

The physical properties of the thermoplastic resin composition specimens prepared in Examples 1 to 2 and Comparative Examples 1 to 3 were measured by the following method, and the results are shown in Table 2 below.

* Impact strength (1/4 "notched at 23 ℃, kg · cm / ㎝)-measured according to ASTM D256.

* Tensile Strength (kg / cm ² )-It was measured according to ASTM D638.

* Flowability (g / cm ² )-measured according to ASTM D1238.

* Heat deflection temperature (1/4 ", ℃)-measured according to ASTM D648.

* Glossiness (45 °)-measured according to ASTM D523.

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Impact Strength (1/4 ", kg · cm / cm) 10.3 10.7 10.8 7.4 5.7 Tensile Strength (㎏ / ㎝ ² ) 452 447 445 473 482 Fluidity (g / cm ² ) 15.7 15.9 20.3 19.7 8.3 Heat Deflection Temperature (1/4 ", ℃) 91 90 85 85 98 Glossiness (45 °) 12 14 20 13 12

As shown in Table 1, it was confirmed that the low-gloss thermoplastic resin composition of Examples 1 to 2 prepared according to the present invention was excellent in impact resistance and heat resistance, but excellent in the low-gloss effect.

On the other hand, Comparative Example 1, which does not include a heat-resistant copolymer, has a low heat resistance, a glossiness is increased, and a low gloss property is deteriorated. In Comparative Example 2, which includes an acrylonitrile copolymer for a low gloss filler in an excessive amount, Including the low gloss effect was improved, but the impact strength was lowered. In addition, Comparative Example 3 containing an excessive amount of the heat resistant copolymer was very excellent in heat resistance, it was confirmed that the fluidity and impact resistance is reduced.

As described above, according to the present invention, there is an effect of providing a thermoplastic resin composition excellent in impact resistance and heat resistance and at the same time excellent in low gloss.

Claims (12)

(a) 30 to 70 parts by weight of the ASA copolymer; (b) 5 to 20 parts by weight of the heat resistant copolymer; (c) 0.1 to 10 parts by weight of acrylonitrile copolymer for low gloss filler; And (d) 10 to 35 parts by weight of the SAN copolymer; Low gloss thermoplastic resin composition. The method of claim 1, The (a) ASA copolymer is (Iii) 5 to 25 parts by weight of at least one monomer selected from the group consisting of an aromatic vinyl compound, a vinyl cyan compound, an alkyl methacrylate compound, and an alkyl acrylate compound, 0.05 to 0.3 part by weight of an electrolyte, and 0.01 to 0.5 weight by weight of a crosslinking agent. Part, a polymer seed prepared by polymerizing 0.01 to 0.5 parts by weight of a grafting agent, 0.05 to 4 parts by weight of a surfactant, 0.01 to 0.3 parts by weight of a polymerization initiator, and distilled water;  (Ii) 20 to 70 parts by weight of an alkylacrylate compound, 0.05 to 0.3 parts by weight of electrolyte, 0.1 to 1 part by weight of crosslinking agent, 0.05 to 0.5 part by weight of grafting agent, and 0.05 to 4 parts by weight of surfactant in the presence of the polymer seed (iii) Parts, 0.01 to 0.3 parts by weight of a polymerization initiator, and a crosslinked alkylacrylate core prepared by polymerizing distilled water; And (Iii) 10 to 50 parts by weight of an aromatic vinyl compound, 5 to 25 parts by weight of a vinyl cyan compound, 0.05 to 4 parts by weight of a surfactant, and polymerization in the presence of 30 to 80 parts by weight (based on solids) of the alkylacrylate core (ii). 0.01 to 0.3 parts by weight of initiator, and graft shell prepared by polymerizing distilled water Low gloss thermoplastic resin composition. The method of claim 2, (Iii) the polymer seed is characterized in that the average particle diameter is 150 to 400 nm Low gloss thermoplastic resin composition. The method of claim 2, The crosslinked alkylacrylate core (ii) has a glass transition temperature of less than 0 ° C., and an average particle diameter of 400 to 800 nm. Low gloss thermoplastic resin composition. The method according to claim 1 or 2, The ASA copolymer is characterized in that the pH is 8 to 11 Low gloss thermoplastic resin composition. The method of claim 1, The (b) heat-resistant copolymer is prepared by polymerizing up to 70 parts by weight of aromatic vinyl compounds, up to 20 parts by weight of vinyl cyan compounds, and 10 to 60 parts by weight of maleimide compounds based on 100 parts by weight of the total content. Low gloss thermoplastic resin composition. The method of claim 6, The maleimide compound is N-cyclohexyl maleimide, N-phenyl maleimide, N-methyl maleimide, N-ethyl maleimide, N-isopropyl maleimide, Nt-butyl maleimide, N-lauryl maleimide , N-benzyl maleimide and N-tribromophenyl maleimide, characterized in that at least one member selected from the group consisting of Low gloss thermoplastic resin composition. The method according to claim 1 or 6, (B) the heat resistant copolymer has a weight average molecular weight of 60,000 to 300,000, the glass transition temperature is 130 to 200 ℃ Low gloss thermoplastic resin composition. The method of claim 1, The acrylonitrile-based copolymer for the low-gloss filler (c) is prepared by adding and polymerizing a diepoxide, which is an epoxide-based electrolyte, to an acrylonitrile monomer. Low gloss thermoplastic resin composition. The method of claim 1, The (d) SAN copolymer is prepared by polymerizing a hard polymer forming monomer having a glass transition temperature of at least 60 ℃. Low gloss thermoplastic resin composition. The method according to claim 1 or 10, The (d) SAN copolymer has an acrylonitrile content of 24 to 28 parts by weight and a weight average molecular weight of 80,000 to 120,000, characterized in that Low gloss thermoplastic resin composition. The method of claim 1, The low gloss thermoplastic resin composition further comprises at least one additive selected from the group consisting of dyes, pigments, lubricants, antioxidants, ultraviolet stabilizers, heat stabilizers, reinforcing agents, fillers, flame retardants, foaming agents, plasticizers, and low gloss agents. doing Low gloss thermoplastic resin composition.