KR20110065848A - Low Gloss Thermoplastic Composition - Google Patents

Abstract

PURPOSE: A low-gloss thermoplastic resin composition is provided to ensure excellent weather resistance capable of maintaining mechanical properties even if the composition is exposed to the outside for a long time. CONSTITUTION: A low-gloss thermoplastic resin composition comprises 30-70 weight% of polycarbonate, 20-50 weight% of polyester, 1-15 weight% of impact reinforcing agents, 1-5 weight% of polyalkylmethacrylate, 0.5-3 weight% of antioxidants, 0.5-1.5 weight% of ultraviolet-absorbing agents, and 0.05-0.15 weight% of photostabilizers. The polycarbonate is an aromatic polycarbonate having viscosity average molecular weight of 21,000-30,000. The polyester is polyalkylene terephthalate.

Description

Low-gloss thermoplastic resin composition {LOW-GLOSS THERMOPLASTIC RESIN COMPOSITION}

The present invention relates to a resin composition, and more particularly to a low-gloss thermoplastic resin composition with improved weather resistance.

Polyester resin is excellent in mechanical strength, chemical resistance, electrical insulation, moldability and wear resistance, and is mixed with various additives such as glass fiber, inorganic filler, flame retardant, impact modifier, or other resins to be used in electrical and electronic parts, automobile parts, general industrial materials, It is used for office products and connector materials.

Polycarbonate resin is a thermoplastic resin with a glass transition temperature of around 150 ° C. It is used for automobile parts, electrical and electronic parts, or building materials because of its excellent mechanical properties, tensile strength and impact strength, numerical stability, heat resistance, and optical transparency. The field is expanding.

However, the polyester resin is difficult to use as a connector material around the automotive engine that requires high temperature heat resistance due to lack of heat resistance. In addition, polycarbonate resins have limited chemical resistance when used in contact with organic solvents, certain detergents, strong alkalis, certain fatty acids, oils and greases.

In order to supplement the above advantages and disadvantages, efforts have been made to blend the two resins and improve their properties. However, the resin composition exhibits high surface gloss, which may be an advantage of a plastic molded article, but may cause eye fatigue due to gloss in certain applications. In order to solve this problem and create a luxurious atmosphere, a low gloss surface is required for some applications. In particular, the automotive industry undergoes a coating process to reduce gloss and increase resistance to discoloration when exposed to ultraviolet light, which has problems of cost increase and environmental pollution.

On the other hand, in the case of the material not to be coated, physical properties and appearance defects due to discoloration generated during long-term exposure to external ultraviolet rays may occur.

In order to solve the above problems, the present invention provides a thermoplastic resin composition having excellent weatherability and low gloss while maintaining mechanical strength, impact resistance, and workability.

Low-gloss thermoplastic resin composition according to embodiments of the present invention, 30 to 70% by weight polycarbonate, 20 to 50% by weight polyester, 1 to 15% by weight impact modifier, 1 to 5% by weight polyalkyl meta Acrylate, 0.5 to 3 weight percent antioxidant, 0.5 to 1.5 weight percent ultraviolet absorber, and 0.05 to 0.15 weight percent light stabilizer.

The polycarbonate may be an aromatic polycarbonate having a viscosity average molecular weight of 21,000 to 30,000.

The polyester may be polyalkylene terephthalate.

The impact modifiers are methacrylonitrile-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES), acrylonitrile- Styrene-butyl acrylate (ASA), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene (SB), styrene-isoprene rubber , Ethylene-vinylacetate (EVA), ethylene-ethyl acrylate (EEA), ethylene-vinyl alcohol (EVOH) copolymer, silicone-acrylic rubber core and methyl methacrylate shell, polybutylene terephthalate It may include one or more selected from the group consisting of an elastomer, a polyethylene terephthalate elastomer and a nylon elastomer.

The polyalkyl methacrylate is polymerized using at least one crosslinking agent selected from divinylbenzene, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, and diethylene glycol dimethacrylate, and the polyalkyl methacrylate. The content of the crosslinking agent in the rate may be 0.1 to 20% by weight.

The polyalkyl methacrylate may be spherical particles having an average particle diameter of 1 to 15㎛.

The antioxidant may include one or more selected from phenolic compounds, phosphite compounds, and thioester compounds.

The ultraviolet absorber may include at least one selected from a benzotriazole compound, a hydroxyphenyl triazine compound, a pyrimidine compound, and a cyanoacrylate compound.

The light stabilizer may be a hindered amine compound.

The low gloss thermoplastic resin composition may further comprise 0.1 to 3% by weight of an ethylene copolymer.

The ethylene copolymer has a structure of Formula 1, and consists of 15 to 30% by weight of alkyl acrylate units, 5 to 12% by weight of glycidyl methacrylate units, and 58 to 80% by weight of ethylene units. Can be.

[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ may each independently represent a substituted or unsubstituted cyclic or chain hydrocarbon having 1 to 10 carbon atoms, R ₂ may include one or more non-carbon elements, , x, y and z may represent 2 to 30,000 as the average degree of polymerization, respectively. The non-carbon element may include sulfur (S), oxygen (O), and nitrogen (N).

The low gloss thermoplastic resin composition may further include a release agent.

The low gloss thermoplastic resin composition according to the embodiments of the present invention may have excellent weather resistance maintaining mechanical properties even when exposed to the outside for a long time. In addition, the low-gloss thermoplastic resin composition is excellent in impact resistance and molding processability can be applied to produce products such as door handles, roof rack cover.

Hereinafter, the present invention will be described in more detail with reference to the following examples. The objects, features and advantages of the present invention will be readily understood through the following examples. The invention is not limited to the embodiments described herein, but may be embodied in other forms. The embodiments introduced herein are provided so that the disclosure may be made thorough and complete, and the spirit of the present invention may be sufficiently delivered to those skilled in the art. Therefore, the present invention should not be limited by the following examples.

Low-gloss thermoplastic resin composition according to embodiments of the present invention, 30 to 70% by weight polycarbonate, 20 to 50% by weight polyester, 1 to 15% by weight impact modifier, 1 to 5% by weight polyalkyl meta Acrylate, 0.5 to 3 weight percent antioxidant, 0.5 to 1.5 weight percent ultraviolet absorber, and 0.05 to 0.15 weight percent light stabilizer. Description of each component of the said low gloss thermoplastic resin composition is as follows.

Polycarbonate

In the low-gloss thermoplastic resin composition according to the embodiments of the present invention, a polycarbonate resin that is commonly used may be used without particular limitation. The polycarbonate resin is prepared by, for example, reacting dihydroxy phenol and phosgen in the presence of a molecular weight regulator and a catalyst, or dihydroxy phenol and diphenyl carbonate. It can be prepared using the ester interchange reaction of the precursor obtained by), but is not limited thereto.

The polycarbonate may have a viscosity average molecular weight (Mv) of 21,000 to 30,000 measured in methylene chloride solution. If the average molecular weight is less than 21,000, the mechanical properties together with weather resistance may be lowered, and if the average molecular weight is more than 30,000, workability may be lowered due to an increase in melt viscosity.

The content of the polycarbonate in the low gloss thermoplastic resin composition may be 30 to 70% by weight. When the content is less than 30% by weight, the impact reinforcing effect may be insignificant, and when the content is more than 70% by weight, fluidity may be lowered.

Polyester

The low gloss thermoplastic resin composition according to the embodiments of the present invention may include at least one resin selected from a polyester resin and a polyester copolymer resin. The polyester can be, for example, polyalkylene terephthalate, preferably polyethylene terephthalate or polybutylene terephthalate.

The polybutylene terephthalate resin preferably has a melting temperature of 210 to 240 ° C and an intrinsic viscosity (Intrinsic Viscostiy, IV) of 0.75 to 1.1 (dl / g). When the melting temperature and the intrinsic viscosity of the polybutylene terephthalate resin are out of the above ranges, workability may be a problem in melt kneading with the polycarbonate, and mechanical properties of the resin composition may be reduced.

The content of the polyester in the low gloss thermoplastic resin composition may be 20 to 50% by weight. If it is less than 20% by weight, mechanical strength and fluidity may be lowered, and if it is more than 50% by weight, impact resistance may be lowered.

Impact modifier

Impact modifiers according to embodiments of the present invention methacrylonitrile-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES ), Acrylonitrile-styrene-butylacrylate (ASA), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene (SB) ), Styrene-isoprene rubber, ethylene-vinylacetate (EVA), ethylene-ethyl acrylate (EEA), ethylene-vinyl alcohol (EVOH) copolymer, silicone-acrylic rubber core and methyl methacrylate shell It may include one or more selected from the group consisting of an elastomer, a polybutylene terephthalate-based elastomer, a polyethylene terephthalate-based elastomer and a nylon-based elastomer.

The impact modifier may improve the impact resistance and may function to prevent physical property degradation due to ultraviolet exposure. In addition, as long as the impact resistance can be improved, any resin other than the above-mentioned resins can be used. As the impact modifier, an acrylic rubber of the core-shell type may be preferably used. The core-shell type acrylic rubber has a two-layer structure consisting of a core and a shell, the core portion is in a soft rubber state, and the shell portion on its surface is in a hard resin state. The graft rubbery elastomer in which the rubbery elastomer itself is powdery (particle state) can be suitably used.

The content of the impact modifier in the low gloss thermoplastic resin composition may be 1 to 15% by weight. If the content is less than 1% by weight, the impact resistance may be improved. If the content is more than 15% by weight, other mechanical properties may be lowered.

Polyalkyl methacrylate

The polyalkyl methacrylate according to the embodiments of the present invention may be prepared using one or more crosslinking agents selected from divinylbenzene, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate, and diethylene glycol dimethacrylate. Can be polymerized.

The content of the crosslinking agent may be 0.1 to 20% by weight based on 100% by weight of the polyalkyl methacrylate. The polyalkyl methacrylate may be spherical particles having an average particle diameter of 1 to 15㎛. The alkyl group of the polyalkyl methacrylate may be a substituted or unsubstituted cyclic or chain hydrocarbon having 1 to 10 carbon atoms. Preferably polymethyl methacrylate may be used as the polyalkyl methacrylate. The polyalkyl methacrylate may function as a matting agent.

The content of the polyalkyl methacrylate in the low gloss thermoplastic resin composition may be 1 to 5% by weight. If the content is less than 1% by weight, the matting effect may be insignificant, and if it is more than 5% by weight, other mechanical properties may be lowered.

Antioxidant

Antioxidant according to embodiments of the present invention may include one or more selected from phenolic compounds, phosphite compounds, thioester compounds.

The phenolic oxidative stabilizer is, for example, hindered phenol or pentaerythritol-tetrakis 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 2,2 ' Methylenebis (4-ethyl-6-t-butylphenol), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) 1,3,5-triazine -2,4,6- (1H, 3H, 5H) -trione, 1,3,5-tris- (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl). Preferably, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate can be used.

The phosphite-based oxidative stabilizer is, for example, bis (2-t-bit-butylphenyl) pentaryl thritol diphosphate, tris (2,4-di-t-butylphenyl) phosphite, 1,3,5 -Triazine- (1H, 3H, 5H) -trione, tris (2,4-di-t-butylphenyl) phosphite. Preferably, bis (2,4-di-butylphenyl) pentaerythritol phosphite can be used.

The content of the antioxidant in the low gloss thermoplastic resin composition may be 0.5 to 3% by weight. When the content is less than 0.5% by weight, the reinforcing effect on the ultraviolet light by the ultraviolet absorber and the hindered amine light stabilizer may be insignificant.

UV absorbers

As the ultraviolet absorber according to embodiments of the present invention, a benzotriazole compound, a hydroxyphenyl triazine compound, a pyrimidine compound, a cyanoacrylate compound, and the like may be used. Preferably, the ultraviolet absorber may include at least one selected from a benzotriazole compound and a triazine compound.

The ultraviolet absorbent may selectively absorb ultraviolet energy, convert the ultraviolet energy into an infrared energy form, and emit the ultraviolet ray to reinforce the resistance of the material by exposure to ultraviolet rays over a long period of time.

In the low gloss thermoplastic resin composition, the content of the ultraviolet absorber may be 0.5 to 1.5% by weight. If the content is less than 0.5% by weight, it is difficult to obtain the effect of improving the weather resistance desired, and if it is more than 1.5% by weight, mechanical properties may be lowered.

Light stabilizer

As a light stabilizer according to embodiments of the present invention, a hindered amine compound may be used. For example, poly [(6-morpholino-s-triazine-2,4-diyl) [2,2,6,6-tetra methyl-4-piperidyl] iminol] -hexamethylene [2, 2,6,6-tetramethyl-4-piperidyl] iminol], N- (2-hydroxy ethyl) -2,2,6,6-tetramethyl-4-piperidinol and the like can be used. have.

The light stabilizer may perform a function of stopping the photooxidation reaction by removing the free radicals generated during the photolysis reaction.

The content of the light stabilizer in the low gloss thermoplastic resin composition may be 0.05 to 0.15% by weight. If the content is less than 0.05% by weight, it is difficult to obtain the effect of improving the weather resistance desired, and if it is more than 0.15% by weight, mechanical properties may be lowered.

Ethylene copolymer

The low gloss thermoplastic resin composition according to the embodiments of the present invention may further include an ethylene copolymer. The ethylene copolymer is an ethylene / alkyl acrylate copolymer having a glycidyl methacrylate functional group, and may be a compound of Formula 5 below.

[Formula 1]

In Formula 1, R ₁ , R ₂ and R ₃ may each independently represent a substituted or unsubstituted cyclic or chain hydrocarbon having 1 to 10 carbon atoms, R ₂ may include one or more non-carbon elements, , x, y and z may represent 2 to 30,000 as the average degree of polymerization, respectively. The non-carbon element may include sulfur (S), oxygen (O), and nitrogen (N).

Preferably, the ethylene copolymer may be an ethylene-alkylacrylate-glycidyl methacrylate copolymer, wherein in Formula 1, R ₁ is alkyl, R ₂ is glycidyl, and R 3 is methyl. More preferably, ethylene-normal butyl acrylate-glycidyl methacrylate may be used. In addition, the ethylene- normal butyl acrylate-glycidyl methacrylate copolymer is 15 to 30% by weight of normal butyl acrylate units, 5 to 12% by weight of glycidyl methacrylate units and 58 to 80% by weight It is preferable that it consists of the ethylene units of.

The copolymer represented by Chemical Formula 1 may perform a function of an impact modifier and a quencher, and react with a carboxyl terminal group of the polybutylene terephthalate resin due to the third repeating unit structure including R ₂ and R ₃ . In addition, the function of improving the hydrolysis resistance can also be performed by reducing the concentration of carboxyl end groups.

The content of the ethylene copolymer in the low gloss thermoplastic resin composition may be 0.1 to 3% by weight. If the content is less than 0.1% by weight, the impact resistance improvement may be insignificant, and if the content is more than 3% by weight, other mechanical properties may be lowered.

Other additives

The low gloss thermoplastic resin composition according to the embodiments of the present invention may further include a stearate-based or fatty acid-based release agent. The content of the release agent in the low gloss thermoplastic resin composition may be 0.05 to 1% by weight.

≪ Examples and Comparative Examples &

The raw materials were mixed in the composition and content as shown in Table 1 below, and kneaded and extruded by a twin screw melt kneading extruder at a temperature of 230 to 260 ° C. to prepare a molding pallet. The prepared pallet was hot-air dried at 100 ° C. for 6 hours, and then injection molded at a temperature of 250 to 270 ° C. to prepare a specimen.

division Example Comparative example One 2 3 One 2 3 4 5 6 PC1 54.3 54.3 54.3 - 54.8 53.5 54.4 54.7 54.7 PC2 - - - 54.3 - - - - - PBT 36.2 36.2 36.2 36.2 36.5 35.5 36.1 36.4 36.4 Impact modifier 1 4 4 4 4 4 4 4 4 4 Impact modifier 2 One One One One One One One One One UVA1 0.7 - 0.7 0.7 - 2.0 0.7 0.7 - UVA2 - 0.7 - - - - - - - UVA3 - - - - - - - - 0.7 Light stabilizer 0.1 0.1 0.1 0.1 - 0.3 - 0.1 0.1 Antioxidant 1 0.2 0.2 0.6 0.2 0.2 0.2 0.2 - 0.2 Antioxidant 2 0.2 0.2 - 0.2 0.2 0.2 0.2 - 0.2 Antioxidant 3 0.2 0.2 - 0.2 0.2 0.2 0.2 - 0.2 Matting agent 3 3 3 3 3 3 3 3 3 Release agent 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1

* PC1: polycarbonate with a molecular weight of 21,000

* PC2: polycarbonate with a molecular weight of 17,000

* PBT: Polybutylene terephthalate (Samyang TRIBIT 1700S)

* Impact modifier 1: W450A manufactured by Mitsubishi Rayon with acrylic rubber as core and polymethyl methacrylate as shell structure

* Impact modifier 2: Ethylene-normal butyl acrylate-glycidyl methacrylate copolymer (Dupont, Elvaloy PTW)

* Matting agent: spherical polyalkyl methacrylate (Ganz Chemical, Ganzpearl GM-0600)

* UVA1: Benzotriazole UV absorber (Cytec, Cyasorb UV-54 11)

* UVA2: Hardoxyphenyl / triazine type ultraviolet absorber (Ciba Specialty Chemicals, Tinu vin 1577)

* UVA3: Benzophenone UV absorber (BASF, Uvinul3040)

* Light stabilizer: Hindered amine light stabilizer (HALs, Ciba Specialty Chemicals, Tinuvin 622) which is N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol oligomer

* Antioxidant 1: Hindered hydroxyphenyl-based antioxidant (Ciba Specialty Chemicals, Irganox 1076),

* Antioxidant 2: phosphite antioxidant (GE Specialty Chemicals, Ultranox 627A)

* Antioxidant 3: Thioester-based antioxidant (RICH NOX, DSTDP or Shipro Kasei Kaisha, Seenox 412S)

The physical properties of the thermoplastic resin compositions of Examples and Comparative Examples were measured and shown in Table 2 below.

division Example Comparative example One 2 3 One 2 3 4 5 6 Tensile Strength (kg _f / ㎠) 590 587 593 530 583 543 586 550 498 Impact Strength (kg _f cm / cm) 70 72 73 55 69 48 70 65 55 Glossiness (%) 48 50 52 48 49 50 52 49 43 Flowability (g / 10min) 20 21 21 26 21 23 20 21 20 ΔE 2.95 3.0 2.98 5.3 7.51 4.56 5.72 4.84 3.24

The measuring method of the said physical property is as follows.

a) Tensile strength: measured according to ASTM D790 under a condition of 50mm / min using a 1/4 "specimen.

b) Impact strength: measured by using 1/8 ”specimen in IZOD NOTCHED type according to ASTM D256.

c) Glossiness: Surface glossiness was measured at an angle of 60 ° according to ASTM D523.

d) Flowability: According to ASTM D1238, after drying for 4 hours at 110 ℃ in the chip state was measured for 10 minutes at 250 ℃ and 5kg load conditions.

e) Weather resistance: Using a weather-O-meter (Atlas Model Ci4,000), the amount of light at xenon lamp 340nm was set at 0.55W / m ² , the black panel temperature was 70 ° C, and the total exposure 3500KJ / It was investigated to 2 m 2. The irradiated specimens were measured for ΔE after irradiation using a color difference meter (konia Minolta, Cm-3700d). Less ΔE indicates better weather resistance.

As shown in Table 2, it can be seen that Examples 1 to 3 according to the present invention have excellent weather resistance while maintaining excellent mechanical properties and quenching characteristics compared to Comparative Examples 1 to 6.

Comparative Example 1 shows that not only mechanical properties but also weather resistance are reduced by using a polycarbonate having a viscosity molecular weight of less than 21,000. Comparative Examples 2 and 4 show that weather resistance is remarkably reduced by not using the hindered amine light stabilizer. Comparative Example 3 shows that the mechanical properties are lowered by the excessive addition of the ultraviolet absorber and the hindered amine light stabilizer as compared to the insignificant effect on the weatherability. Comparative Example 5 shows that the antioxidant acts as a reinforcing action of the ultraviolet absorber and the hindered amine light stabilizer. Comparative Example 6 shows that the use of a benzophenone-based ultraviolet absorber is somewhat effective in terms of weather resistance, but the mechanical properties of the resin are significantly reduced.

Hereinafter, specific embodiments of the present invention have been described. Those skilled in the art will appreciate that the present invention can be implemented in a modified form without departing from the essential features of the present invention. Therefore, the disclosed embodiments should be considered in an illustrative rather than a restrictive sense. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.

Claims (13)

30 to 70 weight percent polycarbonate; 20-50% by weight of polyester; 1 to 15% impact modifier; 1-5% by weight of polyalkyl methacrylate; 0.5 to 3 weight percent antioxidant; 0.5 to 1.5% by weight of an ultraviolet absorbent; And A low gloss thermoplastic resin composition comprising 0.05 to 0.15 wt% light stabilizer. The method of claim 1, The polycarbonate is a low-gloss thermoplastic resin composition, characterized in that the aromatic polycarbonate having a viscosity average molecular weight of 21,000 to 30,000. The method of claim 1, The polyester is a low gloss thermoplastic resin composition, characterized in that the polyalkylene terephthalate. The method of claim 1, The impact modifiers are methacrylonitrile-butadiene-styrene (MBS), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-ethylene-propylene-diene terpolymer-styrene (AES), acrylonitrile -Styrene-butylacrylate (ASA), ethylene-propylene-diene terpolymer (EPDM), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), styrene-butadiene (SB), styrene-isoprene Rubber, Ethylene-vinylacetate (EVA), Ethylene-ethyl acrylate (EEA), Ethylene-vinyl alcohol (EVOH) copolymer, Elastomer of a structure where silicone-acrylic rubber is a core and methyl methacrylate is a shell, Polybutylene tere A low gloss thermoplastic resin composition comprising at least one selected from the group consisting of a phthalate elastomer, a polyethylene terephthalate elastomer and a nylon elastomer. The method of claim 1, The polyalkyl methacrylate is polymerized using at least one crosslinking agent selected from divinylbenzene, ethylene glycol dimethacrylate, diethyl glycol dimethacrylate and diethylene glycol dimethacrylate, The content of the crosslinking agent is a low gloss thermoplastic resin composition, characterized in that 0.1 to 20% by weight relative to 100% by weight of the polyalkyl methacrylate. The method of claim 1, The polyalkyl methacrylate is a low gloss thermoplastic resin composition, characterized in that the spherical particles having an average particle diameter of 1 to 15㎛. The method of claim 1, The antioxidant is a low gloss thermoplastic resin composition, characterized in that it comprises at least one selected from a phenolic compound, a phosphite compound, and a thioester compound. The method of claim 1, The ultraviolet absorber is low gloss thermoplastic resin composition, characterized in that it comprises at least one selected from a benzotriazole compound, a hydroxyphenyl triazine compound, a pyrimidine compound and a cyanoacrylate compound. The method of claim 1, The light stabilizer is a low gloss thermoplastic resin composition, characterized in that the hindered amine compound. The method of claim 1, Low gloss thermoplastic resin composition further comprises 0.1 to 3% by weight of an ethylene copolymer. 11. The method of claim 10, The ethylene copolymer has a structure of Formula 1 below, and is composed of 15 to 30% by weight of alkyl acrylate units, 5 to 12% by weight of glycidyl methacrylate units, and 58 to 80% by weight of ethylene units. Low gloss thermoplastic resin composition, characterized in that. [Formula 1]

(In Formula 1, R ₁ , R ₂ and R ₃ each independently represent a substituted or unsubstituted cyclic or chain hydrocarbon of 1 to 10 carbon atoms, R ₂ includes one or more non-carbon elements, x, y and z represent 2 to 30,000 as the average degree of polymerization, respectively.) The method of claim 11, The non-carbon element is a low gloss thermoplastic resin composition, characterized in that containing sulfur (S), oxygen (O), and nitrogen (N). The method of claim 1, A low gloss thermoplastic resin composition further comprising a release agent.