WO2014208857A1 - Thermoplastic resin composition and moulded article using same - Google Patents

Thermoplastic resin composition and moulded article using same Download PDF

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Publication number
WO2014208857A1
WO2014208857A1 PCT/KR2014/000967 KR2014000967W WO2014208857A1 WO 2014208857 A1 WO2014208857 A1 WO 2014208857A1 KR 2014000967 W KR2014000967 W KR 2014000967W WO 2014208857 A1 WO2014208857 A1 WO 2014208857A1
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Prior art keywords
thermoplastic resin
resin composition
weight
copolymer
glass
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PCT/KR2014/000967
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French (fr)
Korean (ko)
Inventor
이선애
함민경
권영철
박강열
Original Assignee
제일모직주식회사
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Publication of WO2014208857A1 publication Critical patent/WO2014208857A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

  • the present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a styrene-based thermoplastic resin composition for an exterior material having excellent metal texture, gloss characteristics, and appearance characteristics.
  • thermoplastic resins have excellent physical properties such as dimensional stability, molding processability, and impact resistance, but good appearance characteristics are not satisfied.
  • thermoplastic resins are being used for increasing cost and weight reduction of electric and electronic products, and their application ranges are expanding, and the demand for mechanical properties along with their function and appearance as exterior materials is increasing.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • SAN resin styrene-acrylonitrile copolymer resin
  • the ABS resin is widely used in various fields such as automobile parts and interior and exterior materials, electrical and electronic products, office equipment, toys, etc. because of excellent impact resistance, weather resistance, chemical resistance, heat resistance, and mechanical strength, and easy molding process.
  • U.S. Patent No. 7,135,520 discloses improving the appearance by using a mixture of crushed glass fibers and chopped glass fibers, but there is a problem in that the appearance improvement effect is insufficient and mechanical strength is lowered.
  • Japanese Patent Laid-Open No. 2001-262003 discloses the use of metal particles for metal texture, but there is a problem such as a flow mark or weld line during injection.
  • thermoplastic resin composition for an exterior material which exhibits excellent metal texture by preventing flow marks and weld lines that may occur during injection molding while maintaining the physical properties of the thermoplastic resin and having excellent gloss and appearance characteristics is urgently needed.
  • an object of the present invention is to provide a thermoplastic resin composition having excellent metal texture, gloss and appearance properties by preventing flow marks and weld lines that may occur during injection molding. .
  • an object of this invention is to provide the molded article excellent in the external appearance characteristic manufactured from a thermoplastic resin composition.
  • the present invention is a thermoplastic resin comprising any one or more selected from the group consisting of (A) (a1) styrene-based copolymer resin and (a2) rubber-modified vinyl-based aromatic copolymer, ( It provides a thermoplastic resin composition comprising B) hollow microspheres and (C) metal particles.
  • thermoplastic resin composition is 100 wt% of a thermoplastic resin including any one or more selected from the group consisting of (A) (a1) a styrene-based copolymer resin and (a2) a rubber-modified vinyl-based aromatic copolymer. It may contain 1 to 10 parts by weight of (B) hollow microspheres and 0.01 to 10 parts by weight of (C) metal particles.
  • the hollow microspheres may include glass bubbles.
  • the glass bubble may have a diameter of 10 to 80 ⁇ m.
  • the glass bubble may have a compressive strength of 14,000 to 50,000 psi.
  • the glass bubble may have a specific gravity of 0.1 to 0.6 g / cc.
  • the metal particles may have an average particle diameter of 1 to 150 ⁇ m.
  • the metal particles may be selected from aluminum, copper, gold, and combinations thereof.
  • the styrene-based copolymer resin (a1) is 50 to 95% by weight of an aromatic vinyl compound or a mixture thereof, and a (meth) acrylic acid alkyl ester or a mixture thereof. It may be a copolymer prepared by copolymerizing 50% by weight or a mixture of these copolymers.
  • the rubber-modified vinyl graft copolymer (a2) is a graft graft polymerized from 5 to 95% by weight of a vinyl monomer mixture to 5 to 95% by weight of a rubbery polymer. It may be a copolymer.
  • the glass fiber, carbon fiber, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate and wollastonite (wallostonite) may further include at least one.
  • the present invention provides a molded article prepared from the thermoplastic resin composition.
  • thermoplastic resin composition according to the present invention significantly improves metal texture, gloss and appearance by preventing flow marks and weld lines that may occur during injection molding while having excellent dimensional stability, molding processability, impact resistance, weather resistance, and mechanical properties. There is an advantage to this.
  • thermoplastic resin composition of the present invention will be described in detail.
  • the following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art.
  • it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of known functions and configurations that may be omitted.
  • thermoplastic resin composition having excellent appearance characteristics
  • a thermoplastic resin comprising at least one selected from the group consisting of a styrene copolymer resin and a rubber-modified vinyl aromatic copolymer
  • the present invention was found to dramatically improve the surface appearance characteristics by surprisingly improving the metal texture while suppressing the generation of flow marks and weld lines that may occur during injection molding.
  • thermoplastic resin composition of the present invention is based on 100 parts by weight of a thermoplastic resin containing any one or more selected from the group consisting of (A) (a1) a styrenic copolymer resin and (a2) a rubber-modified vinyl aromatic copolymer, B) 1 to 10 parts by weight of the hollow microspheres and 0.01 to 10 parts by weight of (C) the metal particles.
  • thermoplastic resin (A) thermoplastic resin
  • Styrene-based copolymer resin (a1) in the present invention is an aromatic vinyl compound or a mixture of 50 to 95% by weight thereof, an unsaturated nitrile compound, (meth) acrylic acid alkyl ester compound, maleic anhydride, maleimide compound or a mixture thereof It includes the thing which copolymerized 5-50 weight%.
  • the copolymerization method may be a method selected from emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, but is not necessarily limited thereto.
  • the aromatic vinyl compound may include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, and the like, but is not limited thereto.
  • the unsaturated nitrile compound may be acrylonitrile, methacrylonitrile, and the like, but is not necessarily limited thereto.
  • the (meth) acrylic acid alkyl ester compound includes a C1-C8 methacrylic acid alkyl ester compound and a C1-C8 acrylic acid alkyl ester compound.
  • the C1-C8 methacrylic acid alkyl ester compound or the C1-C8 acrylic acid alkyl ester compound is an ester compound obtained from a monohydryl alcohol containing 1 to 8 carbon atoms as an alkyl ester compound of methacrylic acid or acrylic acid, respectively. It includes.
  • methacrylic acid methyl ester methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester, and the like, but are not necessarily limited thereto.
  • the maleimide compound includes C1-C4 alkyl or phenyl N-substituted maleimide, and the like, but is not limited thereto.
  • Styrene-based copolymer resin (a1) in the present invention is 50 to 95% by weight of styrene, ⁇ -methylstyrene, halogen or alkyl substituted styrene or a mixture thereof and acrylonitrile, methacrylonitrile, C1-C8 alkyl methacrylate Styrene-based copolymers obtained by copolymerizing esters, C1-C8 acrylic acid alkyl esters, maleic anhydride, C1-C4 alkyl or phenyl nucleosubstituted maleimides or mixtures thereof, or mixtures thereof. .
  • Preferred styrenic copolymer resins (a1) include monomer mixtures of styrene and acrylonitrile, optionally methacrylic acid methyl ester; monomer mixtures of ⁇ -methylstyrene with acrylonitrile, optionally, methacrylic acid methyl ester; Or prepared from monomer mixtures of styrene, ⁇ -methylstyrene and acrylonitrile, optionally methyl methacrylate.
  • the weight average molecular weight of the styrene-based copolymer (a1) may be 15,000 to 250,000 (g / mol).
  • Another preferred styrene-based copolymer (a1) is a copolymer of styrene and maleic anhydride, and includes one prepared by continuous bulk polymerization or solution polymerization. At this time, the content of maleic anhydride is 5 to 50% by weight, and the weight average molecular weight of the styrene / maleic anhydride copolymer may be 15,000 to 250,000 (g / mol).
  • the rubber-modified vinyl graft copolymer (a2) may be prepared by graft polymerization of 5 to 95 wt% of the rubbery polymer and 5 to 95 wt% of the vinyl monomer mixture.
  • the rubber-modified vinyl graft copolymer (a2) may be prepared by a method selected from emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, and preferably, emulsion polymerization or bulk polymerization may be used. It is not limited.
  • the vinyl monomer mixture may be an aromatic vinyl compound, (meth) acrylic acid alkyl esters, or 50 to 95% by weight of mixtures thereof, and an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleimide compounds, or mixtures thereof. Contains weight percent.
  • the vinyl monomer mixture is an aromatic vinyl compound, (meth) acrylic acid alkyl esters, or 60 to 90% by weight thereof, and an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleimide compounds, or mixtures thereof. 10 to 40% by weight.
  • the aromatic vinyl compound may include styrene, ⁇ -methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, and the like, but is not limited thereto.
  • the (meth) acrylic acid alkyl ester compound includes a C1-C8 methacrylic acid alkyl ester compound and a C1-C8 acrylic acid alkyl ester compound.
  • the C1-C8 methacrylic acid alkyl ester-based or C1-C8 acrylic acid alkyl ester-based compound includes ester compounds obtained from monohydryl alcohols containing 1 to 8 carbon atoms, respectively, as alkyl esters of methacrylic acid or acrylic acid. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester, and the like, but are not limited thereto.
  • the unsaturated nitrile compound includes acrylonitrile, methacrylonitrile, and the like, but is not necessarily limited thereto.
  • the maleimide compound includes C1-C4 alkyl or phenyl N-substituted maleimide, and the like, but is not limited thereto.
  • the rubbery polymers include butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) of ethylene-propylene-diene and polyorganosiloxane / polyalkyl ( Meth) acrylate rubber composites, but is not necessarily limited thereto.
  • the rubbery polymer preferably has an average particle diameter of 0.05 to 4 ⁇ m in order to improve mechanical properties such as molding processability, dimensional stability, impact resistance, and the like.
  • the rubber-modified vinyl graft copolymer (a2) is styrene, ⁇ -methylstyrene, halogen or alkyl substituted styrene, C1-C8 methacrylic acid alkyl esters, C1-C8 acrylic acid alkyl esters, or mixtures thereof.
  • EPDM ethylene-propylene-diene Terpolymers
  • the rubber-modified vinyl-based graft copolymer (a2) is a graft copolymer of styrene, acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers in the form of a mixture of butadiene rubber, acrylic rubber, or styrene / butadiene rubber.
  • butadiene rubber, acrylic rubber, or styrene / butadiene rubber may be graft copolymerized monomers of (meth) acrylic acid methyl ester.
  • it may be an ABS graft copolymer.
  • the hollow microspheres may be hollow spherical microparticles.
  • the hollow microspheres may be glass bubbles.
  • the hollow microspheres are hollow glass particles, which are excellent in rigidity and can lower the specific gravity of the molded article through filling.
  • the hollow microspheres have excellent dispersibility in the base resin and exhibit excellent metal texture in combination with the metal particles due to the permeability and reflection properties in the particles themselves, thereby dramatically improving the surface properties.
  • the hollow microspheres may have a compressive strength of 14,000 to 50,000 psi and a diameter of 10 to 80 ⁇ m.
  • the compressive strength is 25,000 to 45,000psi
  • the diameter may be 20 to 70 ⁇ m. This is a more preferable range for expressing the excellent metal texture and surface property synergistic effect of the molded article due to the permeability and reflectivity in combination with the metal particle component.
  • the hollow microspheres may be 1 to 10 parts by weight based on 100 parts by weight of the base resin (A). More preferably, it may be 1 to 5 parts by weight. Outside the above range, the dispersibility may be lowered surface properties, it may be difficult to express the excellent metal texture.
  • the hollow microspheres may have a specific gravity of 0.1 to 0.6 g / cc. More preferably 0.2 to 0.4 g / cc. In this case, the dispersibility in the base resin is increased, thereby improving the surface properties of the molded article through the metal texture.
  • the metal particles are for imparting a metal texture and include aluminum, gold, copper, or a combination thereof.
  • the metal particles may have a spherical shape rather than a plate shape because a flow mark or weld line may occur due to the dispersion orientation deformation during injection molding.
  • the metal particles may have an average particle diameter of 1 to 150 ⁇ m, preferably 5 to 100 ⁇ m.
  • the metal particles may have a content in the base resin (A) of 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight.
  • the present invention may further include any one or two or more selected from the group consisting of glass fibers, carbon fibers, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate, and wollastonite. .
  • the moldability and appearance characteristics can be further improved.
  • the glass fiber may have an average length of 0.1 to 20 mm, preferably 0.3 to 10 mm, and an aspect ratio of 10 to 2,000, preferably 30 to 1,000.
  • the molded article manufactured from the thermoplastic resin composition may provide a metal texture without additional painting, and expresses excellent metal texture and appearance characteristics by using a flop index as an index of performance of the molded article. You can see that.
  • the flop index is an index indicating the metal texture of the surface, and is measured according to the following definition by measuring the luminance L of each reflected light at 15 °, 45 °, and 110 °.
  • L (x ⁇ ) means luminance measured at x ⁇ .
  • the flop index of the non-metallic surface is 0, the flop index of the metal is about 15 to about 17, and the flop index of the surface which can feel the metallic texture with the naked eye is about 6.5 or more.
  • the molded article produced from the thermoplastic resin composition according to the present invention is characterized by having a flop index of 8 or more.
  • thermoplastic resin composition according to the present invention provides a molded article having almost no flow mark and weld line during injection molding, and having a flop index of 8 or more.
  • SAN styrene-acrylonitrile copolymer resin having a weight average molecular weight of 150,000 prepared by suspension polymerization of 75 parts by weight of styrene and 25 parts by weight of acrylonitrile at 75 ° C. for 5 hours was used.
  • Polybutadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the total amount of monomers, 1.0 parts by weight of potassium oleate, cumene hydroperox, an additive necessary for a mixture of 39 parts by weight of styrene, 16 parts by weight of acrylonitrile, and 150 parts by weight of deionized water. Seed 0.4 parts by weight, 0.3 parts by weight of t-dodecyl mercaptan chain transfer agent, and then reacted while maintaining at 75 °C for 5 hours to prepare an ABS graft latex (g-ABS). A 1% sulfuric acid solution was added to the resulting polymer latex, solidified and dried to prepare a graft copolymer resin in a powder state.
  • g-ABS ABS graft latex
  • a glass bubble having a diameter of 40 ⁇ m, a compressive strength of 40,000 psi, and a specific gravity of 0.3 g / cc was used.
  • Spherical aluminum particles (Micro Metal, product name: Al powder) having an average particle diameter of 10 ⁇ m were used.
  • the extrudate After preparing the thermoplastic resin composition with the composition shown in Table 1 by using the above-mentioned components, and then extruded at 240 °C in a conventional twin screw extruder, the extrudate is prepared in pellet form and then evaluated by physical properties Indicated.
  • a glass bubble was manufactured in the same manner as in Example 1, except that the diameter was 30 ⁇ m.
  • a hollow microsphere was prepared in the same manner as in Example 1, except that the content of 15 parts by weight was used.
  • a hollow microsphere (glass bubble) was prepared in the same manner as in Example 1 except that the diameter of 5 ⁇ m was used.
  • a hollow microsphere (glass bubble) was prepared in the same manner as in Example 1 except that the diameter of 150 ⁇ m was used.
  • a metal particle (aluminum particle) was produced in the same manner as in Example 1 except that a particle diameter of 0.5 ⁇ m was used.
  • a metal particle (aluminum particle) was produced in the same manner as in Example 1 except that the particle diameter was 200 ⁇ m.
  • the flop index was measured using a measuring instrument (manufacturer: BYK, model name: BYK Mac).
  • the flip-flop effect which is the texture of the aluminum particles, was evaluated by combining three angles of 15 °, 45 °, and 110 °, and the values are shown in Table 1 below.
  • Examples 1 to 4 according to the present invention have a high flop index value when compared with the comparative examples, and have a very good metal texture, but do not generate flow marks or weld lines. I could confirm this superiority.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to a thermoplastic resin composition which has outstanding dimensional stability, moulding processability, shock resistance, weather resistance and mechanical properties and yet at the same time prevents the blow marks and weld lines that can occur during injection moulding, and which can thereby dramatically improve metal texture, glossiness and appearance.

Description

열가소성 수지 조성물 및 이를 이용한 성형품Thermoplastic resin composition and molded article using same
본 발명은 열가소성 수지 조성물에 대한 것이다. 보다 상세하게는 우수한 메탈 질감, 광택 특성 및 외관 특성을 갖는 외장재용 스티렌계 열가소성 수지 조성물에 관한 것이다.The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a styrene-based thermoplastic resin composition for an exterior material having excellent metal texture, gloss characteristics, and appearance characteristics.
열가소성 수지는 치수 안정성, 성형 가공성 및 내충격성 등과 같은 우수한 물성을 갖고 있으나, 좋은 외관 특성은 충족되지 못하고 있다. 이러한 가운데 열가소성 수지는 전기 전자 제품의 원가 절감, 경량화에 따른 사용이 증가하면서 그 적용 범위가 확대되고 있으며, 외장재로서의 기능 및 외관 성능과 함께 기계적 물성에 대한 요구도 높아지고 있는 실정이다. Thermoplastic resins have excellent physical properties such as dimensional stability, molding processability, and impact resistance, but good appearance characteristics are not satisfied. Among these, thermoplastic resins are being used for increasing cost and weight reduction of electric and electronic products, and their application ranges are expanding, and the demand for mechanical properties along with their function and appearance as exterior materials is increasing.
이러한 열가소성 수지 중에서도, 아크릴로니트릴-부타디엔-스티렌 공중합체 수지(이하, ABS 수지)는 부타디엔계 고무질 중합체의 존재 하에서 방향족 비닐계 화합물인 스티렌 단량체와 불포화 니트릴계 화합물인 아크릴로니트릴 단량체를 그라프트 중합하여 제조된 그라프트 ABS 수지(이하, g-ABS 수지)와 스티렌-아크릴로니트릴 공중합체 수지(이하, SAN 수지)를 블랜딩하여 제조된다. 이러한 ABS 수지는 내충격성, 내후성, 내화학성, 내열성 및 기계적 강도가 우수하고 성형 가공이 용이하여 자동차 부품 및 내외장재, 전기전자 제품, 사무기기, 완구류 등의 여러 분야에 걸쳐 광범위하게 사용되고 있다. Among these thermoplastic resins, acrylonitrile-butadiene-styrene copolymer resin (hereinafter referred to as ABS resin) is a graft polymerization of a styrene monomer which is an aromatic vinyl compound and an acrylonitrile monomer which is an unsaturated nitrile compound in the presence of a butadiene rubbery polymer. It is prepared by blending a graft ABS resin (hereinafter referred to as g-ABS resin) and a styrene-acrylonitrile copolymer resin (hereinafter referred to as SAN resin) prepared. The ABS resin is widely used in various fields such as automobile parts and interior and exterior materials, electrical and electronic products, office equipment, toys, etc. because of excellent impact resistance, weather resistance, chemical resistance, heat resistance, and mechanical strength, and easy molding process.
최근 전기전자 부품, 자동차 부품 등에 있어서 부품의 하우징에 대한 경향은 다양한 특성이 복합적으로 요구되고 있다. 구체적으로 다양한 색채가 구현된 플라스틱 외장 제품들에 대한 수요가 증대되고 있으며, 보다 고급적인 질감을 느낄 수 있도록 플라스틱 수지에 금속 등을 첨가하여 수지 외관에 메탈 질감을 나타내기도 한다.　Recently, in the electronic and electronic parts, automobile parts and the like, the trend toward the housing of parts has been required to have various characteristics in combination. Specifically, the demand for plastic exterior products with various colors is increasing, and metals may be added to plastic resins by adding metals to plastic resins to feel more luxurious textures.
미국등록특허 제7,135,520호에는 분쇄된 유리섬유와 절단된 유리섬유를 혼용하여 사용함으로써 외관을 향상시키는 것이 개시되어 있으나, 외관 개선 효과가 부족하고 기계적 강도가 저하되는 문제가 있다.U.S. Patent No. 7,135,520 discloses improving the appearance by using a mixture of crushed glass fibers and chopped glass fibers, but there is a problem in that the appearance improvement effect is insufficient and mechanical strength is lowered.
일본공개특허 제2001-262003호에는 금속 질감을 위하여 금속 입자를 사용하는 것이 개시되어 있으나 사출 시 플로우 마크나 웰드 라인이 발생하는 등의 문제가 있다. Japanese Patent Laid-Open No. 2001-262003 discloses the use of metal particles for metal texture, but there is a problem such as a flow mark or weld line during injection.
따라서, 열가소성 수지 본연의 물성을 유지하면서 사출 성형 시 발생할 수 있는 플로우 마크, 웰드 라인을 방지하여 우수한 메탈 질감을 발현하고, 뛰어난 광택 특성 및 외관 특성을 갖는 외장재용 열가소성 수지 조성물에 대한 개발이 절실하다.Therefore, the development of a thermoplastic resin composition for an exterior material which exhibits excellent metal texture by preventing flow marks and weld lines that may occur during injection molding while maintaining the physical properties of the thermoplastic resin and having excellent gloss and appearance characteristics is urgently needed. .
본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로서, 사출 성형 시 발생할 수 있는 플로우 마크, 웰드 라인을 방지하여 우수한 메탈 질감, 광택 특성 및 외관 특성을 갖는 열가소성 수지 조성물을 제공하는 것을 목적으로 한다. The present invention has been made to solve the above problems, an object of the present invention is to provide a thermoplastic resin composition having excellent metal texture, gloss and appearance properties by preventing flow marks and weld lines that may occur during injection molding. .
또한, 본 발명은 열가소성 수지 조성물로부터 제조되는 외관 특성이 뛰어난 성형품을 제공하는 것을 목적으로 한다.Moreover, an object of this invention is to provide the molded article excellent in the external appearance characteristic manufactured from a thermoplastic resin composition.
상기와 같은 목적을 달성하기 위하여, 본 발명은 (A) (a1) 스티렌계 공중합체 수지 및 (a2) 고무 변성 비닐계 방향족 공중합체로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 열가소성 수지, (B) 중공형 미세구체 및 (C) 금속 입자를 포함하는 열가소성 수지 조성물을 제공한다.In order to achieve the above object, the present invention is a thermoplastic resin comprising any one or more selected from the group consisting of (A) (a1) styrene-based copolymer resin and (a2) rubber-modified vinyl-based aromatic copolymer, ( It provides a thermoplastic resin composition comprising B) hollow microspheres and (C) metal particles.
본 발명의 일 실시예에 따른 열가소성 수지 조성물은 (A) (a1) 스티렌계 공중합체 수지 및 (a2) 고무 변성 비닐계 방향족 공중합체로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 열가소성 수지 100중량부에 대하여, (B) 중공형 미세구체 1 내지 10중량부 및 (C) 금속 입자 0.01 내지 10중량부를 포함할 수 있다.The thermoplastic resin composition according to one embodiment of the present invention is 100 wt% of a thermoplastic resin including any one or more selected from the group consisting of (A) (a1) a styrene-based copolymer resin and (a2) a rubber-modified vinyl-based aromatic copolymer. It may contain 1 to 10 parts by weight of (B) hollow microspheres and 0.01 to 10 parts by weight of (C) metal particles.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 중공형 미세구체는 글라스 버블을 포함할 수 있다. In the thermoplastic resin composition according to an embodiment of the present invention, the hollow microspheres may include glass bubbles.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 글라스 버블은 10 내지 80㎛의 직경을 가질 수 있다.In the thermoplastic resin composition according to an embodiment of the present invention, the glass bubble may have a diameter of 10 to 80㎛.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 글라스 버블은 압축강도가 14,000 내지 50,000 psi일 수 있다. In the thermoplastic resin composition according to an embodiment of the present invention, the glass bubble may have a compressive strength of 14,000 to 50,000 psi.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 글라스 버블은 비중이 0.1 내지 0.6 g/cc일 수 있다. In the thermoplastic resin composition according to an embodiment of the present invention, the glass bubble may have a specific gravity of 0.1 to 0.6 g / cc.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 금속 입자는 평균입경이 1 내지 150㎛ 일 수 있다.In the thermoplastic resin composition according to an embodiment of the present invention, the metal particles may have an average particle diameter of 1 to 150 μm.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 금속 입자는 알루미늄, 구리, 금 및 이들의 조합에서 선택될 수 있다.In the thermoplastic resin composition according to an embodiment of the present invention, the metal particles may be selected from aluminum, copper, gold, and combinations thereof.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 상기 스티렌계 공중합체 수지 (a1)는 방향족 비닐 화합물 또는 이들의 혼합물 50∼95 중량%와 (메타)아크릴산 알킬 에스테르계 또는 이들의 혼합물 5∼50 중량%을 공중합하여 제조된 공중합체 또는 이들 공중합체의 혼합물일 수 있다.In the thermoplastic resin composition according to an embodiment of the present invention, the styrene-based copolymer resin (a1) is 50 to 95% by weight of an aromatic vinyl compound or a mixture thereof, and a (meth) acrylic acid alkyl ester or a mixture thereof. It may be a copolymer prepared by copolymerizing 50% by weight or a mixture of these copolymers.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 상기 고무변성 비닐계 그라프트 공중합체 (a2)는 비닐계 단량체 혼합물 5∼95 중량%를 고무질 중합체 5∼95 중량%에 그라프트 중합한 그라프트 공중합체일 수 있다.In the thermoplastic resin composition according to an embodiment of the present invention, the rubber-modified vinyl graft copolymer (a2) is a graft graft polymerized from 5 to 95% by weight of a vinyl monomer mixture to 5 to 95% by weight of a rubbery polymer. It may be a copolymer.
본 발명의 일 실시예에 따른 열가소성 수지 조성물에 있어서, 유리섬유, 탄소섬유, 유리비드, 유리플레이크, 카본블랙, 클레이, 카올린, 탈크, 마이카, 탄산칼슘　및 규회석(wallostonite)으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 더 포함할 수 있다.In the thermoplastic resin composition according to an embodiment of the present invention, the glass fiber, carbon fiber, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate and wollastonite (wallostonite) It may further include at least one.
본 발명은 상기 열가소성 수지 조성물로부터 제조되는 성형품을 제공한다.The present invention provides a molded article prepared from the thermoplastic resin composition.
본 발명에 따른 열가소성 수지 조성물은 치수 안정성, 성형 가공성, 내충격성, 내후성, 기계적 물성이 뛰어나면서도 사출 성형 시 발생할 수 있는 플로우 마크, 웰드 라인을 방지함으로써 메탈 질감, 광택 특성 및 외관 특성을 획기적으로 향상시킬 수 있는 이점이 있다.The thermoplastic resin composition according to the present invention significantly improves metal texture, gloss and appearance by preventing flow marks and weld lines that may occur during injection molding while having excellent dimensional stability, molding processability, impact resistance, weather resistance, and mechanical properties. There is an advantage to this.
이하 본 발명의 열가소성 수지 조성물을 상세히 설명한다. 다음에 소개되는 실시예들은 당업자에게 본 발명의 사상이 충분히 전달될 수 있도록 하기 위해 예로서 제공되는 것이다. 또한, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가지며, 하기의 설명에서 본 발명의 요지를 불필요하게 흐릴 수 있는 공지 기능 및 구성에 대한 설명은 생략한다.Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. The following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art. In addition, unless there is another definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art to which this invention belongs, and unnecessarily obscure the subject matter of the present invention in the following description. Description of known functions and configurations that may be omitted.
본 발명의 발명자들은 외관 특성이 우수한 열가소성 수지 조성물을 개발하기 위하여 연구한 결과, 스티렌계 공중합체 수지 및 고무 변성 비닐계 방향족 공중합체로 이루어진 군으로부터 선택되는 적어도 어느 하나를 포함하는 열가소성 수지를 베이스 수지로 하여, 중공형 미세구체 및 금속 입자를 포함함으로써 놀랍게도 메탈 질감을 고급화하면서도 사출 성형 시 발생할 수 있는 플로우 마크, 웰드 라인의 발생을 억제하여 표면 외관 특성을 획기적으로 향상시킬 수 있음을 발견하여 본 발명을 완성하였다. The inventors of the present invention have been studied to develop a thermoplastic resin composition having excellent appearance characteristics, and as a result, a thermoplastic resin comprising at least one selected from the group consisting of a styrene copolymer resin and a rubber-modified vinyl aromatic copolymer By including the hollow microspheres and metal particles, the present invention was found to dramatically improve the surface appearance characteristics by surprisingly improving the metal texture while suppressing the generation of flow marks and weld lines that may occur during injection molding. Was completed.
본 발명의 열가소성 수지 조성물은 (A) (a1) 스티렌계 공중합체 수지 및 (a2) 고무 변성 비닐계 방향족 공중합체로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 열가소성 수지 100중량부에 대하여, (B) 중공형 미세구체 1 내지 10중량부 및 (C) 금속 입자 0.01 내지 10중량부를 포함한다. The thermoplastic resin composition of the present invention is based on 100 parts by weight of a thermoplastic resin containing any one or more selected from the group consisting of (A) (a1) a styrenic copolymer resin and (a2) a rubber-modified vinyl aromatic copolymer, B) 1 to 10 parts by weight of the hollow microspheres and 0.01 to 10 parts by weight of (C) the metal particles.
(A) 열가소성 수지(A) thermoplastic resin
(a1) 스티렌계 공중합체 수지(a1) Styrene Copolymer Resin
본 발명에서 스티렌계 공중합체 수지(a1)는 방향족 비닐 화합물 또는 이들의 혼합물 50∼95중량%와 불포화니트릴 화합물, (메타)아크릴산 알킬 에스테르계 화합물, 무수말레산, 말레이미드계 화합물 또는 이들의 혼합물 5∼50중량%를 공중합한 것을 포함한다. 이때, 상기 공중합 방법은 유화중합, 현탁중합, 용액중합, 및 괴상중합 중에서 선택되는 방법을 사용할 수 있으며, 반드시 이에 한정되지 않는다. Styrene-based copolymer resin (a1) in the present invention is an aromatic vinyl compound or a mixture of 50 to 95% by weight thereof, an unsaturated nitrile compound, (meth) acrylic acid alkyl ester compound, maleic anhydride, maleimide compound or a mixture thereof It includes the thing which copolymerized 5-50 weight%. In this case, the copolymerization method may be a method selected from emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, but is not necessarily limited thereto.
상기 방향족 비닐 화합물은 스티렌, α-메틸스티렌, p-메틸스티렌, 비닐톨루엔, 2,4-디메틸스티렌, 할로겐 또는 알킬 치환 스티렌 등을 사용할 수 있으며, 반드시 이에 한정되지 않는다. The aromatic vinyl compound may include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, and the like, but is not limited thereto.
상기 불포화 니트릴 화합물은 아크릴로니트릴, 메타크릴로니트릴 등을 사용할 수 있으며, 반드시 이에 한정되지 않는다. The unsaturated nitrile compound may be acrylonitrile, methacrylonitrile, and the like, but is not necessarily limited thereto.
상기 (메타)아크릴산 알킬 에스테르계 화합물은 C1-C8 메타크릴산 알킬 에스테르계 화합물, C1-C8 아크릴산 알킬 에스테르계 화합물을 포함한다. 상기 C1-C8 메타크릴산 알킬 에스테르계 화합물 또는 C1-C8 아크릴산 알킬 에스테르계 화합물은 각각 메타크릴산 또는 아크릴산의 알킬 에스테르계 화합물로 1∼8개의 탄소원자를 포함하는 모노히드릴 알코올로부터 얻어진 에스테르계 화합물을 포함한다. 구체예로서, 메타크릴산 메틸 에스테르, 메타크릴산 에틸 에스테르, 아크릴산 에틸 에스테르, 아크릴산 메틸 에스테르 또는 메타크릴산 프로필 에스테르 등을 들 수 있으며, 반드시 이에 한정되지 않는다. The (meth) acrylic acid alkyl ester compound includes a C1-C8 methacrylic acid alkyl ester compound and a C1-C8 acrylic acid alkyl ester compound. The C1-C8 methacrylic acid alkyl ester compound or the C1-C8 acrylic acid alkyl ester compound is an ester compound obtained from a monohydryl alcohol containing 1 to 8 carbon atoms as an alkyl ester compound of methacrylic acid or acrylic acid, respectively. It includes. Specific examples include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester, and the like, but are not necessarily limited thereto.
상기 말레이미드계 화합물로는 C1-C4 알킬 또는 페닐 N-치환 말레이미드 등이 있으며, 반드시 이에 한정되지 않는다. The maleimide compound includes C1-C4 alkyl or phenyl N-substituted maleimide, and the like, but is not limited thereto.
본 발명에서 스티렌계 공중합체 수지(a1)는 스티렌, α-메틸스티렌, 할로겐 또는 알킬 치환 스티렌 또는 이들의 혼합물 50∼95중량%와 아크릴로니트릴, 메타크릴로니트릴, C1-C8 메타크릴산 알킬 에스테르계, C1-C8 아크릴산 알킬 에스테르계, 무수말레인산, C1-C4 알킬 또는 페닐 핵치환 말레이미드 또는 이들의 혼합물 5∼50중량%를 공중합하여 얻은 스티렌계 공중합체 또는 이들 공중합체의 혼합물을 포함한다.Styrene-based copolymer resin (a1) in the present invention is 50 to 95% by weight of styrene, α-methylstyrene, halogen or alkyl substituted styrene or a mixture thereof and acrylonitrile, methacrylonitrile, C1-C8 alkyl methacrylate Styrene-based copolymers obtained by copolymerizing esters, C1-C8 acrylic acid alkyl esters, maleic anhydride, C1-C4 alkyl or phenyl nucleosubstituted maleimides or mixtures thereof, or mixtures thereof. .
바람직한 스티렌계 공중합체 수지(a1)는 스티렌과 아크릴로니트릴, 선택적으로 메타크릴산 메틸 에스테르의 단량체 혼합물; α-메틸스티렌과 아크릴로니트릴, 선택적으로, 메타크릴산 메틸 에스테르의 단량체 혼합물; 또는 스티렌, α-메틸스티렌과 아크릴로니트릴, 선택적으로 메타크릴산 메틸에스테르의 단량체 혼합물로부터 제조된 것을 포함한다. Preferred styrenic copolymer resins (a1) include monomer mixtures of styrene and acrylonitrile, optionally methacrylic acid methyl ester; monomer mixtures of α-methylstyrene with acrylonitrile, optionally, methacrylic acid methyl ester; Or prepared from monomer mixtures of styrene, α-methylstyrene and acrylonitrile, optionally methyl methacrylate.
이때, 상기 스티렌계 공중합체(a1)의 중량평균분자량은 15,000∼250,000(g/mol)일 수 있다.In this case, the weight average molecular weight of the styrene-based copolymer (a1) may be 15,000 to 250,000 (g / mol).
다른 바람직한 스티렌계 공중합체(a1)는 스티렌과 무수말레인산의 공중합체로서, 연속괴상중합법 또는 용액중합법을 이용하여 제조되는 것을 포함한다. 이때, 무수말레인산의 함량은 5∼50중량%이며, 스티렌/무수말레인산계 공중합체의 중량평균분자량은 15,000∼250,000(g/mol)인 것을 사용할 수 있다.Another preferred styrene-based copolymer (a1) is a copolymer of styrene and maleic anhydride, and includes one prepared by continuous bulk polymerization or solution polymerization. At this time, the content of maleic anhydride is 5 to 50% by weight, and the weight average molecular weight of the styrene / maleic anhydride copolymer may be 15,000 to 250,000 (g / mol).
(a2) 고무변성 비닐계 그라프트 공중합체(a2) Rubber modified vinyl graft copolymer
본 발명에서 고무변성 비닐계 그라프트 공중합체(a2)는 고무질 중합체 5∼95중량%와 비닐계 단량체 혼합물 5∼95중량%을 그라프트 중합하여 제조할 수 있다. 상기 고무변성 비닐계 그라프트 공중합체(a2)는 유화중합, 현탁중합, 용액중합, 및 괴상중합 중에서 선택되는 방법으로 제조될 수 있으며, 바람직하게는 유화중합 또는 괴상중합을 이용할 수 있으나, 반드시 이에 한정되지 않는다. In the present invention, the rubber-modified vinyl graft copolymer (a2) may be prepared by graft polymerization of 5 to 95 wt% of the rubbery polymer and 5 to 95 wt% of the vinyl monomer mixture. The rubber-modified vinyl graft copolymer (a2) may be prepared by a method selected from emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, and preferably, emulsion polymerization or bulk polymerization may be used. It is not limited.
상기 비닐계 단량체 혼합물은 방향족 비닐 화합물, (메타)아크릴산 알킬 에스테르계 또는 이들의 혼합물 50∼95중량%와 불포화니트릴 화합물, (메타)아크릴산 알킬 에스테르계, 말레이미드계 화합물 또는 이들의 혼합물 5∼50 중량%를 포함한다. The vinyl monomer mixture may be an aromatic vinyl compound, (meth) acrylic acid alkyl esters, or 50 to 95% by weight of mixtures thereof, and an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleimide compounds, or mixtures thereof. Contains weight percent.
바람직하게는 상기 비닐계 단량체 혼합물은 방향족 비닐 화합물, (메타)아크릴산 알킬 에스테르계 또는 이들의 혼합물 60∼90중량%와 불포화니트릴 화합물, (메타)아크릴산 알킬 에스테르계, 말레이미드계 화합물 또는 이들의 혼합물 10∼40 중량%을 포함한다. Preferably, the vinyl monomer mixture is an aromatic vinyl compound, (meth) acrylic acid alkyl esters, or 60 to 90% by weight thereof, and an unsaturated nitrile compound, (meth) acrylic acid alkyl esters, maleimide compounds, or mixtures thereof. 10 to 40% by weight.
상기 방향족 비닐 화합물은 스티렌, α-메틸스티렌, p-메틸스티렌, 비닐톨루엔, 2,4-디메틸스티렌, 할로겐 또는 알킬 치환 스티렌 등을 사용할 수 있으며, 반드시 이에 한정되지 않는다.The aromatic vinyl compound may include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, halogen or alkyl substituted styrene, and the like, but is not limited thereto.
상기 (메타)아크릴산 알킬 에스테르계 화합물은 C1-C8 메타크릴산 알킬 에스테르계, C1-C8 아크릴산 알킬 에스테르계 화합물을 포함한다. 상기 C1-C8 메타크릴산 알킬 에스테르계 또는 C1-C8 아크릴산 알킬 에스테르계 화합물은 각각 메타크릴산 또는 아크릴산의 알킬 에스테르계로서 1∼8개의 탄소원자를 포함하는 모노히드릴 알코올로부터 얻어진 에스테르계 화합물을 포함하며, 구체예로 메타크릴산 메틸 에스테르, 메타크릴산 에틸 에스테르, 아크릴산 에틸 에스테르, 아크릴산 메틸 에스테르 또는 메타크릴산 프로필 에스테르 등을 들 수 있으며, 반드시 이에 한정되지 않는다.The (meth) acrylic acid alkyl ester compound includes a C1-C8 methacrylic acid alkyl ester compound and a C1-C8 acrylic acid alkyl ester compound. The C1-C8 methacrylic acid alkyl ester-based or C1-C8 acrylic acid alkyl ester-based compound includes ester compounds obtained from monohydryl alcohols containing 1 to 8 carbon atoms, respectively, as alkyl esters of methacrylic acid or acrylic acid. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester, acrylic acid ethyl ester, acrylic acid methyl ester or methacrylic acid propyl ester, and the like, but are not limited thereto.
상기 불포화 니트릴 화합물은 아크릴로니트릴, 메타크릴로니트릴 등이 있으며, 반드시 이에 한정되지 않는다. The unsaturated nitrile compound includes acrylonitrile, methacrylonitrile, and the like, but is not necessarily limited thereto.
상기 말레이미드계 화합물로는 C1-C4 알킬 또는 페닐 N-치환 말레이미드 등이 있으며, 반드시 이에 한정되지 않는다. The maleimide compound includes C1-C4 alkyl or phenyl N-substituted maleimide, and the like, but is not limited thereto.
상기 고무질 중합체는 부타디엔 고무, 아크릴 고무, 에틸렌/프로필렌 고무, 스티렌/부타디엔 고무, 아크릴로니트릴/부타디엔 고무, 이소프렌 고무, 에틸렌-프로필렌-디엔의 삼원공중합체(EPDM) 및 폴리오가노실록산/폴리알킬(메타)아크릴레이트 고무 복합체를 포함하며, 반드시 이에 한정되지 않는다. 이때, 고무질 중합체는 성형 가공성, 치수 안정성, 내충격성 등의 기계적 물성을 향상시키기 위하여 평균입경이 0.05 ∼ 4㎛인 것이 바람직하다. The rubbery polymers include butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, terpolymer (EPDM) of ethylene-propylene-diene and polyorganosiloxane / polyalkyl ( Meth) acrylate rubber composites, but is not necessarily limited thereto. At this time, the rubbery polymer preferably has an average particle diameter of 0.05 to 4 µm in order to improve mechanical properties such as molding processability, dimensional stability, impact resistance, and the like.
본 발명에서 고무변성 비닐계 그라프트 공중합체(a2)는 스티렌, α-메틸스티렌, 할로겐 또는 알킬 치환 스티렌, C1-C8 메타크릴산 알킬 에스테르계, C1-C8 아크릴산 알킬 에스테르계 화합물 또는 이들의 혼합물 50∼95중량%와 아크릴로니트릴, 메타크릴로니트릴, C1-C8 메타크릴산 알킬 에스테르계 화합물, C1-C8 아크릴산 알킬 에스테르계 화합물, 무수말레인산, C1-C4 알킬 또는 페닐 N-치환 말레이미드 또는 이들의 혼합물 5∼50중량%를 포함하는 단량체 혼합물 5∼95중량%를 부타디엔 고무, 아크릴 고무, 에틸렌/프로필렌 고무, 스티렌/부타디엔 고무, 아크릴로니트릴/부타디엔 고무, 이소프렌 고무, 에틸렌-프로필렌-디엔의 삼원공중합체(EPDM) 및 폴리오가노실록산/폴리알킬(메타)아크릴레이트 고무 복합체로 이루어지는 군으로부터 선택된 하나 또는 이들의 혼합물 5∼95중량%에 그라프트 중합하여 제조된 것을 포함한다.In the present invention, the rubber-modified vinyl graft copolymer (a2) is styrene, α-methylstyrene, halogen or alkyl substituted styrene, C1-C8 methacrylic acid alkyl esters, C1-C8 acrylic acid alkyl esters, or mixtures thereof. 50 to 95% by weight of acrylonitrile, methacrylonitrile, C1-C8 methacrylic acid alkyl ester compound, C1-C8 acrylic acid alkyl ester compound, maleic anhydride, C1-C4 alkyl or phenyl N-substituted maleimide or 5 to 95% by weight of the mixture of monomers including 5 to 50% by weight of these mixtures, butadiene rubber, acrylic rubber, ethylene / propylene rubber, styrene / butadiene rubber, acrylonitrile / butadiene rubber, isoprene rubber, ethylene-propylene-diene Terpolymers (EPDM) and polyorganosiloxane / polyalkyl (meth) acrylate rubber composites of the group consisting of one or a mixture thereof It includes those produced by graft polymerization at 5 to 95% by weight.
상기 고무변성 비닐계 그라프트 공중합체(a2)는 부타디엔 고무, 아크릴 고무, 또는 스티렌/부타디엔 고무에 스티렌과 아크릴로니트릴 및 선택적으로 (메타)아크릴산 알킬 에스테르 단량체를 혼합물의 형태로 그라프트 공중합한 것이거나, 부타디엔 고무, 아크릴 고무, 또는 스티렌/부타디엔 고무에 (메타)아크릴산 메틸 에스테르의 단량체를 그라프트 공중합한 것일 수 있다. 바람직하게는 ABS 그라프트 공중합체일 수 있다.The rubber-modified vinyl-based graft copolymer (a2) is a graft copolymer of styrene, acrylonitrile and optionally (meth) acrylic acid alkyl ester monomers in the form of a mixture of butadiene rubber, acrylic rubber, or styrene / butadiene rubber. Alternatively, butadiene rubber, acrylic rubber, or styrene / butadiene rubber may be graft copolymerized monomers of (meth) acrylic acid methyl ester. Preferably it may be an ABS graft copolymer.
(B) 중공형 미세구체(B) hollow microspheres
본 발명에서 중공형 미세구체는 속이 빈 구형 미세입자일 수 있다. 일 예로, 상기 중공형 미세구체는 글라스 버블(glass bubble)일 수 있다. 상기 중공형 미세구체는 속이 빈 작은 유리 알갱이로서 강성이 뛰어나면서도 충진을 통한 성형품의 비중을 낮출 수 있다. 또한, 상기 중공형 미세구체는 베이스 수지 내에서 분산성이 뛰어나고 입자 자체 내의 투과성 및 반사 특성으로 인하여 금속 입자와의 조합으로 우수한 메탈 질감을 나타냄으로써 표면 특성을 획기적으로 향상시킬 수 있다. In the present invention, the hollow microspheres may be hollow spherical microparticles. For example, the hollow microspheres may be glass bubbles. The hollow microspheres are hollow glass particles, which are excellent in rigidity and can lower the specific gravity of the molded article through filling. In addition, the hollow microspheres have excellent dispersibility in the base resin and exhibit excellent metal texture in combination with the metal particles due to the permeability and reflection properties in the particles themselves, thereby dramatically improving the surface properties.
이때, 상기 중공형 미세구체는 압축강도가 14,000 내지 50,000psi이고, 직경이 10 내지 80㎛일 수 있다. 바람직하게는 압축강도가 25,000 내지 45,000psi이고, 직경이 20 내지 70㎛일 수 있다. 이는, 금속 입자 성분과의 조합으로 투과성 및 반사성으로 인한 성형품의 우수한 메탈 질감과 표면 특성 상승 효과를 발현하기에 보다 바람직한 범위이다. In this case, the hollow microspheres may have a compressive strength of 14,000 to 50,000 psi and a diameter of 10 to 80 μm. Preferably the compressive strength is 25,000 to 45,000psi, the diameter may be 20 to 70㎛. This is a more preferable range for expressing the excellent metal texture and surface property synergistic effect of the molded article due to the permeability and reflectivity in combination with the metal particle component.
상기 중공형 미세구체는 (A) 베이스 수지 100중량부에 대하여 1 내지 10중량부일 수 있다. 보다 바람직하게는 1 내지 5 중량부일 수 있다. 상기 범위를 벗어나면 분산성이 떨어져 표면 특성이 저하될 수 있으며, 우수한 메탈 질감을 발현하기 어려울 수 있다.The hollow microspheres may be 1 to 10 parts by weight based on 100 parts by weight of the base resin (A). More preferably, it may be 1 to 5 parts by weight. Outside the above range, the dispersibility may be lowered surface properties, it may be difficult to express the excellent metal texture.
또한, 상기 중공형 미세구체는 비중이 0.1 내지 0.6g/cc일 수 있다. 보다 바람직하게는 0.2 내지 0.4 g/cc일 수 있다. 이 경우, 베이스 수지 내에서의 분산성이 증대되어 메탈 질감을 통한 성형품의 표면 특성을 향상시키는 이점이 있다. In addition, the hollow microspheres may have a specific gravity of 0.1 to 0.6 g / cc. More preferably 0.2 to 0.4 g / cc. In this case, the dispersibility in the base resin is increased, thereby improving the surface properties of the molded article through the metal texture.
(C) 금속 입자(C) metal particles
본 발명에서 금속 입자는 메탈 질감을 부여하기 위한 것으로서 알루미늄, 금, 동 또는 이들의 조합을 포함한다. 이때, 상기 금속 입자는 사출 성형 시 분산 배향 변형으로 인한 플로우 마크 또는 웰드 라인이 발생할 수 있으므로 판상형 보다는 구형의 형태를 갖는 것이 바람직하다. 또한, 상기 금속 입자는 평균 입경이 1 내지 150㎛일 수 있으며, 바람직하게는 5 내지 100㎛일 수 있다. 상기 범위에서 중공형 미세구체와의 혼합으로 인한 표면 특성을 상승시킬 수 있는 이점이 있다. In the present invention, the metal particles are for imparting a metal texture and include aluminum, gold, copper, or a combination thereof. In this case, the metal particles may have a spherical shape rather than a plate shape because a flow mark or weld line may occur due to the dispersion orientation deformation during injection molding. In addition, the metal particles may have an average particle diameter of 1 to 150㎛, preferably 5 to 100㎛. There is an advantage that can increase the surface properties due to mixing with the hollow microspheres in the above range.
상기 금속 입자는 베이스 수지(A) 내에 함량이 0.01 내지 10중량부, 바람직하게는 0.02 내지 5중량부일 수 있다.The metal particles may have a content in the base resin (A) of 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight.
본 발명은 유리섬유, 탄소섬유, 유리비드, 유리플레이크, 카본블랙, 클레이, 카올린, 탈크, 마이카, 탄산칼슘　및 규회석(wallostonite)으로 이루어진 군으로부터 선택되는 어느 하나 또는 둘 이상을 더 포함할 수 있다. 이 경우, 성형 가공성 및 외관 특성을 더욱 향상시킬 수 있다.The present invention may further include any one or two or more selected from the group consisting of glass fibers, carbon fibers, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate, and wollastonite. . In this case, the moldability and appearance characteristics can be further improved.
이때, 고품질의 표면 특성 및 메탈 질감의 상승 효과를 위하여 유리섬유, 탈크 및 규회석 중에서 선택되는 어느 하나 이상을 사용하는 것이 바람직하다. 상기 유리섬유는 평균 길이가 0.1 내지 20㎜, 바람직하게는 0.3 내지 10㎜이며, 종횡비(aspect ratio)는 10 내지 2,000, 바람직하게는 30 내지 1,000일 수 있다. At this time, it is preferable to use any one or more selected from glass fiber, talc and wollastonite for high quality surface properties and synergistic effect of the metal texture. The glass fiber may have an average length of 0.1 to 20 mm, preferably 0.3 to 10 mm, and an aspect ratio of 10 to 2,000, preferably 30 to 1,000.
본 발명에서 상기 열가소성 수지 조성물로부터 제조되는 성형품은 별도의 도장(painting) 없이 메탈 질감을 제공할 수 있으며, 상기 성형품의 성능 지표로서 플롭 인덱스(flop index)를 사용하여 우수한 메탈 질감 및 외관 특성을 발현하는 것을 확인할 수 있다. In the present invention, the molded article manufactured from the thermoplastic resin composition may provide a metal texture without additional painting, and expresses excellent metal texture and appearance characteristics by using a flop index as an index of performance of the molded article. You can see that.
상기 플롭 인덱스는 표면의 메탈 질감을 나타내는 지표로 통상 15˚, 45˚ 및 110˚에서의 각 반사광의 루미넌스(L)를 측정하여 아래 정의에 따라 구한다. 　L(x˚)는 x˚에서 측정한 루미넌스를 의미한다.The flop index is an index indicating the metal texture of the surface, and is measured according to the following definition by measuring the luminance L of each reflected light at 15 °, 45 °, and 110 °. L (x˚) means luminance measured at x˚.
금속질감이 없는 표면의 플롭 인덱스는 0, 금속의 플롭 인덱스는 약 15 내지 약 17, 육안으로 금속질감을 느낄 수 있는 표면의 플롭 인덱스는 약 6.5 이상이다.The flop index of the non-metallic surface is 0, the flop index of the metal is about 15 to about 17, and the flop index of the surface which can feel the metallic texture with the naked eye is about 6.5 or more.
본 발명에 따른 열가소성 수지 조성물로부터 제조되는 성형품은 플롭 인덱스가 8이상인 것을 특징으로 한다.The molded article produced from the thermoplastic resin composition according to the present invention is characterized by having a flop index of 8 or more.
본 발명에 따른 열가소성 수지 조성물은 사출 성형 시 플로우 마크(flow mark)와 웰드 라인(weld line) 발생이 거의 없으며, 플롭 인덱스가 8 이상인 성형품을 제공한다. The thermoplastic resin composition according to the present invention provides a molded article having almost no flow mark and weld line during injection molding, and having a flop index of 8 or more.
이하, 본 발명을 보다 구체적으로 설명하기 위하여 하기 일 예를 들어 설명하는 바, 본 발명이 하기 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.
하기 실시예 및 비교예에서 사용된 각 성분의 사양은 다음과 같다.Specifications of each component used in the following Examples and Comparative Examples are as follows.
(a1) 스티렌계 공중합체 수지(a1) Styrene Copolymer Resin
스티렌 75 중량부 및 아크릴로니트릴 25 중량부를 75 ℃에서 5 시간 동안 현탁 중합하여 제조한 중량 평균 분자량 150,000인 스티렌-아크릴로니트릴(SAN) 공중합체 수지를 사용하였다. A styrene-acrylonitrile (SAN) copolymer resin having a weight average molecular weight of 150,000 prepared by suspension polymerization of 75 parts by weight of styrene and 25 parts by weight of acrylonitrile at 75 ° C. for 5 hours was used.
(a2) 고무 변성 비닐계 방향족 공중합체(a2) Rubber-modified vinyl-based aromatic copolymer
단량체 전량에 대하여 부타디엔 함량이 45 중량부가 되도록 폴리부타디엔 고무 라텍스를 투입하고, 스티렌 39 중량부, 아크릴로니트릴 16 중량부 및 탈이온수 150 중량부의 혼합물에 필요한 첨가제인 올레인산 칼륨 1.0 중량부, 큐멘히드로퍼옥시드 0.4 중량부, t-도데실 메르캅탄 연쇄이동제 0.3 중량부를 부가한 후 5 시간 동안 75 ℃로 유지하면서 반응시켜 ABS 그라프트 라텍스(g-ABS)를 제조하였다. 생성된 중합체 라텍스에 1% 황산용액을 첨가하고, 응고시킨 후 건조하여 그라프트 공중합체 수지를 분말 상태로 제조하였다.Polybutadiene rubber latex was added so that the butadiene content was 45 parts by weight based on the total amount of monomers, 1.0 parts by weight of potassium oleate, cumene hydroperox, an additive necessary for a mixture of 39 parts by weight of styrene, 16 parts by weight of acrylonitrile, and 150 parts by weight of deionized water. Seed 0.4 parts by weight, 0.3 parts by weight of t-dodecyl mercaptan chain transfer agent, and then reacted while maintaining at 75 ℃ for 5 hours to prepare an ABS graft latex (g-ABS). A 1% sulfuric acid solution was added to the resulting polymer latex, solidified and dried to prepare a graft copolymer resin in a powder state.
(B) 중공형 미세구체(B) hollow microspheres
3M사의 직경 40㎛, 압축강도 40,000psi, 비중 0.3g/cc인 글라스 버블을 사용하였다. A glass bubble having a diameter of 40 μm, a compressive strength of 40,000 psi, and a specific gravity of 0.3 g / cc was used.
(C) 금속 입자(C) metal particles
평균 입경이 10㎛인 구형 알루미늄 입자(마이크로 메탈사, 제품명:Al 분말)를 사용하였다.Spherical aluminum particles (Micro Metal, product name: Al powder) having an average particle diameter of 10 µm were used.
(실시예 1 및 2)(Examples 1 and 2)
상기에서 언급된 구성성분들을 이용하여 하기 표 1에 나타낸 조성으로 열가소성 수지 조성물을 제조한 뒤, 통상의 이축 압출기에서 240℃에서 압출한 후, 압출물을 펠렛 형태로 제조한 후 물성 평가하여 그 결과를 나타내었다. 표 1의 함량은 (a1) 및 (a2)의 함량은 중량%이며, 중공형 미세구체 및 금속 입자는 상기 (a1)+(a2)=100 중량부 대비 상대 함량(중량부)로 나타내었다. After preparing the thermoplastic resin composition with the composition shown in Table 1 by using the above-mentioned components, and then extruded at 240 ℃ in a conventional twin screw extruder, the extrudate is prepared in pellet form and then evaluated by physical properties Indicated. In Table 1, the contents of (a1) and (a2) are in weight percent, and the hollow microspheres and metal particles are expressed as relative contents (parts by weight) relative to (a1) + (a2) = 100 parts by weight.
(실시예 3)(Example 3)
글라스 버블의 압축 강도가 30,000psi인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.It was prepared in the same manner as in Example 1 except that the compressive strength of the glass bubble is 30,000psi.
(실시예 4)(Example 4)
글라스 버블의 직경이 30㎛인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다. A glass bubble was manufactured in the same manner as in Example 1, except that the diameter was 30 μm.
(비교예 1)(Comparative Example 1)
중공형 미세구체를 사용하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다. It was prepared in the same manner as in Example 1 except that no hollow microspheres were used.
(비교예 2)(Comparative Example 2)
중공형 미세구체의 함량이 0.5 중량부를 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다It was prepared in the same manner as in Example 1 except that the content of the hollow microspheres was 0.5 parts by weight.
(비교예 3)(Comparative Example 3)
중공형 미세구체의 함량이 15 중량부를 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다A hollow microsphere was prepared in the same manner as in Example 1, except that the content of 15 parts by weight was used.
(비교예 4)(Comparative Example 4)
중공형 미세구체의 압축 강도가 5,000psi인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.Except that the compressive strength of the hollow microspheres of 5,000 psi was prepared in the same manner as in Example 1.
(비교예 5)(Comparative Example 5)
중공형 미세구체의 압축 강도가 70,000psi인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.Except that the compressive strength of the hollow microspheres of 70,000psi was prepared in the same manner as in Example 1.
(비교예 6)(Comparative Example 6)
중공형 미세구체(글라스 버블)의 직경이 5㎛인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.A hollow microsphere (glass bubble) was prepared in the same manner as in Example 1 except that the diameter of 5 μm was used.
(비교예 7)(Comparative Example 7)
중공형 미세구체(글라스 버블)의 직경이 150㎛인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.A hollow microsphere (glass bubble) was prepared in the same manner as in Example 1 except that the diameter of 150 µm was used.
(비교예 8)(Comparative Example 8)
금속 입자(알루미늄 입자)의 입경이 0.5㎛인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.A metal particle (aluminum particle) was produced in the same manner as in Example 1 except that a particle diameter of 0.5 µm was used.
(비교예 9)(Comparative Example 9)
금속 입자(알루미늄 입자)의 입경이 200㎛인 것을 사용하는 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.A metal particle (aluminum particle) was produced in the same manner as in Example 1 except that the particle diameter was 200 μm.
(물성 평가)(Property evaluation)
1) 메탈 질감1) metal texture
플롭 지수(Flop index)를 측정 기기 (제조사: BYK, 모델명: BYK Mac)를 사용하여 측정하였다. 　15˚, 45˚ 및 110˚세 가지 각도를 종합하여 알루미늄 입자 고유의 질감인 플립-플랍 효과(flip-flop effect)를 평가하였고, 그 값을 하기 표 1에 기재하였다.The flop index was measured using a measuring instrument (manufacturer: BYK, model name: BYK Mac). The flip-flop effect, which is the texture of the aluminum particles, was evaluated by combining three angles of 15 °, 45 °, and 110 °, and the values are shown in Table 1 below.
2) 사출 외관: 상기 사출 성형시 게이트(gate)를 2개 가지고 있는 금형을 사용하여 사출하였기 때문에 웰드 라인(weld line)이 발생할 수 있다. 　사출물의 외관을 육안으로 관찰하여 하기 평가 기준에 따라 판단한 결과를 하기 표 1에 나타내었다.2) Injection appearance: A weld line may occur since the injection molding is performed using a mold having two gates. The appearance of the injection molding was visually observed, and the results determined according to the following evaluation criteria are shown in Table 1 below.
◎ : 플로우 마크(flow mark)나 웰드 라인에서 이색이 전혀 없는 상태.(Double-circle): No abnormal color in a flow mark and a weld line.
○ : 플로우 마크가 없으나 웰드 라인에서 이색이 조금 있는 상태.(Circle): There is no flow mark but there is a little difference in weld line.
△ : 플로우 마크와 웰드 라인에서 이색이 나타나는 상태.(Triangle | delta): A state where a different color appears in a flow mark and a weld line.
× : 플로우 마크와 웰드 라인에서 이색이 심하게 나타나는 상태.X: The state which aberrant color appears badly in a flow mark and a weld line.
Figure PCTKR2014000967-appb-I000001
Figure PCTKR2014000967-appb-I000001
상기 표 1에서 볼 수 있는 바와 같이, 본 발명에 따른 실시예 1 내지 4는 비교예들과 비교 시 플롭 인덱스값이 높게 나타나 매우 우수한 메탈 질감을 가지면서도 플로우 마크나 웰드 라인이 발생하지 않아 외관 특성이 뛰어남을 확인할 수 있었다. As can be seen in Table 1, Examples 1 to 4 according to the present invention have a high flop index value when compared with the comparative examples, and have a very good metal texture, but do not generate flow marks or weld lines. I could confirm this superiority.
이상과 같이 본 발명에서는 한정된 실시예에 의해 설명되었으나 이는 본 발명의 보다 전반적인 이해를 돕기 위해서 제공된 것일 뿐, 본 발명은 상기의 실시예에 한정되는 것은 아니며, 본 발명이 속하는 분야에서 통상의 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형이 가능하다. As described above in the present invention has been described by a limited embodiment, but this is only provided to help a more general understanding of the present invention, the present invention is not limited to the above embodiments, the present invention is not limited to the common knowledge Those having a variety of modifications and variations are possible from these descriptions.
따라서, 본 발명의 사상은 설명된 실시예에 국한되어 정해져서는 아니되며, 후술하는 특허청구범위뿐 아니라 이 특허청구범위와 균등하거나 등가적 변형이 있는 모든 것들은 본 발명 사상의 범주에 속한다고 할 것이다.Therefore, the spirit of the present invention should not be limited to the described embodiments, and all the things that are equivalent to or equivalent to the claims as well as the following claims will belong to the scope of the present invention. .

Claims (13)

  1. (A) (a1) 스티렌계 공중합체 수지 및 (a2) 고무 변성 비닐계 방향족 공중합체로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 열가소성 수지,(A) a thermoplastic resin containing at least one selected from the group consisting of (a1) a styrene copolymer resin and (a2) a rubber-modified vinyl aromatic copolymer,
    (B) 중공형 미세구체 및 (B) hollow microspheres and
    (C) 금속 입자를 포함하는 열가소성 수지 조성물.(C) A thermoplastic resin composition containing metal particles.
  2. 제 1항에 있어서,The method of claim 1,
    상기 열가소성 수지 조성물은 (A) (a1) 스티렌계 공중합체 수지 및 (a2) 고무 변성 비닐계 방향족 공중합체로 이루어진 군으로부터 선택되는 어느 하나 이상을 포함하는 열가소성 수지 100중량부에 대하여, (B) 중공형 미세구체 1 내지 10중량부 및 (C) 금속 입자 0.01 내지 10중량부를 포함하는 열가소성 수지 조성물.The thermoplastic resin composition is based on 100 parts by weight of a thermoplastic resin containing any one or more selected from the group consisting of (A) (a1) a styrene copolymer resin and (a2) a rubber-modified vinyl aromatic copolymer, (B) 1 to 10 parts by weight of the hollow microspheres and 0.01 to 10 parts by weight of the metal particles (C).
  3. 제 1항에 있어서,The method of claim 1,
    상기 중공형 미세구체는 글라스 버블(glass buble)을 포함하는 열가소성 수지 조성물.The hollow microsphere is a thermoplastic resin composition comprising a glass bubble (glass buble).
  4. 제3항에 있어서,The method of claim 3,
    상기 중공형 미세구체는 10 내지 80㎛의 직경을 가지는 열가소성 수지 조성물. The hollow microspheres have a thermoplastic resin composition having a diameter of 10 to 80㎛.
  5. 제 3항에 있어서,The method of claim 3, wherein
    상기 글라스 버블은 압축강도가 14,000 내지 50,000psi인 열가소성 수지 조성물. The glass bubble has a compressive strength of 14,000 to 50,000 psi thermoplastic resin composition.
  6. 제 3항에 있어서,The method of claim 3, wherein
    상기 글라스 버블은 비중이 0.1 내지 0.6g/cc인 열가소성 수지 조성물. The glass bubble has a specific gravity of 0.1 to 0.6 g / cc thermoplastic resin composition.
  7. 제 1항에 있어서,The method of claim 1,
    상기 금속 입자는 평균입경이 1 내지 150㎛ 인 열가소성 수지 조성물. The metal particles have an average particle diameter of 1 to 150 μm.
  8. 제 1항에 있어서,The method of claim 1,
    상기 금속 입자는 알루미늄, 구리, 금 및 이들의 조합에서 선택되는 열가소성 수지 조성물.The metal particles are selected from aluminum, copper, gold, and combinations thereof.
  9. 제 1항에 있어서,The method of claim 1,
    상기 스티렌계 공중합체 수지(a1)는 방향족 비닐 화합물 또는 이들의 혼합물 50∼95 중량%와 (메타)아크릴산 알킬 에스테르계 또는 이들의 혼합물 5∼50 중량%을 공중합하여 제조된 공중합체 또는 이들 공중합체의 혼합물인 열가소성 수지 조성물.The styrene copolymer resin (a1) is a copolymer prepared by copolymerizing 50 to 95% by weight of an aromatic vinyl compound or a mixture thereof and 5 to 50% by weight of a (meth) acrylic acid alkyl ester or a mixture thereof. Thermoplastic resin composition.
  10. 제 1항에 있어서,The method of claim 1,
    상기 고무변성 비닐계 그라프트 공중합체(a2)는 비닐계 단량체 혼합물 5∼95 중량%를 고무질 중합체 5∼95 중량%에 그라프트 중합한 그라프트 공중합체인 것을 열가소성 수지 조성물.The rubber modified vinyl graft copolymer (a2) is a thermoplastic resin composition which is a graft copolymer obtained by graft polymerization of 5 to 95% by weight of a vinyl monomer mixture to 5 to 95% by weight of a rubbery polymer.
  11. 제 1항에 있어서,The method of claim 1,
    유리섬유, 탄소섬유, 유리비드, 유리플레이크, 카본블랙, 클레이, 카올린, 탈크, 마이카, 탄산칼슘　및 규회석(wallostonite)으로 이루어진 군으로부터 선택되는 적어도 어느 하나를 더 포함하는 열가소성 수지 조성물.A thermoplastic resin composition further comprising at least one selected from the group consisting of glass fibers, carbon fibers, glass beads, glass flakes, carbon black, clay, kaolin, talc, mica, calcium carbonate, and wollastonite.
  12. 제 1항 내지 제 11항 중에서 선택되는 어느 한 항의 조성물로부터 제조되는 성형품.A molded article prepared from the composition of any one of claims 1 to 11.
  13. 제 12항에 있어서,The method of claim 12,
    상기 성형품은 플롭 인덱스(flop index)가 8 이상인 것을 특징으로 하는 성형품.The molded article is a molded article, characterized in that the flop index (flop index) is 8 or more.
PCT/KR2014/000967 2013-06-28 2014-02-05 Thermoplastic resin composition and moulded article using same WO2014208857A1 (en)

Applications Claiming Priority (2)

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KR101899638B1 (en) * 2015-12-31 2018-09-17 롯데첨단소재(주) Thermoplastic resin composition and molded article using thereof
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KR20130066942A (en) * 2011-12-13 2013-06-21 제일모직주식회사 Thermoplastic resin composition and molded product using the same

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