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WO2014208857A1 - Composition de résine thermoplastique et article moulé obtenu au moyen de celle composition - Google Patents

Composition de résine thermoplastique et article moulé obtenu au moyen de celle composition 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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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
resin composition
weight
copolymer
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/000967
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English (en)
Korean (ko)
Inventor
이선애
함민경
권영철
박강열
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cheil Industries Inc
Original Assignee
Cheil Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cheil Industries Inc filed Critical Cheil Industries Inc
Publication of WO2014208857A1 publication Critical patent/WO2014208857A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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

L'invention concerne une composition de résine thermoplastique présentant une stabilité dimensionnelle, une aptitude au moulage, une résistance aux chocs, une résistance aux intempéries et des propriétés mécaniques exceptionnelles et, dans un même temps, elle permet d'empêcher les marques de soufflage et les lignes de soudure pouvant apparaître pendant le moulage par injection et elle permet d'améliorer considérablement la texture, le brillant et l'apparence du métal.
PCT/KR2014/000967 2013-06-28 2014-02-05 Composition de résine thermoplastique et article moulé obtenu au moyen de celle composition Ceased WO2014208857A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020130075196A KR20150001991A (ko) 2013-06-28 2013-06-28 열가소성 수지 조성물 및 이를 이용한 성형품
KR10-2013-0075196 2013-06-28

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WO2014208857A1 true WO2014208857A1 (fr) 2014-12-31

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Publication number Priority date Publication date Assignee Title
KR101899638B1 (ko) * 2015-12-31 2018-09-17 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품
KR20180071835A (ko) 2016-12-20 2018-06-28 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품
KR102294339B1 (ko) * 2017-12-20 2021-08-26 (주)엘엑스하우시스 경량 바닥재
KR20190101133A (ko) * 2018-02-22 2019-08-30 롯데첨단소재(주) 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR102453651B1 (ko) * 2018-11-06 2022-10-12 (주)엘엑스하우시스 타일 바닥재 및 이의 제조방법

Citations (4)

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KR0168873B1 (ko) * 1990-10-09 1999-03-20 로저 퀘스텔 고체 금속소재의 질감을 가지는 플라스틱 성형소재
KR20110079466A (ko) * 2009-12-31 2011-07-07 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20120115981A (ko) * 2009-12-18 2012-10-19 바이엘 인텔렉쳐 프로퍼티 게엠베하 우수한 기계적 특성 ⅱ을 갖는 내스크래치성 내충격성 폴리카르보네이트 성형 조성물
KR20130066942A (ko) * 2011-12-13 2013-06-21 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0168873B1 (ko) * 1990-10-09 1999-03-20 로저 퀘스텔 고체 금속소재의 질감을 가지는 플라스틱 성형소재
KR20120115981A (ko) * 2009-12-18 2012-10-19 바이엘 인텔렉쳐 프로퍼티 게엠베하 우수한 기계적 특성 ⅱ을 갖는 내스크래치성 내충격성 폴리카르보네이트 성형 조성물
KR20110079466A (ko) * 2009-12-31 2011-07-07 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20130066942A (ko) * 2011-12-13 2013-06-21 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품

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