WO2021221429A1 - Composition de résine thermoplastique et produit moulé faisant appel à celle-ci - Google Patents

Composition de résine thermoplastique et produit moulé faisant appel à celle-ci Download PDF

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Publication number
WO2021221429A1
WO2021221429A1 PCT/KR2021/005297 KR2021005297W WO2021221429A1 WO 2021221429 A1 WO2021221429 A1 WO 2021221429A1 KR 2021005297 W KR2021005297 W KR 2021005297W WO 2021221429 A1 WO2021221429 A1 WO 2021221429A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
resin composition
thermoplastic resin
styrene
vinyl cyanide
Prior art date
Application number
PCT/KR2021/005297
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English (en)
Korean (ko)
Inventor
최우진
임재석
황동근
권기혜
Original Assignee
롯데케미칼 주식회사
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
Priority claimed from KR1020210053888A external-priority patent/KR102717806B1/ko
Application filed by 롯데케미칼 주식회사 filed Critical 롯데케미칼 주식회사
Priority to CN202180029836.2A priority Critical patent/CN115516029A/zh
Publication of WO2021221429A1 publication Critical patent/WO2021221429A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • 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

Definitions

  • thermoplastic resin composition relates to a thermoplastic resin composition and a molded article using the same.
  • Styrene-based resins represented by acrylonitrile-butadiene-styrene copolymer (ABS) resins, are widely used in automobiles, home appliances, OA devices, etc. due to their excellent moldability, mechanical properties, appearance, secondary processability, and the like.
  • ABS acrylonitrile-butadiene-styrene copolymer
  • a molded article using a styrene-based resin may be applied to various products requiring painting/unpainted, for example, may be applied to interior/exterior materials for automobiles.
  • the existing vehicle rear lamp (rear lamp) has a separate left and right, but recently, it has become a trend for the rear lamp of the vehicle to have an integrated structure without separating the left and right.
  • the rear lamp portion of the recent vehicle has more intermediate connecting portions connecting the left and right lamps.
  • excessive stress is likely to occur in a specific area, and thus, there is a problem in that chemical resistance is likely to occur in the corresponding area.
  • the styrene-based resin needs to have excellent flow characteristics.
  • thermoplastic resin composition having excellent fluidity and heat resistance suitable for large-sized automobile lamp housings, and having excellent chemical resistance.
  • An object of the present invention is to provide a high-flowing thermoplastic resin composition excellent in both heat resistance and chemical resistance, and a molded article using the same.
  • One embodiment is (A) 25 to 50% by weight of a butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer, (B) 30 to 50% by weight of an aromatic vinyl-vinyl cyanide copolymer, and (C) N-phenyl maleate
  • a thermoplastic resin composition comprising 15 to 25 wt% of a mid-maleic anhydride-styrene-acrylonitrile copolymer.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a core comprising a butadiene-based rubber polymer having an average particle diameter of 250 to 350 nm, and an aromatic vinyl compound and a vinyl cyanide compound are graft-polymerized onto the core. It may be a core-shell structure including a formed shell.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
  • the (B) aromatic vinyl compound-vinyl cyanide compound copolymer has a weight average molecular weight of 90,000 to 100,000 g/mol, and may include 20 to 28 wt% of a component derived from a vinyl cyanide compound.
  • the aromatic vinyl compound is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, It may be selected from the group consisting of dibromostyrene, vinylnaphthalene, and combinations thereof.
  • the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.
  • the (B) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer may include 30 to 50 wt% of a component derived from N-phenyl maleimide.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer comprises 35 to 45 wt% of N-phenyl maleimide-derived component, 1 to 5 wt% of maleic anhydride-derived component, and 45 wt% of styrene-derived component to 55% by weight, and 5 to 15% by weight of an acrylonitrile-derived component.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer may have a weight average molecular weight of 100,000 to 150,000 g/mol.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer may have a glass transition temperature (Tg) of 150 to 180°C.
  • the thermoplastic resin composition may further include at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, a UV stabilizer, a flame retardant, an antistatic agent, and a colorant.
  • at least one additive selected from a nucleating agent, a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, a UV stabilizer, a flame retardant, an antistatic agent, and a colorant.
  • Another embodiment provides a molded article including the above-described thermoplastic resin composition.
  • the molded article may have a melt flow index of 10 to 15 g/10min measured at 220°C and a load of 10 kg according to ASTM D1238.
  • the molded article may have a heat deflection temperature (HDT) measured at 0.45 MPa according to ASTM D648 of 107° C. or higher.
  • HDT heat deflection temperature
  • thermoplastic resin composition according to an embodiment and a molded article using the same can exhibit excellent chemical resistance while having excellent fluidity and heat resistance, and thus can be widely applied to various products used for painting and unpainting, for example, automotive exterior materials. , in particular, can be usefully applied to applications requiring heat resistance and/or chemical resistance, such as a housing for automobile lamps.
  • 'copolymerization means block copolymerization or random copolymerization
  • 'copolymer' means block copolymer or random copolymer.
  • the term 'average particle diameter' is a volume average diameter, and means a Z-average particle diameter measured using a dynamic light scattering analyzer.
  • a powder sample of 'weight average molecular weight' is dissolved in tetrahydrofuran (THF) and then measured using gel permeation chromatography (GPC, Agilent Technologies 1200 series) (column). indicates that Shodex's LF-804 was used, and the standard sample used was Shodex's polystyrene).
  • thermoplastic resin composition comprising 15 to 25 wt% of a phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer.
  • thermoplastic resin composition is demonstrated in detail.
  • (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer imparts excellent impact resistance to the thermoplastic resin composition.
  • the average particle diameter of the rubber polymer of the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is 250 nm or more, 260 nm or more, or 270 nm or more, and 350 nm or less, 340 nm or less, 330 nm or less, 320 nm or less, or 310 nm or less.
  • the thermoplastic resin composition may secure excellent impact resistance and appearance characteristics.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a core comprising a butadiene-based rubber polymer, and an aromatic vinyl compound and a vinyl cyanide compound are graft-polymerized onto the core. It may be a core-shell structure including a formed shell.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is a butadiene-based rubber polymer by adding an anti-aromatic vinyl compound and a vinyl cyanide compound to the butadiene-based rubber polymer, and graft polymerization through conventional polymerization methods such as emulsion polymerization and bulk polymerization. can be manufactured.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is 45 wt% or more, 48 wt% or more, 50 wt% or more, 53 wt% or more, or 55 wt% of the core based on 100 wt% or more, and 65% by weight or less, 63% by weight or less, or 60% by weight or less.
  • the aromatic vinyl compound and the vinyl cyanide compound may be copolymerized in a weight ratio of 6:4 to 8:2.
  • the butadiene-based rubbery polymer may be selected from the group consisting of butadiene rubbery polymers, butadiene-styrene rubbery polymers, butadiene-acrylonitrile rubbery polymers, butadiene-acrylate rubbery polymers, and mixtures thereof.
  • the aromatic vinyl compound may be selected from the group consisting of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and combinations thereof. may be selected.
  • the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer may be an acrylonitrile-butadiene-styrene graft copolymer.
  • the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is 25 wt% or more, 26 wt% or more, 27 wt% or more, 28 wt% or more, 29 wt% or more, 30 wt% or more, 31 wt% or more, or 32 wt% or more, and 50 wt% or less, 49 wt% or less, 48 wt% or less, 47 wt% or less, 46 wt% or more or less, or 45% by weight or less.
  • the thermoplastic resin composition can secure excellent impact resistance and appearance characteristics.
  • thermoplastic resin composition when the (A) butadiene-based rubber-modified aromatic vinyl-vinyl cyanide graft copolymer is included in an amount of less than 25% by weight, it is difficult for the thermoplastic resin composition to achieve excellent chemical resistance and high flowability, and when it exceeds 50% by weight There exists a possibility that the heat resistance of a thermoplastic resin composition may fall.
  • (B) aromatic vinyl-vinyl cyanide copolymer provides excellent fluidity to the thermoplastic resin composition and performs a function of maintaining compatibility between components at a certain level.
  • the (B) aromatic vinyl-vinyl cyanide copolymer may include 20 to 28 wt% of a component derived from a vinyl cyanide compound.
  • the vinyl cyanide compound-derived component When the vinyl cyanide compound-derived component is included in an amount of less than 20% by weight, the fluidity of the thermoplastic resin composition may be increased, but there is a risk of lowering chemical resistance. Therefore, there is a need to include the vinyl cyanide compound-derived component in an appropriate range, and when included in an amount of 20 to 28% by weight, the thermoplastic resin composition having an appropriate level of excellent fluidity and excellent chemical resistance at the same time can provide
  • the (B) aromatic vinyl-vinyl cyanide copolymer may be a copolymer of a monomer mixture comprising 72 to 80 wt% of an aromatic vinyl compound and 20 to 28 wt% of a vinyl cyanide compound based on 100 wt%.
  • the (B) aromatic vinyl-vinyl cyanide copolymer has a weight average molecular weight (Mw) of 90,000 g/mol or more, 91,000 g/mol or more, 92,000 g/mol or more, or 93,000 g/mol or more, and 100,000 g/mol or more. mol or less, 99,000 g/mol or less, 98,000 g/mol or less, or 97,000 g/mol or less.
  • Mw weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer
  • the (B) aromatic vinyl-vinyl cyanide copolymer may have the above weight average molecular weight range by mixing two or more aromatic vinyl-vinyl cyanide copolymers having different weight average molecular weights.
  • the aromatic vinyl compound is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibro It may be selected from the group consisting of parent styrene, vinyl naphthalene, and combinations thereof.
  • the vinyl cyanide compound may be selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, and combinations thereof.
  • the (B) aromatic vinyl-vinyl cyanide copolymer may be a styrene-acrylonitrile copolymer.
  • the (B) aromatic vinyl-vinyl cyanide copolymer is 30 wt% or more, 31 wt% or more, 32 wt% or more, 33 wt% or more, 34 % by weight or more, or 35% by weight or more, and 50% by weight or less, 49% by weight or less, 48% by weight or less, 47% by weight or less, 46% by weight or less, or 45% by weight or less.
  • thermoplastic resin composition when the (B) aromatic vinyl-vinyl cyanide copolymer is less than 30% by weight, there is a fear that the fluidity of the thermoplastic resin composition may decrease, and if it exceeds 50% by weight, the heat resistance of the thermoplastic resin composition may decrease.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer imparts excellent heat resistance to the thermoplastic resin composition.
  • thermoplastic resin composition when the weight average molecular weight of the (B) aromatic vinyl-vinyl cyanide copolymer increases, it is advantageous in terms of chemical resistance, but as the weight average molecular weight increases, the fluidity of the thermoplastic resin composition decreases, so there is a limit to realizing high fluidity. have. Accordingly, when the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer is introduced, the thermoplastic resin composition may have high fluidity while maintaining excellent chemical resistance.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer may include 30 to 50 wt% of an N-phenyl maleimide-derived component based on 100 wt%.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer contains 35 to 45% by weight of a component derived from N-phenyl maleimide and 1 to 5% by weight of a component derived from maleic anhydride based on 100% by weight of the N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer %, 45 to 55% by weight of a component derived from styrene, and 5 to 15% by weight of a component derived from acrylonitrile.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer contains less than 30% by weight of the N-phenyl maleimide-derived component based on 100% by weight, the heat resistance improvement effect is difficult to be expressed, If it exceeds 50% by weight, there is a fear that the appearance characteristics of the thermoplastic resin composition and the molded article using the same may be greatly reduced.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer may have a weight average molecular weight of 100,000 to 150,000 g/mol.
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer has a glass transition temperature (Tg) of 150°C or more, 155°C or more, 160°C or more, or 165°C or more, and 180°C or less , 178° C. or less, or 175° C. or less.
  • Tg glass transition temperature
  • the (C) N-phenyl maleimide-maleic anhydride-styrene-acrylonitrile copolymer is 15 wt% or more, 16 wt% or more, 17 % by weight or more, 18% by weight or more, or 19% by weight or more, and 25% by weight or less, 24% by weight or less, or 23% by weight or less.
  • thermoplastic resin composition in addition to the components (A) to (C), in order to balance the respective physical properties under conditions of maintaining excellent fluidity, heat resistance, and chemical resistance, or the final composition of the thermoplastic resin composition It may further include one or more additives required depending on the use.
  • a nucleating agent a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, an antistatic agent, a colorant.
  • a nucleating agent a coupling agent, a filler, a plasticizer, a lubricant, a mold release agent, an antibacterial agent, a heat stabilizer, an antioxidant, an ultraviolet stabilizer, a flame retardant, an antistatic agent, a colorant.
  • additives may be appropriately included within a range that does not impair the physical properties of the thermoplastic resin composition, and specifically, may be included in an amount of 20 parts by weight or less based on 100 parts by weight of components (A) to (C), but is limited thereto no.
  • thermoplastic resin composition according to the present invention may be prepared by a known method for preparing a thermoplastic resin composition.
  • thermoplastic resin composition according to the present invention may be prepared in the form of pellets by mixing the components of the present invention and other additives at the same time and then melt-kneading in an extruder.
  • the molded article according to an embodiment of the present invention may be prepared from the above-described thermoplastic resin composition.
  • the molded article has a melt flow index of 10 g/10min or more, 10.5 g/10min or more, 11 g/10min or more, 11.5 g/10min or more, measured at 220°C and 10 kg load condition according to ASTM D1238, or 12 g/10 min or more, and 15 g/10 min or less, 14.5 g/10 min or less, 14 g/10 min or less, 13.5 g/10 min or less, or 13 g/10 min or less.
  • the heat deflection temperature (HDT) measured at 0.45 MPa condition according to ASTM D648 may be 107 ° C. or higher, for example 108 ° C. or higher, for example 109 ° C. or higher, for example 110 ° C. or higher.
  • thermoplastic resin composition Since the thermoplastic resin composition satisfies high flow and high heat resistance characteristics and exhibits excellent chemical resistance at the same time, it can be widely applied to the molding of various products used for painting and unpainting, for example, automotive exterior materials, in particular, automotive lamps. It can be usefully applied to applications requiring high fluidity as well as heat resistance and chemical resistance, such as a housing for a vehicle, more specifically, a vehicle head lamp housing and/or a rear lamp housing.
  • thermoplastic resin compositions of Examples 1 to 3 and Comparative Examples 1 to 4 were prepared according to the component content ratios shown in Table 1 below.
  • thermoplastic resin composition pelletized through a twin-screw extruder was dried at about 80° C. for about 4 hours, and then a specimen for evaluation of physical properties was prepared using a 6 oz injection molding machine having a cylinder temperature of about 240° C. and a mold temperature of about 60° C.
  • Acrylonitrile comprising about 58% by weight of a core comprising a butadiene rubbery polymer having an average particle diameter of about 260 nm, and a shell in which styrene and acrylonitrile are graft polymerized in a weight ratio of about 7.5:2.5 to the core- Butadiene-styrene graft copolymer (Lotte Chemical)
  • N-phenyl maleimide-maleic anhydride-styrene copolymer comprising about 21 wt% of an N-phenyl maleimide-derived component, about 7 wt% of a maleic anhydride-derived component, and about 72 wt% of a styrene-derived component (Polyscope)
  • Flowability (unit: g/10min): Melt-flow index (MI) was measured at 220° C. and 10 kg load condition according to ASTM D1238.

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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

La présente invention concerne une composition de résine thermoplastique et un produit moulé faisant appel à celle-ci, la composition de résine thermoplastique comprenant : (A) de 25 à 50 % en poids de copolymère greffé de cyanure de vinyle-vinyle aromatique modifié par du caoutchouc butadiène ; (B) de 30 à 50 % en poids de copolymère cyanure de vinyle-vinyle aromatique ; et (C) de 15 à 25 % en poids de copolymère N-phénylmaléimide-anhydride maléique-styrène-acrylonitrile.
PCT/KR2021/005297 2020-04-29 2021-04-27 Composition de résine thermoplastique et produit moulé faisant appel à celle-ci WO2021221429A1 (fr)

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CN202180029836.2A CN115516029A (zh) 2020-04-29 2021-04-27 热塑性树脂组合物及利用它而成的成型品

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KR10-2020-0052875 2020-04-29
KR20200052875 2020-04-29
KR10-2021-0053888 2021-04-26
KR1020210053888A KR102717806B1 (ko) 2020-04-29 2021-04-26 열가소성 수지 조성물 및 이를 이용한 성형품

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Citations (6)

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KR20000048600A (ko) * 1996-09-26 2000-07-25 스타르크, 카르크 열가소성 물질의 제조 방법
KR20130062779A (ko) * 2011-12-05 2013-06-13 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20160067675A (ko) * 2014-12-04 2016-06-14 주식회사 엘지화학 열가소성 수지 조성물 및 이를 적용한 성형품
US20180346708A1 (en) * 2015-11-23 2018-12-06 Elix Polymers, S.L. Thermoplastic abs composition reinforced with natural fibres
KR20190082074A (ko) * 2017-12-29 2019-07-09 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품

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KR100781963B1 (ko) * 2006-12-29 2007-12-06 제일모직주식회사 발포 압출용 내열성 열가소성 수지 조성물
JP2011169921A (ja) * 2008-06-12 2011-09-01 Denki Kagaku Kogyo Kk 光学成形体用樹脂組成物及びその光学成形体
KR102264007B1 (ko) * 2017-12-29 2021-06-11 롯데첨단소재(주) 블로우 몰딩용 열가소성 수지 조성물 및 이를 이용한 성형품

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5047470A (en) * 1989-07-28 1991-09-10 General Electric Company High impact blends of copolyether-ester elastomers, rubber graft polymers and styrene-acrylonitrile rigid polymers
KR20000048600A (ko) * 1996-09-26 2000-07-25 스타르크, 카르크 열가소성 물질의 제조 방법
KR20130062779A (ko) * 2011-12-05 2013-06-13 제일모직주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20160067675A (ko) * 2014-12-04 2016-06-14 주식회사 엘지화학 열가소성 수지 조성물 및 이를 적용한 성형품
US20180346708A1 (en) * 2015-11-23 2018-12-06 Elix Polymers, S.L. Thermoplastic abs composition reinforced with natural fibres
KR20190082074A (ko) * 2017-12-29 2019-07-09 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 이용한 성형품

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