WO2020091371A1 - Composition de résine thermoplastique - Google Patents

Composition de résine thermoplastique Download PDF

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Publication number
WO2020091371A1
WO2020091371A1 PCT/KR2019/014351 KR2019014351W WO2020091371A1 WO 2020091371 A1 WO2020091371 A1 WO 2020091371A1 KR 2019014351 W KR2019014351 W KR 2019014351W WO 2020091371 A1 WO2020091371 A1 WO 2020091371A1
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WO
WIPO (PCT)
Prior art keywords
thermoplastic resin
weight
resin composition
copolymer
monomer
Prior art date
Application number
PCT/KR2019/014351
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English (en)
Korean (ko)
Inventor
조준휘
김성룡
이대우
서재범
Original Assignee
주식회사 엘지화학
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 KR1020190134501A external-priority patent/KR102298296B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP19878064.5A priority Critical patent/EP3875534A4/fr
Priority to US17/054,459 priority patent/US11608401B2/en
Priority to CN201980030295.8A priority patent/CN112105690A/zh
Priority to JP2020560816A priority patent/JP7205976B2/ja
Publication of WO2020091371A1 publication Critical patent/WO2020091371A1/fr

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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
    • 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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • 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

Definitions

  • the present invention relates to a thermoplastic resin composition, and relates to a thermoplastic resin composition excellent in colorability, weather resistance, tensile strength, flexural strength and impact strength.
  • thermoplastic resin composition comprising a diene-based graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer on a diene-based rubbery polymer has excellent impact resistance, stiffness, chemical resistance, and processability, and provides electrical, electronic, and construction , Used in various fields such as automobiles. However, it is not suitable as an outdoor material due to its weak weather resistance.
  • thermoplastic resin composition having excellent weather resistance and aging resistance, and an acrylic graft copolymer obtained by graft polymerization of an aromatic vinyl-based monomer and a vinyl cyan-based monomer on an acrylic rubbery polymer has been spotlighted as an alternative.
  • the thermoplastic resin composition containing the acrylic graft copolymer is difficult to be applied to products requiring high quality due to poor colorability.
  • thermoplastic resin composition having excellent weatherability as well as coloring properties is continuing.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in weather resistance, colorability, tensile strength, flexural strength and impact strength.
  • the present invention is a first graft copolymer comprising a C 4 to C 10 alkyl (meth) acrylate monomer units, aromatic vinyl monomer units and vinyl cyan monomer units; A second graft copolymer comprising C 4 to C 10 alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units; And a first styrenic copolymer that is a copolymer of a monomer mixture comprising a C 1 to C 3 alkyl substituted styrene monomer, a vinyl cyan monomer, and a C 1 to C 3 alkyl (meth) acrylate monomer,
  • the first graft copolymer and the second graft copolymer provide a thermoplastic resin composition having different average particle diameters of the core.
  • thermoplastic resin composition according to the present invention is excellent in mechanical properties such as tensile strength, flexural strength, impact strength, etc., while also significantly improving colorability and weatherability.
  • the thermoplastic resin composition according to the present invention is a copolymer of a monomer mixture comprising a C 1 to C 3 alkyl-substituted styrene-based monomer, a vinyl cyan-based monomer, and a C 1 to C 3 alkyl (meth) acrylate-based monomer.
  • the average particle diameter of the first and second graft copolymers can be measured using a dynamic light scattering method, and specifically, measured using Nicomp 380 HPL equipment (product name, manufacturer: Nicomp). can do.
  • the arithmetic mean particle size in the particle size distribution measured by the dynamic light scattering method that is, the average particle size of the scattering intensity.
  • the graft ratio of the first and second graft copolymers can be calculated by the following equation.
  • Graft ratio (%) weight of grafted monomer (g) / weight of crosslinked polymer (g) ⁇ 100
  • Weight of grafted monomer (g) weight of insoluble material (gel) after dissolving 1 g of graft copolymer in 30 g of acetone and centrifuging
  • Weight of crosslinked polymer (g) The weight of C 4 to C 10 alkyl (meth) acrylate monomers theoretically added in the graft copolymer powder
  • the weight average molecular weight of the first styrene-based copolymer, the second styrene-based copolymer, and the (meth) acrylic-based polymer is tetrahydrofuran as an eluent, and is subjected to a standard PS (standard polystyrene) sample through gel permeation chromatography. It can be measured as a relative value for.
  • PS standard polystyrene
  • the polymer should be understood as a concept including both a homopolymer formed by polymerizing one monomer and a copolymer formed by polymerizing two or more monomers.
  • the thermoplastic resin composition according to an embodiment of the present invention is 1) C 4 to C 10 alkyl (meth) acrylate monomer unit, an aromatic vinyl-based monomer unit and a first graft copolymer comprising a vinyl cyan-based monomer unit ; 2) a second graft copolymer comprising C 4 to C 10 alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units; And 3) a first styrenic copolymer that is a copolymer of a monomer mixture comprising a C 1 to C 3 alkyl substituted styrene monomer, a vinyl cyan monomer, and a C 1 to C 3 alkyl (meth) acrylate monomer. And, the first graft copolymer and the second graft copolymer have different average particle diameters of the core.
  • thermoplastic resin composition according to an embodiment of the present invention can realize both excellent weather resistance and mechanical properties.
  • thermoplastic resin composition according to an embodiment of the present invention may further include a second styrene copolymer that is a copolymer of a monomer mixture comprising 4) an aromatic vinyl monomer and a vinyl cyan monomer.
  • thermoplastic resin composition according to an embodiment of the present invention may further include a (meth) acrylic polymer comprising 5) C 1 to C 3 alkyl (meth) acrylate monomer units.
  • thermoplastic resin composition according to an embodiment of the present invention will be described in detail.
  • the first graft copolymer includes C 4 to C 10 alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units.
  • the first graft copolymer may impart excellent weather resistance, tensile strength, flexural strength, and impact strength to the thermoplastic resin composition.
  • the C 4 to C 10 alkyl (meth) acrylate-based monomer unit may impart excellent weather resistance to the thermoplastic resin composition.
  • the average particle diameter of the first graft copolymer may impart excellent tensile strength, flexural strength and impact strength to the thermoplastic resin composition.
  • the first graft copolymer may be a graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyan monomer on an acrylic rubber polymer that is a crosslinked polymer of C 4 to C 10 alkyl (meth) acrylate monomers. have.
  • the acrylic rubber polymer may mean a core.
  • the first graft copolymer has an average particle diameter of the core of 350 to 600 nm, 370 to 550 nm, or 400 to 500 nm, of which 400 to 500 nm is preferred. If the above-described range is satisfied, mechanical properties such as tensile strength, flexural strength, and impact strength of the thermoplastic resin composition may be further improved. In addition, the coloring property of the thermoplastic resin composition can be remarkably improved.
  • the C 4 to C 10 alkyl (meth) acrylate monomer units are butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylic It may be a unit derived from at least one monomer selected from the group consisting of acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate and decyl (meth) acrylate, , Of these, units derived from butyl acrylate are preferred.
  • the C 4 to C 10 alkyl (meth) acrylate-based monomer unit may be included in an amount of 30 to 70% by weight, or 40 to 60% by weight, based on the total weight of the first graft copolymer, 40 of which It is preferably included to 60% by weight. If the above-described range is satisfied, weather resistance and mechanical properties of the first graft copolymer can be further improved.
  • the aromatic vinyl-based monomer unit may be a unit derived from at least one monomer selected from the group consisting of styrene, ⁇ -methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, of which an alkyl unsubstituted styrene
  • the unit derived from styrene which is a system monomer is preferred.
  • the aromatic vinyl-based monomer unit may be included in 5 to 25% by weight, or 10 to 20% by weight, based on the total weight of the first graft copolymer, and is preferably included in 10 to 20% by weight. . If the above-described range is satisfied, the processability of the first graft copolymer can be further improved.
  • the vinyl cyan monomer unit may be a unit derived from one or more monomers selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile, of which units derived from acrylonitrile are preferred. .
  • the vinyl cyan monomer unit may be included in 15 to 55% by weight, or 25 to 45% by weight relative to the total weight of the first graft copolymer, and is preferably included in 25 to 45% by weight. . If the above-described range is satisfied, chemical resistance and rigidity of the first graft copolymer can be further improved.
  • the first graft copolymer may have a graft ratio of 10 to 50% or 20 to 40%, of which 20 to 40% is preferred. If the above-described range is satisfied, mechanical properties of the first graft copolymer, that is, tensile strength, flexural strength, and impact strength may be further improved.
  • the first graft copolymer may be included in 1 to 20% by weight or 5 to 15% by weight based on the total weight of the thermoplastic resin composition, and preferably 5 to 15% by weight. If the above-described range is satisfied, excellent mechanical properties of the thermoplastic resin composition can be realized.
  • the second graft copolymer includes C 4 to C 10 alkyl (meth) acrylate monomer units, aromatic vinyl monomer units, and vinyl cyan monomer units.
  • the second graft copolymer may impart excellent weather resistance to the thermoplastic resin composition. Specifically, due to the C 4 to C 10 alkyl (meth) acrylate-based monomer unit and the above-described average particle diameter, excellent weatherability can be imparted to the thermoplastic resin composition.
  • the second graft copolymer may be a graft copolymer obtained by graft polymerization of an aromatic vinyl monomer and a vinyl cyan monomer on an acrylic rubber polymer that is a crosslinked polymer of C 4 to C 10 alkyl (meth) acrylate monomers. have.
  • the acrylic rubber polymer may mean a core.
  • the second graft copolymer has a core having an average particle diameter of 30 to 200 nm or 50 to 150 nm, of which 30 to 200 nm is preferred. If the above-mentioned range is satisfied, the specific surface area of the second graft copolymer is widened, so that weatherability can be remarkably improved.
  • the types of the C 4 to C 10 alkyl (meth) acrylate monomer units are as described above.
  • the C 4 to C 10 alkyl (meth) acrylate-based monomer unit may be included in 30 to 70% by weight, or 40 to 60% by weight, based on the total weight of the second graft copolymer, 40 of which It is preferably included to 60% by weight. If the above-described range is satisfied, weatherability and mechanical properties of the second graft copolymer can be further improved.
  • the types of the aromatic vinyl monomer units are as described above.
  • the aromatic vinyl-based monomer unit may be included in 5 to 25% by weight, or 10 to 20% by weight, based on the total weight of the second graft copolymer, and is preferably included in 10 to 20% by weight. . If the above-described range is satisfied, the processability of the second graft copolymer can be further improved.
  • the type of the vinyl cyan monomer unit is as described above.
  • the vinyl cyan monomer unit may be included in an amount of 15 to 55% by weight, or 25 to 45% by weight, and preferably 25 to 45% by weight, based on the total weight of the second graft copolymer. . If the above-described range is satisfied, chemical resistance and rigidity of the second graft copolymer may be further improved.
  • the second graft copolymer may have a graft ratio of 10 to 50% or 20 to 40%, of which 20 to 40% is preferred. If the above-described range is satisfied, mechanical properties of the first graft copolymer, that is, tensile strength, flexural strength, and impact strength may be further improved.
  • the second graft copolymer may be included in an amount of 20 to 45% by weight or 25 to 40% by weight, and preferably 25 to 40% by weight, based on the total weight of the thermoplastic resin composition. If the above-mentioned ranges are satisfied, excellent weatherability and coloring properties of the thermoplastic resin composition can be realized.
  • the first styrene copolymer is a copolymer of a monomer mixture comprising a C 1 to C 3 alkyl substituted styrene monomer, a vinyl cyan monomer, and a C 1 to C 3 alkyl (meth) acrylate monomer.
  • the first styrene-based copolymer may impart remarkably excellent weather resistance, heat resistance, and colorability to the thermoplastic resin composition.
  • the C 1 to C 3 alkyl-substituted styrene-based monomers introduced during the preparation of the first styrene-based copolymer may impart remarkably excellent weather resistance and heat resistance to the thermoplastic resin composition.
  • the C 1 to C 3 alkyl (meth) acrylate-based monomers introduced during the preparation of the first styrene-based copolymer may impart remarkably excellent coloring properties to the thermoplastic resin composition.
  • the C 1 to C 3 alkyl-substituted styrene-based monomers may be at least one selected from the group consisting of ⁇ -methyl styrene, p-methyl styrene, and 2,4-dimethyl styrene, of which ⁇ -methyl styrene is preferred. Do.
  • the C 1 to C 3 alkyl-substituted styrene-based monomer may be included in an amount of 50 to 75% by weight, 55 to 70% by weight, or 60 to 65% by weight, based on the total weight of the monomer mixture, of which 60 to 65% by weight It is preferred to be included in%. When included in the above-described range, it is possible to impart remarkably excellent weather resistance and heat resistance to the thermoplastic resin composition.
  • the type of the vinyl cyan monomer is as described above.
  • the vinyl cyan monomer may be included in an amount of 15 to 40% by weight, 20 to 35% by weight, or 25 to 30% by weight, and preferably 25 to 30% by weight, based on the total weight of the monomer mixture. . When included in the above-described range, it can give excellent chemical resistance and rigidity to the thermoplastic resin composition.
  • the C 1 to C 3 alkyl (meth) acrylate-based monomers may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate, of which Methyl methacrylate is preferred.
  • the alkyl (meth) acrylate-based monomer of C 1 to C 3 may be included in 1 to 20% by weight, 5 to 15% by weight, or 9 to 13% by weight based on the total weight of the monomer mixture, of which 9 It is preferably included at 13% by weight.
  • 9 It is preferably included at 13% by weight.
  • the first styrene-based copolymer may have a weight average molecular weight of 80,000 to 105,000 g / mol, 85,000 to 100,000 g / mol, or 90,000 to 95,000 g / mol, of which 90,000 to 95,000 g / mol is preferred. If the above-described range is satisfied, the processability of the thermoplastic resin composition can be further improved.
  • the first styrene-based copolymer based on the total weight of the thermoplastic resin composition, may be included in 40 to 70% by weight or 45 to 65% by weight, preferably 45 to 60% by weight. If the above-mentioned ranges are satisfied, excellent weatherability and coloring properties of the thermoplastic resin composition can be realized.
  • the second styrene-based copolymer may be a copolymer of a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer.
  • the second styrene-based copolymer may impart excellent processability, chemical resistance, rigidity, and heat resistance to the thermoplastic resin composition.
  • the monomer mixture may include the aromatic vinyl-based monomer and the vinyl cyan-based monomer in a weight ratio of 55:45 to 80:20 or 60:40 to 75:25, of which in a weight ratio of 60:40 to 75:25 It is preferred to include. If the above-mentioned range is satisfied, the second styrene-based copolymer can balance workability, chemical resistance, rigidity, and heat resistance.
  • the type of the aromatic vinyl-based monomer is as described above, and among them, one or more selected from the group consisting of styrene and ⁇ -methyl styrene is preferable.
  • the type of the vinyl cyan monomer is as described above, and acrylonitrile is preferable.
  • the second styrene-based copolymer may be at least one selected from the group consisting of styrene-acrylonitrile copolymer and ⁇ -methyl styrene-acrylonitrile copolymer, in order to further improve the processability of the thermoplastic resin composition, styrene -Acrylonitrile copolymers are preferred.
  • the second styrene-based copolymer may be included in 1 to 20% by weight or 5 to 15% by weight, and preferably 5 to 15% by weight, based on the total weight of the thermoplastic resin composition. If the above-mentioned range is satisfied, the processability of the thermoplastic resin composition can be further improved.
  • the (meth) acrylic polymer may include C 1 to C 3 alkyl (meth) acrylate monomer units.
  • the (meth) acrylic polymer may impart excellent weather resistance and colorability to the thermoplastic resin composition.
  • the types of the C 1 to C 3 alkyl (meth) acrylate monomers are as described above.
  • the (meth) acrylic polymer may have a weight average molecular weight of 80,000 to 100,000 g / mol or 85,000 to 95,000 g / mol, of which 85,000 to 95,000 g / mol is preferred.
  • the coloring property of the thermoplastic resin composition may be further improved.
  • the (meth) acrylic polymer further includes at least one selected from the group consisting of aromatic vinyl monomer units and vinyl cyan monomer units in addition to C 1 to C 3 alkyl (meth) acrylate monomer units ( It may be a metha) acrylic copolymer.
  • the (meth) acrylic copolymer is a copolymer of an alkyl (meth) acrylate monomer of C 1 to C 3 and at least one monomer mixture selected from the group consisting of an aromatic vinyl monomer and a vinyl cyan monomer.
  • an alkyl (meth) acrylate monomer of C 1 to C 3 and at least one monomer mixture selected from the group consisting of an aromatic vinyl monomer and a vinyl cyan monomer.
  • the monomer mixture is 30 to 55 parts by weight of one or more selected from the group consisting of aromatic vinyl monomers and vinyl cyan monomers, based on 100 parts by weight of the alkyl (meth) acrylate monomers of C 1 to C 3 or It may include 35 to 50 parts by weight, and it is preferable to include 35 to 55 parts by weight.
  • compatibility with the first and second styrene-based copolymers may be further improved.
  • the (meth) acrylic polymer based on the total weight of the thermoplastic resin composition, may be included in 1 to 10 or 2 to 7% by weight, preferably 2 to 7% by weight. If the above-described range is satisfied, weatherability and colorability of the thermoplastic resin composition may be further improved.
  • a polymerization solution was prepared by adding 0.075 parts by weight of peroxy) cyclohexane and 0.195 parts by weight of polyether poly-t-butylperoxy carbonate. The polymerization solution was continuously added to a reactor at a temperature of 110 ° C. to perform a polymerization reaction.
  • the prepared polymerization product was transferred to a devolatilization tank, and unreacted monomers and reaction solvents were recovered and removed under a temperature of 235 ° C. and a pressure of 20.6 torr to prepare a pellet-type heat-resistant styrene resin.
  • (A-1) 1st graft copolymer SA927 (a graft copolymer obtained by graft polymerization of styrene and acrylonitrile on a butyl acrylate rubbery polymer having an average particle diameter of 450 nm) was used.
  • (A-2) 2nd graft copolymer SA100 of LG Chemical (graft copolymer obtained by graft polymerization of styrene and acrylonitrile on a butyl acrylate rubber polymer having an average particle diameter of 100 nm) was used.
  • (C-2) SAN copolymer 95RF (a copolymer of styrene and acrylonitrile) of LG Chemical was used.
  • (D-2) (meth) acrylic-based copolymer: XT510 (a copolymer of methyl methacrylate, styrene and acrylonitrile) manufactured by LG Chemical was used.
  • thermoplastic resin composition The above-mentioned components were mixed and stirred according to the contents described in [Table 1] to prepare a thermoplastic resin composition.
  • thermoplastic resin compositions of Examples and Comparative Examples were put into an extrusion kneader (cylinder temperature: 240 ° C.) and extruded to prepare pellets, and physical properties were evaluated by the methods described below, and the results are shown in [Table 1].
  • (C-3) MSAN copolymer 60% by weight of styrene, acrylic 30% by weight of nitrile and methyl methacrylate 10% by weight of monomers copolymerized is water the copolymer (D-1) a mixture comprising a poly (methyl methacrylate): LG PMMA ⁇ of IH830 (D-2) (meth) acrylic copolymer of: LG Chemical ⁇ XT510 (methyl Copolymers of methacrylate, styrene and acrylonitrile)
  • Example 1 to 4 were excellent in basic physical properties and also excellent in colorability and weatherability.
  • Example 1 and Comparative Example 1 Example 1 and Comparative Example 5, Example 2 and comparison
  • Example 3 and Comparative Example 3 Example 4 and Comparative Example 4 were compared, the L value differed by 0.3 or more, and thus it was confirmed that the coloring property was significantly improved.
  • Example 4 and Comparative Example 4 were compared, it was confirmed that the effect of improving not only coloration but also weather resistance was large.

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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, comprenant : un premier polymère greffé comprenant une unité monomère à base de(méth)acrylate d'alkyle en C4-C10, une unité monomère à base de vinyle aromatique et une unité monomère à base de cyan de vinyle ; un second copolymère greffé comprenant une unité monomère à base de (méth)acrylate d'alkyle en C4-C10, une unité monomère à base de vinyle aromatique et une unité monomère à base de cyan de vinyle ; et un premier copolymère à base de styrène qui est un copolymère d'un mélange de monomères comprenant un monomère à base de styrène à substitution alkyle en C1-C3, un monomère à base de cyan de vinyle et un monomère à base de (méth)acrylate d'alkyle en C1-C3, le premier copolymère greffé et le second copolymère greffé étant différents en termes de diamètre moyen de noyau. La composition de résine thermoplastique a une excellente aptitude à la coloration, une excellente résistance aux intempéries, à la traction, à la flexion et aux chocs.
PCT/KR2019/014351 2018-10-31 2019-10-29 Composition de résine thermoplastique WO2020091371A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP19878064.5A EP3875534A4 (fr) 2018-10-31 2019-10-29 Composition de résine thermoplastique
US17/054,459 US11608401B2 (en) 2018-10-31 2019-10-29 Thermoplastic resin composition
CN201980030295.8A CN112105690A (zh) 2018-10-31 2019-10-29 热塑性树脂组合物
JP2020560816A JP7205976B2 (ja) 2018-10-31 2019-10-29 熱可塑性樹脂組成物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2018-0132192 2018-10-31
KR20180132192 2018-10-31
KR1020190134501A KR102298296B1 (ko) 2018-10-31 2019-10-28 열가소성 수지 조성물
KR10-2019-0134501 2019-10-28

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WO2020091371A1 true WO2020091371A1 (fr) 2020-05-07

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JP2022550104A (ja) * 2020-06-26 2022-11-30 エルジー・ケム・リミテッド 熱可塑性樹脂組成物及びそれを含む成形品

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022550104A (ja) * 2020-06-26 2022-11-30 エルジー・ケム・リミテッド 熱可塑性樹脂組成物及びそれを含む成形品
JP7342252B2 (ja) 2020-06-26 2023-09-11 エルジー・ケム・リミテッド 熱可塑性樹脂組成物及びそれを含む成形品

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