WO2012091299A2 - Composition de résine thermoplastique à faible brillant présentant une excellente résistance à la chaleur et aux intempéries - Google Patents

Composition de résine thermoplastique à faible brillant présentant une excellente résistance à la chaleur et aux intempéries Download PDF

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WO2012091299A2
WO2012091299A2 PCT/KR2011/008986 KR2011008986W WO2012091299A2 WO 2012091299 A2 WO2012091299 A2 WO 2012091299A2 KR 2011008986 W KR2011008986 W KR 2011008986W WO 2012091299 A2 WO2012091299 A2 WO 2012091299A2
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compound
thermoplastic resin
resin composition
weight
copolymer
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PCT/KR2011/008986
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English (en)
Korean (ko)
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WO2012091299A3 (fr
WO2012091299A9 (fr
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홍재근
진영섭
이병도
선호룡
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제일모직 주식회사
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Priority claimed from KR1020110121904A external-priority patent/KR20120076301A/ko
Application filed by 제일모직 주식회사 filed Critical 제일모직 주식회사
Priority to CN201180062755.9A priority Critical patent/CN103282431B/zh
Publication of WO2012091299A2 publication Critical patent/WO2012091299A2/fr
Publication of WO2012091299A9 publication Critical patent/WO2012091299A9/fr
Publication of WO2012091299A3 publication Critical patent/WO2012091299A3/fr
Priority to US13/927,601 priority patent/US9000094B2/en
Priority to US14/627,019 priority patent/US9279049B2/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and 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 a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • 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
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a low light thermoplastic resin composition excellent in heat resistance and weather resistance. More specifically, the present invention relates to a low-light thermoplastic resin composition having excellent heat and weather resistance, as well as heat resistance, weather resistance and low light properties, and excellent balance of physical properties such as laminar strength and fluidity by introducing a heat-resistant aromatic vinyl copolymer into a resin having a specific morphology. will be.
  • ABS resin is excellent layer toughness and processability, and has excellent mechanical strength and heat deformation temperature.Because of its beautiful appearance, it can be used in automobiles, electrical and electronic equipment, office equipment, home appliances, toys, It is widely used in various applications such as stationery. Butadiene-based rubber components used in ABS resins contain chemically labile double bonds and are easily aged by sunlight and ultraviolet rays. Therefore, ABS resin is used only for electric and electronic parts, agricultural equipment, road signs, building finishing materials, door panels, windows, leisure / household goods, sporting goods, automobile goods, etc., which are used outdoors.
  • ASA acrylate-styrene-acrylonitrile
  • Such a method includes a method of producing a low light effect through an injection or painting process using a corrosion mold.
  • the third method is to adjust the size of the dispersed phase particles in the matrix to form a microscale rough surface. The surface thus formed scatters incident light to lower gloss.
  • the first method the matting additive-quenching agent to implement the low light effect is convenient in many aspects, but the uniformity of the gloss is not constant depending on the dispersion state of the additive has a limitation in quality.
  • the high specific gravity of the additives commonly used may result in a higher specific gravity of the final product.
  • the second method of injection or painting through a corrosive mold also introduces an additional process, which increases manufacturing costs and may cause pollution, which is disadvantageous in terms of environment.
  • US Patent Nos. 6,696 and 165 add about 0.1 to about 20 parts by weight of a crystalline polymer, which can be represented by polyalkyl terephthalate
  • US Patent No. 6,395,828 discloses compounds 0.5 to 0.5 produced by reaction of epoxy and amine compounds. A method of lowering the glossiness of an ASA resin by adding 15 parts by weight is disclosed.
  • U.S. Patent Nos. 5,475,053, Crab 4,652,614 and the like disclose a method of lowering the gloss of resin by using a spherical graft copolymer as a matting agent
  • U.S. Patents 4,169,869, Crab 4, 460, 742, 5,580,924, Korean Patent Publication No. 2008- 0036790 and the like discloses a method for lowering the gloss using various copolymers as an additive.
  • a method of lowering gloss is disclosed using rubber particles having a large particle diameter of a core / shell structure of 2-15.
  • An object of the present invention is to provide a low-light thermoplastic resin composition excellent in heat resistance and weather resistance while maintaining the lamella strength and mechanical properties.
  • Another object of the present invention is to provide a low light thermoplastic resin composition excellent in low light properties and fluidity.
  • Still another object of the present invention is to provide a low light thermoplastic resin composition which is particularly suitable for outdoor products, road signs, building finishes, automobile parts, etc. due to excellent balance of physical properties such as heat resistance, weather resistance, low light properties, and mechanical strength.
  • One aspect of the present invention relates to a low light thermoplastic resin composition excellent in heat resistance and weather resistance.
  • the composition comprises (A) a thermoplastic resin forming a first dispersed phase; And (B) an acrylic resin forming a second dispersed phase, wherein the first dispersed phase has a network shape.
  • the low light thermoplastic resin composition may further include (C) a heat resistant aromatic vinyl copolymer.
  • thermoplastic resin (A) is a (al) (meth) acrylic acid alkyl ester polymer and
  • (a2) an aromatic vinyl-vinyl cyanide copolymer, wherein the (meth) acrylic acid alkyl ester polymer (al) forms a dispersed phase in a network shape, and the aromatic vinyl-vinyl cyanide copolymer (a2) is a continuous phase Can be reached.
  • the acrylic resin (B) forming the system 2 dispersed phase may be an acrylic graft copolymer resin.
  • the second dispersed phase may be in the form of particles.
  • the low light thermoplastic resin composition comprises (A) about 20 to about 50 weight percent of a thermoplastic resin having a network-shaped dispersed phase; (B) about 5 to about 40 weight of acrylic resin and (C) about 10 to about 50 heat resistant aromatic vinyl copolymer And may comprise a weight of 3 ⁇ 4.
  • the thermoplastic resin (A) may comprise about 5 to about 35 weight 3 ⁇ 4 of the (meth) acrylic acid alkyl ester polymer (al) and about 65 to about 95 weight% of the aromatic vinyl-vinyl cyanide copolymer (a2). have.
  • the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or an anhydride thereof, and a compound having two or more hydroxyl groups.
  • the (meth) acrylic acid alkyl ester polymer (al) comprises about 60 to about 95 weight percent of the (meth) acrylic acid alkyl ester compound; About 1 to about 20 weight percent of an unsaturated carboxylic acid or anhydride thereof; About 0 to about 20 weight percent of an aromatic vinyl compound about 0 to about 10 weight% of a vinyl cyanide compound; And about 0.1 to about 3 equivalents of a compound having two or more hydroxyl groups per 1 equivalent of the unsaturated carboxylic acid or its anhydride.
  • the compound having two or more hydroxy groups may be one or more selected from the group consisting of alkanediol, polyalkylene glycol, poly and combinations thereof having 2 to 10 carbon atoms.
  • the (meth) acrylic acid alkyl ester polymer (al) comprises (meth) acrylic acid alkyl ester units, and unsaturated carboxylic acid or anhydride units thereof as a main chain, and the saturated carboxylic acid or anhydride thereof.
  • the carboxyl group of the unit may be linked by an ester bond with the hydroxy group of the compound having two or more hydroxy groups to form a network-shaped dispersed phase.
  • the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, an unsaturated compound having a hydroxy group, and a compound having two or more carboxyl groups. .
  • the (meth) acrylic acid alkyl ester polymer (al) is
  • the aromatic vinyl-vinyl cyanide copolymer (a2) may contain about 60 to about 95 wt% of an aromatic vinyl compound unit, about 5 to about 40 wt% of a vinyl cyanide compound unit, and about 0 of (meth) acrylic acid alkyl ester compound unit. To about 10% by weight.
  • the weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (a2) may be about 150,000 to 300,000 g / n l.
  • the acrylic resin (B) is (bl) (meth) acrylic rubber about 10 to about 60 From about 40% to about 90% by weight (b2) of the aromatic vinyl compound-vinyl cyanide compound copolymer may be grafted.
  • the aromatic vinyl compound-vinyl cyanide compound copolymer (b2) may be a copolymer of about 60 to about 80 weight% of the aromatic vinyl compound and about 20 to about 40 weight% of the vinyl cyanide compound.
  • the (bl) (meth) acrylic rubber particles may have an average particle diameter of about 0.05 to about 1.
  • the (C) heat resistant aromatic vinyl copolymer may include an aromatic vinyl compound unit, a vinyl cyanide compound unit, and a crosslinkable monomer unit.
  • the (C) heat-resistant aromatic vinyl copolymer is based on 100 parts by weight of the monofunctional vinyl compound containing about 60 to about 80 weight% of the aromatic vinyl compound and about 20 to about 40 weight% of the vinyl cyanide compound. About 0.01 to about 0.05 parts by weight of the crosslinkable monomer.
  • the resin composition may further include (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, (E) a copolymer including a maleic anhydride compound, or a mixture thereof.
  • the (D) aromatic vinyl compound-vinyl cyanide compound copolymer may include more than about 0 and about 40 wt% or less of the total resin composition.
  • the copolymer including the maleic anhydride-based compound (E) may include more than about 0 and about 20% by weight or less of the total resin composition. In embodiments, the copolymer including the maleic anhydride-based compound (E) may include about 40 to about 60% by weight of maleic anhydride, N-substituted maleate or a mixture thereof.
  • the composition includes antimicrobial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, compatibilizers, stabilizers, lubricants, antistatic agents, colorants, flame retardants, weather agents, colorants, UV absorbers, ultraviolet rays. It may contain one or more additives such as a barrier, flame retardant, layering agent, nucleating agent, adhesion aid, pressure-sensitive adhesive.
  • the composition has a glossiness of about 30 GU or less, measured using a 75 degree polisher, a Vicat softening point of about 100 to 150 ° C., a ⁇ of about 2.8 or less, as measured by UL 746C, and ASTM D256.
  • the Izod notch layer strength measured by 1/8 "thick may be about 8 kgf. Cm / cm or more.
  • the viewpoint relates to a molded article molded from the composition.
  • the molded article has a morphology of a continuous phase and a dispersed phase, and the continuous phase includes an aromatic vinyl-vinyl cyanide copolymer and a heat resistant aromatic vinyl copolymer, wherein the dispersed phase is a network-shaped first dispersion phase and a particle-type type 2 dispersed phase.
  • the first disperse phase is formed of a (meth) acrylic acid alkyl ester polymer
  • the second disperse phase is formed of an acrylic resin
  • Vicat softening point can form a molded article of about 100 ⁇ 150t :.
  • thermoplastic resin composition according to the present invention has excellent heat resistance and weather resistance while maintaining impact strength and mechanical properties, excellent light properties and fluidity, and excellent physical property balance, making it particularly suitable for outdoor products, road signs, building finishes, automobile parts, etc. It has the effect of providing the thermoplastic resin composition.
  • thermoplastic resin (A) which has a network-shaped dispersion phase used in the Example. ((a) magnification 7,000 times (b) magnification 12,000 times)
  • the low-light thermoplastic resin composition excellent in heat resistance and weather resistance of the present invention includes (A) a thermoplastic resin forming a monodisperse phase; And (B) an acrylic resin forming a second dispersed phase, wherein the first dispersed phase has a network shape.
  • (C) may include a heat-resistant aromatic vinyl copolymer.
  • the resin composition may further include a copolymer including (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, (E) a maleic anhydride compound, or a mixture thereof.
  • thermoplastic resin having a network-shaped first dispersed phase
  • the thermoplastic resin (A) of the present invention is an (al) (meth) acrylic acid alkyl ester polymer And (a2) aromatic vinyl-vinyl cyanide copolymers.
  • the (meth) acrylic acid alkyl ester polymer 1) forms a network-shaped first dispersed phase
  • the aromatic vinyl-vinyl cyanide copolymer 2 forms a continuous phase.
  • the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or an anhydride thereof, and a compound having two or more hydroxyl groups. .
  • the (meth) acrylic acid alkyl ester polymer (al) includes (meth) acrylic acid alkyl ester units and unsaturated carboxylic acid or anhydride units thereof as a main chain, and the carboxyl groups of the unsaturated carboxylic acid or anhydride units thereof are two
  • the hydroxyl group of the compound which has the above hydroxyl group is connected by ester bond, and can form the Crab 1 dispersed phase of network shape.
  • the (meth) acrylic acid alkyl ester polymer (al) is a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or an anhydride thereof, an aromatic vinyl compound, a vinyl cyanide compound, and a compound having two or more hydroxyl groups. It may include units derived from.
  • the (meth) acrylic acid alkyl ester polymer (al) may comprise about 60 to about 95 weight percent of the (meth) acrylic acid alkyl ester compound ⁇ about 1 to about 20 weight percent of an unsaturated carboxylic acid or anhydride thereof; Aromatic vinylic compound about 0 to about 20 weight 3 ⁇ 4>; From about 0 to about 10 weight 3 ⁇ 4 of vinyl cyanide compound; And about 0.1 to about 3 equivalents of a compound having two or more hydroxyl groups per 1 equivalent of the unsaturated carboxylic acid or its anhydride.
  • the (meth) acrylic acid alkyl ester polymer (al) can be divided into chains to form a dispersed phase, and the heat resistance is excellent.
  • an unsaturated carboxyl compound or anhydride thereof is included in the chains of the thermoplastic resin (A) as part of the repeating unit, and the compound having two or more hydroxy groups serves to connect the chains.
  • the compound having two or more hydroxyl groups may be polymerized in a ratio of about 0.1 to 2.5 equivalents relative to the unsaturated carboxylic acid or anhydride thereof.
  • (meth) acrylic acid alkyl ester compound about 1 to about 5% by weight of unsaturated carboxylic acid or anhydride thereof, about 2 to about 8% by weight of aromatic vinyl compound, vinyl cyanide compound About 1 to about 5% by weight, wherein the compound having two or more hydroxy groups is about about unsaturated carboxylic acid or anhydride thereof It may be polymerized in a ratio of 0.5 to about 2.0 equivalents.
  • the (meth) acrylic acid alkyl ester compound is a (meth) acrylic acid alkyl ester compound having an alkyl group having 1 to 10 carbon atoms.
  • methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, nuclear chamber methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethyl nuclear chamber methacrylate Acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, nucleus acrylate, heptyl acrylate, octyl acrylate, 2-ethyl nucleus acrylate and the like can be used, preferably butyl Acrylate, but is not necessarily limited thereto. These may be applied alone or in combination of two or more.
  • aromatic vinyl compound styrene, alpha methyl styrene, ⁇ -methyl styrene, p-methyl styrene, etc. may be used, and preferably, styrene, but is not limited thereto. These may be applied alone or in combination of two or more.
  • vinyl cyanide compound acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like may be used, and preferably acrylonitrile, but is not limited thereto. . These may be applied alone or in combination of two or more.
  • the unsaturated carboxylic acid or anhydride thereof may include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, and the like. May be used, preferably acrylic acid, but is not necessarily limited thereto. These may be applied alone or in combination of two or more.
  • the compound having two or more hydroxy groups preferably has 2 to 10 hydroxy groups, more preferably 2 to 5 hydroxy groups.
  • the compound having two or more hydroxy groups is preferably a saturated compound in which all carbon atoms in the molecule are bonded with only a single bond.
  • Examples of the compound having two or more hydroxy groups include alkanediols, polyalkylene glycols, polyols and mixtures thereof having 2 to 10 carbon atoms. These may be applied alone or in combination of two or more.
  • alkanediol having 2 to 10 carbon atoms examples include ethylene glycol, propylene glycol, 1,4-butanedi, 1,5-pentanediol, 1,6-nucleic acid diol, 1,7-heptanediol, 1, 8 -Octanediol, and the like, but not necessarily limited thereto.
  • Examples of the polyalkylene glycol may include polyethylene glycol, polypropylene glycol, and the like, and polyethylene glycol (PEG) may vary depending on molecular weight. PEG300, PEG600, PEG1500, and the like, but are not necessarily limited thereto.
  • polyol examples include xyl, glycerin, erythriitol, sorbitol, and acrylic or ether polys having a hydroxy value of about 50-500 and a molecular weight of about 500-5000 g / mol. It includes, but is not necessarily limited thereto.
  • Units derived from a (meth) acrylic acid alkyl ester compound, an unsaturated compound having a hydroxy group, and a compound having two or more carboxyl groups may be included.
  • (meth) acrylic acid alkyl ester compound about 1% to about 20% by weight of unsaturated compound having hydroxy group, about 0% to about 20% by weight of aromatic vinyl compound, about 0% to vinyl cyanide compound
  • aromatic vinyl compound about 0% to vinyl cyanide compound
  • the (meth) acrylic acid alkyl ester polymer (al) can be divided into chains to form a dispersed phase, and the heat resistance is excellent.
  • an unsaturated compound having a hydroxy group is included in the chains of the thermoplastic resin (A) as part of the repeating unit, and the compound having two or more carboxyl groups serves to link the chains.
  • an alkyl (meth) acrylate containing a hydroxy group may be used as the unsaturated compound having a hydroxy group.
  • an alkyl (meth) acrylate containing a hydroxy group may be used.
  • hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. are mentioned.
  • the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid glycidyl ester compound, and a compound having two or more hydroxyl groups. Can be.
  • (meth) acrylic acid alkyl ester compound about 60 to about 95 weight percent of (meth) acrylic acid alkyl ester compound, about 1 to about 20 weight% of (meth) acrylic acid glycidyl ester compound, about 0 to about 20 weight% of aromatic vinyl-based compound, vinyl cyanide From about 0.1 to about 3 equivalents, preferably from about 0.5 to about 2 equivalents, of the compound having from about 0 to about 10 weight 3 ⁇ 4, and the compound having at least two hydroxyl groups relative to one equivalent of the (meth) acrylic acid alkyl ester compound It may include. Within this range, the (meth) acrylic acid alkyl ester polymer (al) can be divided into chains to form a dispersed phase, and the heat resistance is excellent.
  • the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid glycidyl ester compound, and a compound having two or more carboxyl groups.
  • the (meth) acrylic acid alkyl ester compound and the (meth) acrylic acid glycidyl ester compound are polymerized to contain (meth) acrylic acid alkyl ester units and (meth) acrylic acid glycidyl ester units as main chains, and (meth) acrylic acid It constitutes the chains of the alkyl ester polymer.
  • the epoxy group of the (meth) acrylic acid glycidyl ester unit is connected by an hydroxy group and an ester bond of a compound having two or more carboxyl groups or a compound having two or more hydroxy groups. Accordingly, the chains of the (meth) acrylic acid alkyl ester polymer (al) are connected to each other to form a dispersed phase.
  • (meth) acrylic acid alkyl ester compound about 60 to about 95 weight percent of (meth) acrylic acid alkyl ester compound, about 1 to about 20 weight% of (meth) acrylic acid glycidyl ester compound, about 0 to about 20 weight% of aromatic vinyl-based compound, vinyl cyanide From about 0 to about 10 percent by weight of the compound, and about 0.1 to about 3 equivalents, preferably about 0.5 to about 2 equivalents, of the compound having two or more carboxyl groups relative to one equivalent of the (meth) acrylic acid alkyl ester compound can do.
  • the (meth) acrylic acid alkyl ester polymer (al) can be divided into chain-linked all-layers to form a dispersed phase, and the heat resistance is excellent.
  • glycidyl acrylate As the (meth) acrylic acid glycidyl ester compound, glycidyl acrylate, glycidyl methacrylate, and the like may be used, but are not necessarily limited thereto. These may be applied alone or in combination of two kinds. Among these, glycidyl methacrylate is preferable.
  • the compound having two or more carboxyl groups preferably has 2 to 10 carboxyl groups, and more preferably 2 to 5 carboxyl groups.
  • the compound having two or more carboxyl groups is preferably a saturated compound in which all carbon atoms in the molecule are bonded by a single bond only.
  • Examples of the compound having two or more carboxyl groups include alkanedioic acid having 2 to 10 carbon atoms, polyacid, a mixture thereof, and the like.
  • alkanedioic acid having 2 to 10 carbon atoms examples include butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), nucleic acid diioic acid (adipic acid), heptanedioic acid (pimelic acid), and octanodioic acid. (Suberic acid), nonanodioic acid (azelaic acid), decandioic acid (watermelon), and the like, but are not necessarily limited thereto.
  • the poly acid has an acid value of about 30-300 and a weight average molecular weight of about 1,000-5,000 g / mol.
  • Specific examples of the polyacid include poly (meth) acrylic acid, styrene- (meth) acrylic acid polymer, styrene-maleic acid polymer, and the like, but are not necessarily limited thereto.
  • Rohm as the polyacid Morez-101, Morez-100 from Haas; Joncry 1—678, Joncry 1-690 by BASF, Soluryl-20, Sol ury 1-70, etc. of Hanwha Chemical Co., Ltd. may be used.
  • the aromatic vinyl-vinyl cyanide copolymer 2) forming the continuous phase of the thermoplastic resin composition of the present invention may be prepared by polymerizing an aromatic vinyl compound and a vinyl cyanide compound, and further comprising a (meth) acrylic acid alkyl ester compound. It can be included and polymerized.
  • Each component constituting the aromatic vinyl-vinyl cyanide co-polymer (a2) is about 60 to about 95 wt% of an aromatic vinyl compound, about 5 to about 40 wt% of a vinyl cyanide compound, and about 0 to about (meth) acrylic acid alkyl ester compound.
  • the aromatic vinyl cyanide copolymer As the aromatic vinyl compound forming (b), styrene, alphamethyl styrene, paramethyl styrene, or the like may be used, preferably styrene, but is not necessarily limited thereto. These may be applied alone or in combination of two or more.
  • Acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like may be used as the vinyl cyanide compound used in the aromatic vinyl-vinyl cyanide copolymer (b). It is not limited. These may be applied alone or in combination of two or more.
  • the (meth) acrylic acid alkyl ester compound constituting the aromatic vinyl-vinyl cyanide copolymer (b) is preferably a (meth) acrylic acid alkyl ester compound having an alkyl group having 1 to 10 carbon atoms.
  • methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, nuclear chamber methacrylate, heptyl methacrylate, octyl methacrylate 2-ethyl nuclear chamber methacrylate , Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, nucleus acrylate, heptyl acrylate, octyl acrylate, 2-ethyl nucleus acrylate can be used, preferably butyl acrylate However, it is not necessarily limited thereto. These may be applied alone or in combination of two or more.
  • the weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (b) is about 150,000 to about 300,000 g / mol, preferably about 180,000 to about 250,000 g / ti) l.
  • the size of the dispersed phase can be properly maintained in the above range Impact strength and low light characteristics can be obtained and peeling can be prevented.
  • thermoplastic resin (A) having a network-shaped first dispersed phase can be produced by continuous bulk polymerization.
  • the dispersion phase described above is not easy to be produced by the method of preparing the rubber phase, such as the emulsion polymer polymerization method or the suspension polymerization method, and the aromatic vinyl-vinyl cyanide copolymers constituting the continuous phase are separately prepared. This is because it is difficult to efficiently manufacture a weather-resistant thermoplastic resin composition excellent in low light properties since the final product must be manufactured by a method such as melt extrusion.
  • (meth) acrylic acid alkyl ester about 60% to about 95% by weight of (meth) acrylic acid alkyl ester, about 1% to about 20% by weight of unsaturated carboxylic acid or anhydride thereof, about 0% to about 20% by weight of aromatic vinyl compound and about 0% to about 0% of vinyl cyanide compound About 10% by weight of the mixture is mixed to prepare the first monomer mixture.
  • the C 1 monomer mixture is continuously added to a first reactor in a plurality of reactors connected in series, and the system 1 monomer mixture is polymerized to obtain a polymerization conversion of 85 to 95% to prepare a polymer.
  • the polymer When the polymer is prepared from the first monomer mixture in the first reactor, the polymer is continuously added to the second reaction vessel, and at the same time, about 60 to about 95 weight of the aromatic vinyl compound and about 5 to about 40 weight of the vinyl cyanide compound %, And about 2 to about 10% by weight of a (meth) acrylic acid alkyl ester and a compound having two or more hydroxy groups and a compound having two or more hydroxy groups are continuously added to the crab 2 reactor.
  • the compound having two or more hydroxy groups is added at a ratio of about 0.1 to about 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof added to the first reaction group.
  • the solvent is preferably added in an amount of about 0 to about 20 parts by weight
  • the initiator is added in an amount of about 0.01 to about 0.05 parts by weight
  • the molecular weight regulator is about 0 to about 0.5 based on 100 parts by weight of the second monomer mixture. It is preferred to be added in parts by weight.
  • the plurality of reactions may be made up of two to five reactions, and the polymerization reaction may proceed continuously through each reaction.
  • the final polymerization conversion to the thermoplastic resin is adjusted to about 50 to about 70%, preferably about 50 to about 65%.
  • thermoplastic resin (A) having the dispersed phase of the network shape is described in detail in Korean Patent Publication No. 2010-47672, and the present invention is incorporated by reference.
  • the thermoplastic resin (A) having the network-shaped dispersed phase comprises about 5 to about 35 weight% of (meth) acrylic acid alkyl ester polymer (al) and about 65 to about 95 weight% of aromatic vinyl-vinyl cyanide copolymer (a2) And preferably about 5% to about 25% by weight of the (meth) acrylic acid alkyl ester polymer (a) and about 75% to about 95% by weight of the aromatic vinyl-vinyl cyanide copolymer (b). Within this range, it is possible to obtain a good balance of low light properties and layer strength.
  • thermoplastic resin (A) having the network-shaped dispersed phase also comprises from about 20 to about 50 weight percent of the total composition. It is possible to implement the target low light characteristics in the above range, it is possible to prevent the degradation of the layer resistance. Preferably from about 25 to about 45 weight percent.
  • the acrylic resin (B) forms a crab 2 dispersed phase.
  • the acrylic resin (B) can be produced by graft polymerization of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in a (meth) acrylic rubber.
  • the acrylic resin (B) is a copolymer in which about 40 to about 90 weight% of the aromatic vinyl compound-vinyl cyanide compound copolymer is grafted to about 10 to about 60 weight% of the (meth) acrylic rubber.
  • the polymerization method of the acrylic graft copolymer resin may be used a conventional method known in the art, for example, emulsion polymerization, suspension polymerization, etc. are possible, preferably using an emulsion graft polymerization method.
  • a polymer of alkyl (meth) acrylate having 2 to 8 carbon atoms may be used. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylnuclear acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate may be used, These may be used alone or in combination of two or more. Among these, butyl acrylate is preferable.
  • the average particle diameter of the acrylic rubber particles may be in the range of about 0.05 to about 1, preferably in the range of about 0.07 to about 0.7 /, more preferably in the range of about 0.1 to about 0.5; It is possible to implement the stratification strength in the above range.
  • Aromatic vinyl compound-vinyl cyanide compound grafted to the said acrylic rubber may be a copolymer of about 60 to about 80 weight percent aromatic vinyl compound and about 20 to about 40 increments 3 ⁇ 4 of the vinyl cyanide compound.
  • aromatic vinyl compound styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, vinyl toluene, and the like may be used, and these may be used alone or in combination of two or more thereof.
  • Acrylonitrile, methacrylonitrile, ethacrylonitrile and the like may be used as the vinyl cyanide compound. These may be used alone or in combination of two or more thereof.
  • the acrylic graft copolymer ( ⁇ ) comprises about 5 to about 40 weight percent of the total composition. Within this range, the balance between layer resistance, low light characteristics and fluidity can be obtained. Preferably from about 15 to about 30 weight percent.
  • the heat resistant aromatic vinyl copolymer (C) may include an aromatic vinyl compound unit, a vinyl cyanide compound unit, and a crosslinkable monomer unit.
  • the (C) heat-resistant aromatic vinyl copolymer is based on 100 parts by weight of the monofunctional vinyl compound containing about 60 to about 80 weight% of the aromatic vinyl compound and about 20 to about 40 weight% of the vinyl cyanide compound.
  • About 0.01 to about 0.2 parts by weight of the crosslinkable monomer Preferably about 0.01 to about 0.05 parts by weight of the crosslinkable monomer based on 100 parts by weight of the monofunctional vinyl compound comprising about 65 to about 75 weight percent of the aromatic vinyl compound and about 25 to about 35 weight% of the vinyl cyanide compound. do.
  • aromatic vinyl compound styrene, alphamethylstyrene, or a mixture thereof may be used.
  • vinyl cyanide compound acrylonitrile, methacrylonitrile or a mixture thereof may be used.
  • the crosslinkable monomer is a monomer containing two or more unsaturated groups, for example, divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, Diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene Glycol Dimethacrylate, Triethylene Glycol Diacrylate, Trimethylol Propane Trimethacrylate, Trimethylol Propane Triacrylate Tetramethylol Methane Tetramethacrylate, tetramethylolmethane tetraacrylate, dipropylene glycol dimethacrylate and dipropylene glycol diacrylate, 3—butanediol diacrylate, 1,3
  • the crosslinkable monomer is included in an amount of about 0. to about 0.2 parts by weight based on 100 parts by weight of the monofunctional vinyl compound.
  • the (C) heat-resistant aromatic vinyl copolymer may optionally further add monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide as necessary to impart processability and heat resistance.
  • the (C) heat-resistant aromatic vinyl copolymer can be produced by a method such as a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or the like, which are conventional polymerization methods. Preferred of these is continuous bulk polymerization.
  • the present invention is prepared by sequentially polymerizing the mixed raw materials containing an aromatic vinyl compound, a vinyl cyan compound and a polyfunctional vinyl compound containing ⁇ - methylstyrene in a plurality of reactors connected in series with each other in sequence At this time, it is characterized by adjusting the conversion rate for each semi-ungunggi to about 10-25%. Three to five reactors are suitable.
  • the method for producing the heat resistant aromatic vinyl copolymer (C) is disclosed in Korean Patent Application No. 2007-115737, and the present invention includes it as a whole.
  • the weight average molecular weight of the heat-resistant aromatic vinyl copolymer (C) that can be used in the present invention may be used in the range of about 80,000 to about 120,000 g / mol, it can be given heat resistance with excellent layer resistance and fluidity in the above range Can be.
  • the heat resistant aromatic vinyl copolymer (C) comprises from about 10 to about 50 weight percent of the total composition. Within this range, it is possible to obtain a balance of layer resistance, fluidity and heat resistance. Preferably from about 15 to about 30 weight 3 ⁇ 4.
  • the aromatic vinyl compound-vinyl cyanide compound copolymer (D) is mixed with about 10 to about 60 parts by weight of the vinyl cyanide compound to about 40 to about 90 parts by weight of the aromatic vinyl compound, and is a bulk polymerization method and a solution polymerization. It can be manufactured by a method such as a method, an emulsion polymerization method or a suspension polymerization method.
  • the aromatic vinyl compound used in the (D) aromatic vinyl copolymer resin styrene, alphamethyl styrene, paramethyl styrene, or the like may be used, but is not necessarily limited thereto. These may be applied alone or in combination of two or more. Among these, styrene is preferable.
  • Acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used as the vinyl cyanide compound used in the aromatic vinyl copolymer resin (D), but is not necessarily limited thereto. These may be applied alone or in combination of two or more. Among these, acrylonitrile is preferable.
  • the weight average molecular weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (D) may be used in the range of about 80,000 to about 300,000 g / mol, it can give a good balance of physical properties of fluidity and layer resistance in the above range.
  • the aromatic vinyl compound-vinyl cyanide compound copolymer (D) may comprise within about 40% by weight of the total composition. In embodiments, greater than about 0 and up to about 40 weight percent, preferably about 10 to about 35 weight percent. It is possible to obtain a good balance of physical properties of fluidity and layer resistance within the above range.
  • the copolymer (E) comprising the maleic anhydride compound is mixed with maleic anhydride, N-substituted maleate or a mixture thereof and an aromatic vinyl compound to form a bulk polymerization method, a solution polymerization method, and an emulsion polymerization. It can be produced by the method of suspension, suspension polymerization method.
  • aromatic vinyl compound used in the copolymer (E) including the maleic anhydride compound styrene, alphamethyl styrene, paramethyl styrene, etc. may be used, but are not necessarily limited thereto. These may be applied alone or in combination of two or more. Among these, styrene is preferable.
  • Copolymer (E) comprising the maleic anhydride-based compound may include within 20 weight 3 ⁇ 4 »of the total composition. In embodiments, greater than about 0 and up to about 20 weight%, preferably 3 to 15 weight%. It is possible to obtain a good balance of physical properties of fluidity, layer resistance and heat resistance in the above range.
  • the resin composition of the present invention may further add a conventional additive in addition to the above components. have.
  • antibacterial agents heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, compatibilizers, stabilizers, lubricants, antistatic agents, colorants, flame retardants, weather agents, colorants, UV absorbers, Additives, such as a sunscreen, a flame retardant, a layer agent, a nucleating agent adhesion
  • thermoplastic resin composition of the present invention has very low light properties compared to conventional weather resistant thermoplastic resin compositions.
  • the thermoplastic resin composition has a glossiness of about 30 G.U. Or less, and preferably about 21 G.U. or less.
  • the resin composition has a Vicat softening point of about 100 to 150 ° C., ⁇ measured by UL 746C is about 2.8 or less, preferably about 0.1 to about 2.5.
  • the resin composition has an Izod notched lamella strength of at least about 8 kgf cm / cm, preferably about 10 to about 50 kgf cm / cm, as measured by ASTM D256.
  • thermoplastic resin composition according to the present invention has excellent balance of physical properties such as impact strength, mechanical strength and fluidity while maintaining excellent weather resistance, heat resistance and low light properties. Therefore, the thermoplastic resin can be widely used in electrical and electronic parts, agricultural equipment, road signs, building finishing materials, door panels, windows, leisure / life supplies, sporting goods, automotive supplies and the like.
  • thermoplastic resin composition according to the present invention As a method of molding the thermoplastic resin composition according to the present invention to manufacture such products, extrusion, injection, or casting may be widely applied, but is not necessarily limited thereto.
  • the molding method can be easily carried out by those skilled in the art.
  • the molded article is a continuous phase comprising 2) an aromatic vinyl-vinyl cyanide copolymer and (C) a heat-resistant aromatic vinyl copolymer, wherein the (al) (meth) acrylic acid alkyl ester polymer forms a network-shaped first dispersed phase.
  • the acrylic resin (B) may form a dispersed phase in the form of particles.
  • thermoplastic resin having a network-shaped dispersed phase
  • a first reactant 90 parts by weight of butyl acrylate (BA), 5 parts by weight of styrene (SM), 2 parts by weight of acrylonitrile (AN) and 3 parts by weight of acrylic acid (AA) to 100 parts by weight of toluene 100 parts by weight, benzoyl peroxide (BP0) 0.2 part by weight and 0.05 part by weight of t-dodecyl mercaptan (TDM) were mixed to prepare a first reactant.
  • the prepared first reaction product was introduced at a rate of 1 kg / hr into a first reactor (R-1) of a continuous polymerization reaction reactor in which three reaction reactors, in which a jacket was installed and easy to control reaction temperature, were connected in series, at a temperature of 80 ° C.
  • Polymerization was prepared by allowing the polymerization to proceed for a residence time of 8 hours. At this time, the polymerization conversion rate was 90%, and the polymer prepared in the first reactor (R-1) was continuously added to the second reactor (R-2) of the continuous polymerization reactor.
  • 1,1-bis 100 parts by weight of a second monomer mixture consisting of 72 parts by weight of styrene (SM), 25 parts by weight of acrylonitrile (AN), and 3 parts by weight of butyl acrylate (BA)).
  • PHX-C t-butylperoxy) cyclonucleic acid
  • TDM t-dodecyl mercaptan
  • PEG600 polyethylene glycol having a molecular weight of 600 (1.0 equivalent ratio) 2 reactions were prepared.
  • the prepared crab 2 reactant was introduced into the second reaction vessel (R-2) of the continuous polymerization reaction reactor at a rate of 8.5 kg / hr, and the polymerization was performed at a temperature of 110 ° C. for 2 hours. At this time, the polymerization conversion rate was 25%.
  • the polymer produced in the second reactor (R-2) was continuously added to the third reactor (R-3) of the continuous polymerization reactor to proceed for a residence time of 2 hours at 130 ° C temperature.
  • the polymerization conversion rate at this time was 55%.
  • thermoplastic resin (A) was produced.
  • the prepared thermoplastic resin (A) confirmed the network dispersed phase through a TEM photograph, and is shown in FIG. 1 ((a) magnification of 7,000 times (b) magnification of 12,000 times).
  • ASA resin (trade name: CHAS) manufactured by Cheil Industries Co., Ltd. was used.
  • TJ-5380 containing 0.05 parts by weight of divinylbenzene was used in 100 parts by weight of the monomer mixture including 70% by weight of ⁇ -methylstyrene and 30% by weight of acrylonitrile manufactured by Cheil Industries Co., Ltd.
  • SAN resin (trade name: AP-30) containing 71.5% by weight of styrene and 28.5% by weight of acrylonitrile, manufactured by Cheil Industries, Ltd., and having a weight average molecular weight of 130,000 g / mol was used.
  • DENKA IP a copolymer of styrene-N-phenylmaleimide from DENKA, was used. Examples 1-7, Comparative Examples 1-2
  • octadil-3 (4—hydroxy-3,5-di-tert-butylphenyl) propionate as a hindered phenolic antioxidant after each component was added in an amount as shown in Table 1 below.
  • a part was added and extruded by a twin screw extruder having a L / B of 29 and a diameter of 45 mm to prepare pellets. After drying the prepared pellets at 80 ° C for 3 hours, using a 6 oz injection molding machine, by injection molding under the conditions of the molding temperature 180 ⁇ 280 ° C, mold temperature 40-80 ° C to prepare a physical specimen.
  • the prepared physical property specimens were measured for physical properties by the following method and the results are shown in Table 1 below.
  • MI Flow index
  • Izod impact strength measured in 1/8 "Notched condition by ASTM D256. (Unit: kgfcm / cm)
  • Vicat softening point measured at 5kg, 5C C / HR conditions by ISO R 306. (Unit: ° C)
  • thermoplastic resin composition of the present invention prepared in Examples 1 to 7 was confirmed that the excellent low light properties, heat resistance and weather stability while maintaining the laminar strength and other physical properties .
  • Comparative Example 1 which does not use the thermoplastic resin having the first dispersed phase of the network shape, can not realize the target low light characteristics, and it can be seen that the flow characteristics and weather resistance is significantly reduced.
  • Comparative Example 2 that does not use the acrylic resin can be confirmed that can not implement the target excellent layer strength. Simple modifications and variations of the present invention can be easily made by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention. [Range of request]
  • thermoplastic resin forming a first dispersed phase
  • the first dispersed phase has a network shape, wherein the low-light thermoplastic resin composition is excellent in heat resistance and weather resistance.
  • thermoplastic resin (A) comprises (al) (meth) acrylic acid alkyl ester polymer and 2) aromatic vinyl-vinyl cyanide copolymer
  • the (meth) acrylic acid alkyl ester polymer (al) forms a dispersed phase in a network shape
  • aromatic vinyl-vinyl cyanide copolymer (a2) forms a continuous phase, wherein the low-light thermoplastic resin composition having excellent heat resistance and weather resistance.
  • the low light thermoplastic resin composition of claim 2 wherein the low light thermoplastic resin composition comprises (A) about 20 to about 50 weight percent of a thermoplastic resin having a network-shaped dispersed phase; (B) about 5 to about 40 weight percent of an acrylic resin; And (C) about 10 to about 50% by weight of a heat resistant aromatic vinyl copolymer.
  • the thermoplastic resin (A) is about 5 to about 35 weight% of the (meth) acrylic acid alkyl ester polymer (al) and the aromatic vinyl-vinyl cyanide copolymer 2) about 65 to about A low-light thermoplastic resin composition having excellent heat resistance and weather resistance, comprising 95% by weight.

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Abstract

La présente invention concerne une composition de résine thermoplastique à faible brillant présentant une excellente résistance à la chaleur et aux intempéries. La composition de résine thermoplastique à faible brillant comprend : une résine thermoplastique formant une première phase dispersée ; et une résine à base acrylique formant une deuxième phase dispersée. La première phase dispersée se trouve dans une configuration en réseau.
PCT/KR2011/008986 2010-12-29 2011-11-23 Composition de résine thermoplastique à faible brillant présentant une excellente résistance à la chaleur et aux intempéries WO2012091299A2 (fr)

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CN201180062755.9A CN103282431B (zh) 2010-12-29 2011-11-23 具有优良的耐热性和耐候性的低光泽度热塑性树脂组合物
US13/927,601 US9000094B2 (en) 2010-12-29 2013-06-26 Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance
US14/627,019 US9279049B2 (en) 2010-12-29 2015-02-20 Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9000094B2 (en) 2010-12-29 2015-04-07 Cheil Industries Inc. Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004509193A (ja) * 2000-09-12 2004-03-25 バイエル・コーポレーシヨン 熱可塑性成形組成物の製造方法
KR20080036790A (ko) * 2006-10-24 2008-04-29 주식회사 엘지화학 내충격성과 내열성이 우수한 저광택 열가소성 수지 조성물
KR20100047672A (ko) * 2008-10-29 2010-05-10 제일모직주식회사 저광 특성이 우수한 내후성 열가소성 수지 및 그 제조 방법

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004509193A (ja) * 2000-09-12 2004-03-25 バイエル・コーポレーシヨン 熱可塑性成形組成物の製造方法
KR20080036790A (ko) * 2006-10-24 2008-04-29 주식회사 엘지화학 내충격성과 내열성이 우수한 저광택 열가소성 수지 조성물
KR20100047672A (ko) * 2008-10-29 2010-05-10 제일모직주식회사 저광 특성이 우수한 내후성 열가소성 수지 및 그 제조 방법

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9000094B2 (en) 2010-12-29 2015-04-07 Cheil Industries Inc. Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance
US9279049B2 (en) 2010-12-29 2016-03-08 Cheil Industries Inc. Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance

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