WO2019132388A1 - Composition de résine thermoplastique et article moulé formé à partir de celle-ci - Google Patents

Composition de résine thermoplastique et article moulé formé à partir de celle-ci Download PDF

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Publication number
WO2019132388A1
WO2019132388A1 PCT/KR2018/016175 KR2018016175W WO2019132388A1 WO 2019132388 A1 WO2019132388 A1 WO 2019132388A1 KR 2018016175 W KR2018016175 W KR 2018016175W WO 2019132388 A1 WO2019132388 A1 WO 2019132388A1
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WO
WIPO (PCT)
Prior art keywords
aromatic vinyl
weight
thermoplastic resin
resin composition
monomer
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PCT/KR2018/016175
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English (en)
Korean (ko)
Inventor
양천석
김연경
김주성
박강열
심인식
Original Assignee
롯데첨단소재(주)
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Publication of WO2019132388A1 publication Critical patent/WO2019132388A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

  • the present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in surface hydrophobicity and the like, and a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin rubber-modified aromatic vinyl copolymer resins such as acrylonitrile-butadiene-styrene copolymer resin (ABS resin) and the like have excellent mechanical properties, processability, appearance and the like, Automobile interior / exterior materials, building exterior materials, and the like.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • thermoplastic resin composition When such a thermoplastic resin composition is applied to a product installed outdoors such as a building exterior material, the surface can be modified to have hydrophobicity in order to reduce contamination due to precipitation, snowfall, dust adhesion, and the like.
  • thermoplastic resin composition hydrophobic
  • a method of adding a hydrophobic film coating process or the like is used, but this method has drawbacks such as an increase in cost and a decrease in productivity due to the addition of the process.
  • thermoplastic resin composition excellent in surface hydrophobicity and the like without such a problem.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in surface hydrophobicity and the like.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition comprises about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; From about 0.05 to about 5 parts by weight of maleic anhydride-aromatic vinyl-based copolymer; And about 0.1 to about 10 parts by weight of an aliphatic carboxylic acid ester compound.
  • the rubber-modified aromatic vinyl-based copolymer resin comprises about 10 to about 50% by weight of a rubber-modified vinyl-based graft copolymer; And about 50 to about 90 weight percent of an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer may be one obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer in a rubbery polymer.
  • the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
  • the maleic anhydride-aromatic vinyl-based copolymer may be a polymer of about 5 to about 40% by weight of maleic anhydride and about 60 to about 95% by weight of an aromatic vinyl monomer.
  • the weight average molecular weight of the maleic anhydride-aromatic vinyl-based copolymer may be from about 50,000 to about 150,000 g / mol.
  • the aliphatic carboxylic acid ester compound may be a dehydration condensate of an aliphatic carboxylic acid having 10 to 100 carbon atoms and a monohydric or polyhydric alcohol having 2 to 50 carbon atoms.
  • the weight ratio of the maleic anhydride-aromatic vinyl copolymer and the aliphatic carboxylic acid ester compound may be about 1: about 1: about 1: about 30.
  • thermoplastic resin composition may further comprise a polyamide resin.
  • thermoplastic resin composition according to any one of 1 to 8 above, wherein 3 ⁇ ⁇ of distilled water is dropped to a 100 mm ⁇ 100 mm size specimen, the contact angle of water on the surface of the specimen measured by a contact angle meter is about 90 to about 105 ⁇ have.
  • Another aspect of the present invention relates to a molded article.
  • the molded article is formed from the thermoplastic resin composition according to any one of 1 to 9 above.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in surface hydrophobicity and the like and a molded article formed therefrom.
  • thermoplastic resin composition according to the present invention comprises (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) maleic anhydride-aromatic vinyl-based copolymer; And (C) an aliphatic carboxylic acid ester compound.
  • the rubber-modified aromatic vinyl-based copolymer resin of the present invention may comprise (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention may be one obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer in a rubber-like polymer.
  • the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer to a rubbery polymer, and if necessary, The graft polymerization may be further carried out by further including a monomer which imparts heat resistance.
  • the polymerization may be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization.
  • the rubber-modified vinyl-based graft copolymer may form a core (rubbery polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.
  • the rubbery polymer examples include a diene rubber such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), a saturated rubber which is hydrogenated with the diene rubber, an isoprene rubber, A copolymer of an alkyl (meth) acrylate rubber having 2 to 10 carbon atoms, an alkyl (meth) acrylate having 2 to 10 carbon atoms and styrene, and an ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more.
  • diene rubber, (meth) acrylate rubber and the like can be used.
  • butadiene rubber, butyl acrylate rubber and the like can be used.
  • the rubbery polymer (rubber particles) may have an average particle size of from about 0.05 to about 6 microns, such as from about 0.15 to about 4 microns, and specifically from about 0.25 to about 3.5 microns.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the average particle size (z-average) of the rubbery polymer (rubber particles) can be measured using a light scattering method in a latex state.
  • a rubbery polymer latex was smeared on a mesh to remove coagulum formed during the polymerization of the rubbery polymer, and a solution prepared by mixing 0.5 g of latex and 30 ml of distilled water was poured into a 1,000 ml flask and filled with distilled water to prepare a sample , 10 ml of the sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size analyzer (malvern, nano-zs).
  • a light scattering particle size analyzer malvern, nano-zs
  • the content of the rubbery polymer may be from about 20 to about 70 weight percent, such as from about 25 to about 60 weight percent, of the total 100 weight percent of the rubber modified vinyl based graft copolymer, and the monomer mixture Vinyl monomers and vinyl cyanide monomers) may be from about 30 to about 80 wt%, for example from about 40 to about 75 wt%, of 100 wt% of the total rubber modified vinyl-based graft copolymer.
  • the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.
  • the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and may be selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more.
  • the content of the aromatic vinyl monomer may be about 10 to about 90 wt%, for example about 40 to about 90 wt%, based on 100 wt% of the monomer mixture. Within the above range, the processability and impact resistance of the thermoplastic resin composition can be excellent.
  • the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, For example. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used.
  • the content of the vinyl cyanide monomer may be about 10 to about 90% by weight, for example about 10 to about 60% by weight, based on 100% by weight of the monomer mixture.
  • the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.
  • examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like.
  • the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight, based on 100% by weight of the monomer mixture.
  • the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.
  • g-ABS butadiene rubber- Styrene-acrylonitrile graft copolymer
  • g-ASA butadiene rubber- Styrene-acrylonitrile graft copolymer
  • the rubber-modified vinyl-based graft copolymer (A1) is used in an amount of about 10 to about 50% by weight, for example about 15 to about 45% by weight, %. ≪ / RTI > Within the above range, the thermoplastic resin composition may have excellent impact resistance and moldability.
  • the aromatic vinyl-based copolymer resin according to one embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a usual rubber-modified vinyl-based copolymer resin.
  • the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture comprising an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
  • the aromatic vinyl-based copolymer resin can be obtained by mixing an aromatic vinyl monomer, a vinyl cyanide monomer or the like and then polymerizing the aromatic vinyl monomer, and the polymerization can be carried out by known polymerization such as emulsion polymerization, suspension polymerization, Method. ≪ / RTI >
  • the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used alone or in combination of two or more.
  • the content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example about 30 to about 80% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin.
  • the impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.
  • examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used.
  • the content of the vinyl cyanide monomer may be about 10 to about 80% by weight, for example about 20 to about 70% by weight, based on 100% by weight of the total aromatic vinyl copolymer resin.
  • the impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.
  • the aromatic vinyl-based copolymer resin may be a polymer obtained by further comprising a monomer for imparting processability and heat resistance to the monomer mixture.
  • a monomer for imparting processability and heat resistance examples include (meth) acrylic acid, N-substituted maleimide and the like, but are not limited thereto.
  • the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight, based on 100% by weight of the monomer mixture.
  • the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.
  • the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 10,000 to about 300,000 g / mol, such as from about 15,000 to about 150,000 g / .
  • Mw weight average molecular weight
  • the thermoplastic resin composition may have excellent mechanical strength and moldability.
  • the aromatic vinyl-based copolymer resin (A2) is used in an amount of about 50 to about 90% by weight, for example, about 55 to about 85% by weight, based on 100% by weight of the whole rubber-modified aromatic vinyl- .
  • the thermoplastic resin composition may have excellent impact resistance and moldability.
  • the maleic anhydride-aromatic vinyl-based copolymer of the present invention is a polymer of maleic anhydride and aromatic vinyl-based monomer capable of improving surface hydrophobicity and the like of the thermoplastic resin composition together with an aliphatic carboxylic acid ester compound .
  • the maleic anhydride-aromatic vinyl-based copolymer may be obtained by mixing maleic anhydride and aromatic vinyl-based monomer or the like and then polymerizing the monomer.
  • the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used alone or in combination of two or more.
  • the maleic anhydride may comprise from about 5 to about 40 weight percent, for example from about 10 to about 35 weight percent, of the total maleic anhydride-aromatic vinyl-based copolymer
  • the monomers may comprise from about 60 to about 95 weight percent, for example from about 65 to about 90 weight percent, of 100 weight percent of the total maleic anhydride-aromatic vinyl copolymer.
  • the surface hydrophobicity and impact resistance of the thermoplastic resin composition may be excellent in the above range.
  • the maleic anhydride-aromatic vinyl-based copolymer has a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 50,000 to about 150,000 g / mol, such as from about 60,000 to about 120,000 g / mol.
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the surface hydrophobicity and impact resistance of the thermoplastic resin composition may be excellent in the above range.
  • the maleic anhydride-aromatic vinyl-based copolymer is included in about 0.05 to about 5 parts by weight, for example about 0.1 to about 4 parts by weight, relative to about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin .
  • the content of the maleic anhydride-aromatic vinyl-based copolymer is less than about 0.05 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the surface hydrophobicity and impact resistance of the thermoplastic resin composition may decrease And when it is more than about 5 parts by weight, the fluidity and the like of the thermoplastic resin composition may be lowered.
  • the aliphatic carboxylic acid ester compound of the present invention can improve the surface hydrophobicity and the like of the thermoplastic resin composition together with the maleic anhydride-aromatic vinyl copolymer.
  • the aliphatic carboxylic acid ester compound having an aliphatic carboxylic acid having a carbon number of 10 to 100 and an aliphatic carboxylic acid having a carbon number of 2 to 50 And may be a dehydration condensate of a monovalent or polyvalent alcohol.
  • examples of the aliphatic carboxylic acid ester compound include pentaerythritol tetrastearate, glycerol monostearate, palmityl palmitate, stearyl stearate, and combinations thereof.
  • the aliphatic carboxylic acid ester compound may be included in an amount of about 0.1 to about 10 parts by weight, for example about 0.5 to about 5 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • the content of the aliphatic carboxylic acid ester compound is less than about 0.1 part by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the surface hydrophobicity and the like of the thermoplastic resin composition may be lowered. The heat resistance and flexural strength of the thermoplastic resin composition may be lowered.
  • the weight ratio ((B) :( C)) of the maleic anhydride-aromatic vinyl copolymer (B) and the aliphatic carboxylic acid ester compound (C) is from about 1: about 1 to about 1: 30, such as about 1: about 1 to about 1: about 10.
  • the surface hydrophobicity and impact resistance of the thermoplastic resin composition may be more excellent in the above range.
  • the thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition.
  • the additives include, but are not limited to, flame retardants, fillers, antioxidants, anti-drop agents, lubricants, mold release agents, nucleating agents, stabilizers, pigments, dyes, and mixtures thereof.
  • its content may be from about 0.001 to about 40 parts by weight, for example from about 0.1 to about 10 parts by weight, relative to about 100 parts by weight of the thermoplastic resin.
  • thermoplastic resin composition according to one embodiment of the present invention is prepared by mixing the above components and melt-extruding at a temperature of about 200 to about 280 ⁇ , for example, about 220 to about 250 ⁇ , using a conventional twin-screw extruder. .
  • thermoplastic resin composition is prepared by dropping 3 ⁇ l of distilled water on a 100 mm ⁇ 100 mm specimen, measuring the contact angle of water on the surface of the specimen with a contact angle meter of about 90 to about 105 °, for example, about 93 to about 105 < / RTI >
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be produced in the form of pellets, and the produced pellets may be manufactured into various molded products through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains.
  • the molded article is excellent in surface hydrophobicity and the like, and thus is useful as a building exterior material.
  • G-ABS in which 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) were graft-copolymerized was used in a butadiene rubber having a Z-average of 310 nm of 45% by weight.
  • SAN resin (weight average molecular weight: 130,000 g / mol) in which 75% by weight of styrene and 25% by weight of acrylonitrile were polymerized was used.
  • Styrene-maleic anhydride copolymer (SMA resin, weight average molecular weight: 80,000 g / mol, styrene / maleic anhydride (weight ratio): 74/26) was used.
  • PMI-SAN resin weight average molecular weight: 130,000 g / mol
  • PMI-SAN resin weight average molecular weight: 130,000 g / mol
  • Pentaerythritol tetrastearate manufactured by NOF Corporation, product name: UNISTER H-476, was used.
  • the above components were added in the amounts shown in Tables 1 and 2, and then extruded at 230 ° C to prepare pellets.
  • the pellets were extruded at a temperature of 230 ° C. and a mold temperature of 60 ° C. in a 6 Oz extruder at 80 ° C. for 2 hours or more, .
  • the properties of the prepared specimens were evaluated by the following methods, and the results are shown in Tables 1 and 2 below.
  • MI Melt-flow Index
  • VST Vicat Softening Temperature
  • Example One 2 3 4 5 6 (A) (parts by weight) 100 100 100 100 100 100 100 (B1) (parts by weight) 0.1 0.5 One 3 0.5 0.5 (B2) (parts by weight) - - - - - - (C) (parts by weight) 3 3 3 3 3
  • thermoplastic resin compositions of the present invention are excellent in surface hydrophobicity, impact resistance, fluidity, heat resistance and the like.
  • Comparative Example 1 in which a small amount of the maleic anhydride-aromatic vinyl copolymer was applied, surface hydrophobicity and the like were lowered, and in Comparative Example 1 in which the maleic anhydride-aromatic vinyl copolymer was excessively applied, Able to know.
  • Comparative Example 3 in which a small amount of the aliphatic carboxylic acid ester compound was applied, surface hydrophobicity and the like were lowered, and in Comparative Example 4 in which the aliphatic carboxylic acid ester compound was excessively applied, heat resistance and the like were lowered.
  • Comparative Examples 5 and 6 in which a maleimide-vinyl copolymer was used instead of the maleic anhydride-aromatic vinyl copolymer, surface hydrophobicity and the like were lowered.

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

Abstract

L'invention concerne une composition de résine thermoplastique qui comprend : environ 100 parties en poids d'une résine copolymère à base de vinyle aromatique modifiée par du caoutchouc ; environ 0,05 à environ 5 parties en poids d'un copolymère à base de vinyle aromatique anhydride maléique ; et environ 0,1 à environ 10 parties en poids d'un composé ester d'acide carboxylique aliphatique. La composition de résine thermoplastique est supérieure en termes d'hydrophobicité de surface, etc.
PCT/KR2018/016175 2017-12-28 2018-12-19 Composition de résine thermoplastique et article moulé formé à partir de celle-ci WO2019132388A1 (fr)

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Application Number Priority Date Filing Date Title
KR1020170182004A KR102012105B1 (ko) 2017-12-28 2017-12-28 열가소성 수지 조성물 및 이로부터 형성된 성형품
KR10-2017-0182004 2017-12-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024115634A1 (fr) * 2022-12-02 2024-06-06 Sabic Global Technologies B.V. Composition thermoplastique pour le placage de métaux

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR910003772B1 (ko) * 1986-12-20 1991-06-12 스태미카본 베. 뷔. 열가소성 폴리머 조성물
JPH04126745A (ja) * 1990-03-07 1992-04-27 Monsant Kasei Kk 耐衝撃性熱可塑性樹脂組成物
JPH0660270B2 (ja) * 1983-10-01 1994-08-10 デーエスエム ナムローゼ フェンノート シャップ 耐衝撃性の熱可塑性成形コンパウンドの製造法
JPH11140266A (ja) * 1997-11-10 1999-05-25 Mitsubishi Chemical Corp ゴム変成スチレン系樹脂組成物
JP2003502469A (ja) * 1999-06-11 2003-01-21 バイエル アクチェンゲゼルシャフト 熱可塑性成型用組成物
WO2017089222A1 (fr) * 2015-11-23 2017-06-01 Elix Polymers, S.L. Composition abs thermoplastique renforcée par des fibres naturelles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0660270B2 (ja) * 1983-10-01 1994-08-10 デーエスエム ナムローゼ フェンノート シャップ 耐衝撃性の熱可塑性成形コンパウンドの製造法
KR910003772B1 (ko) * 1986-12-20 1991-06-12 스태미카본 베. 뷔. 열가소성 폴리머 조성물
JPH04126745A (ja) * 1990-03-07 1992-04-27 Monsant Kasei Kk 耐衝撃性熱可塑性樹脂組成物
JPH11140266A (ja) * 1997-11-10 1999-05-25 Mitsubishi Chemical Corp ゴム変成スチレン系樹脂組成物
JP2003502469A (ja) * 1999-06-11 2003-01-21 バイエル アクチェンゲゼルシャフト 熱可塑性成型用組成物
WO2017089222A1 (fr) * 2015-11-23 2017-06-01 Elix Polymers, S.L. Composition abs thermoplastique renforcée par des fibres naturelles

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024115634A1 (fr) * 2022-12-02 2024-06-06 Sabic Global Technologies B.V. Composition thermoplastique pour le placage de métaux

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