EP0693095A1 - Compositions polymeres melangees presentant une brillance limitee - Google Patents

Compositions polymeres melangees presentant une brillance limitee

Info

Publication number
EP0693095A1
EP0693095A1 EP94913386A EP94913386A EP0693095A1 EP 0693095 A1 EP0693095 A1 EP 0693095A1 EP 94913386 A EP94913386 A EP 94913386A EP 94913386 A EP94913386 A EP 94913386A EP 0693095 A1 EP0693095 A1 EP 0693095A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
rubber
composition
monovinylidene aromatic
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP94913386A
Other languages
German (de)
English (en)
Inventor
Henricus J. M. Van Dijk
Sarada P. Namhata
Martin J. Guest
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0693095A1 publication Critical patent/EP0693095A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment

Definitions

  • the present invention relates to thermoplastic polymer blends, more specifically, it relates to blends containing a styre ⁇ ic polymer and a polycarbonate Injection molding of many thermoplastic polymers and blends thereof give parts having a glossy appearance
  • a range of applications can be identified for which a matte or low gloss surface is desirable
  • surface finishing techniques are available for reducing the gloss of molded parts, these techniques can require a separate process, such as surface embossing or coating
  • Blends of aromatic carbonate polymers with other thermoplastics are known in the art
  • polycarbonate blends with styrenic copolymers include those systems using acrylonit ⁇ le-butadiene-styrene (ABS) components produced either via mass or mass- -suspension techniques, such as described in U S Patent 4,624,986, or those produced via emulsion techniques, such as described in U S Patent 3, 130,177
  • ABS Patent 4,526,926 discloses polycarbonate/ABS blends having large rubber particles wherein the ABS is prepared via a mass process, via an emulsion process or a combination of both These blend systems are noted for their good processing characteristics and balance of physical properties which include impact strength and high heat distortion
  • Epoxy functional polymers are one class of polymers known to act as matting agents, resulting in reduced gloss of parts molded from thermoplastic polymers and their blends
  • EP 89,042-B1 describes polycarbonate/ABS compositions which additionally include an epoxy-functional olefin polymer and these are disclosed as having good weld line strength
  • EP 249,998-A and EP 375,940-A describe compositions where epoxy functionality is incorporated via copolyme ⁇ zation in the production of the grafted rubbers, and these compositions are disclosed to give low gloss appearance in molded parts
  • EP 375,941 -A2 describes polycarbonate/emulsion ABS compositions, including an epoxy modified styrenic copolymer, which compositions give low gloss, molded parts
  • the preferred ABS polymers often contain high amounts of rubber
  • thermoplastic blend systems which have low gloss characteristics, retain physical properties such as impact strength and heat resistance, and additionally have good processability
  • thermoplastic polymer blend compositions having low gloss in combination with improved processability and good physical properties
  • this invention covers blends comprising a polycarbonate polymer, at least one monovinylidene aromatic copolymer which is rubber-modified and produced via a mass process, at least one monovinylidene aromatic copolymer which is rubber-modified and produced via an emulsion process, low levels of an epoxy-group-containing copolymer, and optionally additional monovinylidene aromatic copolymers These compositions retain good low gloss characteristics, and show improved processability
  • compositions of the invention are useful in the preparation of molded goods such as components in automobiles, business machines, and other consumer products
  • the thermoplastic polymer blend composition of this invention comprises (A) from 35 to 90 weight parts of an aromatic carbonate polymer; (B) from 10 to 65 weight parts of a combination of monovinylidene aromatic copolymers, including (B1 ) from 1 to 99 weight percent of a mass polymerized rubber-modified copolymer, (B2) from 1 to 99 weight percent of an emulsion polymerized rubber-modified copolymer; and (B3) from 0 to 98 percent of a monovinylidene aromatic copolymer; and (C) from 0 1 to 15 weight parts of an epoxy- -containing alkene copolymer
  • the thermoplastic polymer blend composition of this invention preferably comprises: (A) from 40 to 85 weight parts of an aromatic carbonate polymer, (B) from 15 to 60 weight parts of a combination of monovinylidene aromatic copolymers, and (C) from 1 to 10 weight parts of an epoxy-containing alkene copolymer
  • component (B) comprises (B1) from 20
  • polycarbonate resins suitable for use as component (A) herein include aromatic polycarbonates which contain the repetitive carbonate group,
  • the polycarbonate can be characterized as possessing recurring structural units of the following formula and structural isomers thereof:
  • A is a single bond or is a divalent aliphatic radical such as an alkylene or an alkylidene radical usually with 1 to 7 carbon atoms, or a cycloalkylene or cycloalky dene radical usually with 5 to 15 carbon atoms, with all including their aromatically and aliphatically substituted derivatives
  • A can also represent -0-, -S-, -CO-, -SO- or -S ⁇ 2-
  • R' and R" are substituents other than hydrogen such as, for example, halogen or a saturated or unsaturated monovalent aliphatic radical having usually 1 to 7 carbon atoms, and each n is independently from 0 to 4
  • Typical of the above-mentioned structural unit are those which result from the reaction of phosgene (or other carbonyl-providing species) with b ⁇ s-(hydroxyphenyl) alkanes, b ⁇ s-(hydroxyphenyl) cycloalkanes, b ⁇ s-(hydroxyphenyl) sulfides, b ⁇ s-(hydroxyphenyl) ethers, bis- (hydroxyphenyl) ketones, b ⁇ s-(hydroxyphenyl) sulfoxides, b ⁇ s-(hydroxyphenyl) sulfones, ⁇ , ⁇ '-b ⁇ s- (hydroxyphenyl) isopropyl benzene, b ⁇ s-(3,5-bromo-4-hydroxyphenyl) sulfone, b ⁇ s-(tetrabromo- 4-hydroxyphenyl) propane, b ⁇ s-(3,5,6-tr ⁇ -chloro-2-hydroxyphenyl) methane, 2,2'
  • the carbonate polymer may be derived from two or more different hydric phenols or a copolymer of a hydric phenol with a glycol if a copolymer carbonate rather than a carbonate homopolymer is desired
  • a copolymer carbonate rather than a carbonate homopolymer is desired
  • polycarbonate and "aromatic carbonate polymer” are the ester carbonate copolymers of the types described in U S Patents 3J69J 21 , 4,330,662 and 4,105,633 Typical comonomers are dicarboxy c acids such as, for example, terephthahc acid Additionally included in the scope of this invention are so-called “branched polycarbonates” which are made by using the above-described polyhyd ⁇ c monomers in combination with a suitable branching agent, normally tn- or higher polyfunctional molecules
  • the polycarbonate resins employed herein preferably have a melt flow rate, measured according to ASTM D-1238 (condition O 300°C, 1 2 kg load), of from 0 5 to 200 g/10 mm, preferably from 2 5 to 100 g/10 minutes, more preferably from 5 to 90 g/10 minutes and especially preferred from 8 to 75 g/10 minutes
  • Component (B) comprises a combination of monovinylidene aromatic copolymers which are rubber-modified (B1 and B2) and optionally a non-rubber-modified monovinylidene aromatic copolymer (B3)
  • suitable monovinylidene aromatic monomer constituents include styrene, alkyl-substituted styrenes such as alpha-alkylstyrene (for example, alpha-methylstyrene and alpha-ethylstyrene), various ring-substituted styrenes such as para-methylstyrene, ortho-ethylstyrene and 2,4-d ⁇ methylstyrene, and ring-substituted halo-styrenes such as chloro-styrene and 2,4-d ⁇ chloro-styrene Styrene is the preferred monovinylidene
  • the polymer blend compositions have two or more components (for example, B 1 and B2) wherein the monovinylidene aromatic copolymers are rubber-modified, for example, having dispersed particles of a rubbery polymer with a glass transition temperature of 0°C or lower
  • Especially preferred rubbery polymers for use herein are those having a glass transition temperature of -20°C or lower
  • suitable such rubbery polymers include homopolymers of 1 ,3-conjugated alkadiene monomers, copolymers of from 60 to 99 weight percent of said 1 ,3-conjugated alkadienes with from 1 to 40 weight percent of a monoethylenically unsaturated monomer such as, for example, monovinylidene aromatic monomers (for example, styrene) and ethylenically unsaturated nit ⁇ les such as acrylonitrile and methacrylonit ⁇ le, ethylene/propylene copolymer rubbers, and ethylene/propylene/n
  • Rubber-modified copolymers such as ABS, consist of a rigid matrix or continuous phase having dispersed therein particles of the elastomer, such particles usually having grafted thereto amounts of the rigid copolymer Component (B1) includes rubber-modified monovinylidene aromatic copolymers produced via mass or mass-suspension techniques, resulting in grafted rubber particles which have a portion of the rigid copolymer occluded in the rubber phase
  • the rubber types described above are present in an amount of from 1 to 40 percent, preferably 3 to 25 percent, and most preferably 5 to 20 percent
  • the rubber particles generally have a volume average particle size of from 0 4 to 10 micron
  • Mass or bulk polymerized rubber-modified monovinylidene aromatic copolymers are commercially available and are known to those skilled in the art. See, for example, U S. Patents 3,243,481 ; 3,509,237; 3,660,535, 4,221 ,833 and 4,239,863
  • Component (B2) includes rubber-modified monovinylidene aromatic copolymers in which the rubber particles are produced via emulsion techniques At least a portion of the rubber particles are grafted to the matrix copolymer
  • the rubber types described above advantageously are present in amounts of from 10 to 85 percent, preferably from 20 to 75 percent, and more preferably from 35 to 60 percent
  • the rubber particles generally have a volume average particle size of from 0 05 to 5 micron
  • emulsion polymerization techniques are generally economically feasible for the production of rubber particles having diameters less than about 0.25 ⁇ m
  • Such particles must usually be agglomerated or coagulated in some way before, during and/or after grafting in order to achieve rubber particles having diameters greater than about 0.5 ⁇ m
  • Agglomerating and coagulating techniques are well known in the art See, for example, U S Patents 3, 551 ,370, 3,666,704; 3,956,218 and 3,825,621 A particularly desirable technique for the controlled agglomeration of the
  • Emulsion polymerized monovinylidene aromatic copolymers are commercially available, and preferably are in the form of butadiene rubber particles grafted with a mixture of styrene and acrylonitrile (SAN), and having a relatively high (greater than 20 percent) rubber content
  • SAN styrene and acrylonitrile
  • rubber-reinforced copolymers can be prepared using techniques known to those skilled in the art and including, for example, the method taught in U S Patent 3J 30,177
  • the rubber particles which advantageously can be butadiene or acrylate based rubbers, can be grafted with a mixture of styrene and/or (methyl meth)acrylate monomers.
  • the epoxy group-containing alkene copolymer, component (C), is a copolymer of at least one unsaturated epoxy compound and at least one alkene with or without at least one ethylenically unsaturated compound. While no special limitation is present in the composition of these monomers, the content of the unsaturated epoxy compound(s) is preferred to be from 0.05 to 95 percent by weight.
  • the unsaturated epoxy compound(s) there may be used the ones having an unsaturated group copolymerizable with an olefin and ethylenically unsaturated compound as well as an epoxy group in the molecule. For instance, unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxyalkenes or p-glycidylstyrenes are usable. Those of the following formulas are also usable:
  • R is a C 2 -C ⁇ s hydrocarbon group having ethylenic unsaturation
  • Z is a hydrogen atom or a methyl group
  • X is:
  • glycidyl acrylate glycidyl methacrylate
  • glycidyl itaconate butenecarboxylates
  • allyl glycidyl ether 2-methylallyl glycidyl ether
  • styrene-p-glycidyl ether 3,4-epoxybutene, 3,4-epoxy-3-methyl-1 -butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and p-glycidylstyrene
  • Mixtures of unsaturated epoxy compounds can be employed
  • alkene examples include olef ins such asJor example, ethylene, propylene, butene-1 , pentene-1 , and 4-methylpentene-1 , and alkenyl aromatic compounds including the monovinylidene aromatic monomers mentioned hereinabove
  • alkenes include ethylene and styrene Mixtures of alkenes can be employed
  • ethylenically unsaturated compound(s) there are exemplified olefins, vinyl esters having a C 2 -C ⁇ saturated carboxy c acid moiety, acrylic and methacrylic esters having a C--Cg saturated alcohol moiety, maleic esters having a Ci- s saturated alcohol moiety, vinyl hahdes, vinyl ethers, N-vinyllactams and carbonamides
  • olefins vinyl esters having a C 2 -C ⁇ saturated carboxy c acid moiety
  • acrylic and methacrylic esters having a C--Cg saturated alcohol moiety maleic esters having a Ci- s saturated alcohol moiety
  • vinyl hahdes vinyl ethers
  • preferred ethylenically unsaturated compounds include vinyl acetate and methyl acrylate
  • These ethylenically unsaturated compounds may be copolyme ⁇ zed with the unsaturated epoxy compounds and the
  • the epoxy group-containing alkene copolymer (C) may be prepared by various procedures, of which one typical example comprises contacting an unsaturated epoxy compound and an alkene, with or without an ethylenically unsaturated compound, with a radical generating agent at a temperature of 40°C to 300°C under a pressure of 50 to 4000 atm Another typical example comprises irradiating gamma-rays into a mixture of poly-propylene with an unsaturated epoxy compound under a high degree of reduced pressure Typical methods of preparation are taught in U S Patent 4,721 ,761
  • Component (C) is used in amounts of from 0 1 to 15 parts by weight of the blend composition, preferably from 1 to 10 parts by weight and most preferably from 2 to 8 parts by weight Greater amounts of component (C) are found to adversely affect the blend properties, especially heat resistance
  • blends of the invention may be further modified by the addition of other types of conventional additives known in the art of plastics compounding
  • additives can include fillers (such as clay or talc), reinforcing agents (such as glass fibers), impact modifiers, other resins, plasticizers, flow promoters and other processing aids, stabilizers, colorants, mold release agents, flame retardants and ultraviolet screening agents
  • compositions of the invention advantageously contain from 1 to 40 percent by weight of rubber, preferably from 2 to 30 percent by weight and most preferably from 3 to 25 percent by weight
  • compositions of the invention are prepared via any of the blending operations known for the blending of thermoplastics, such as solvent blending or blending in a kneading machine, such as a Banbury mixer, or an extruder.
  • the sequence of addition is not critical but all main components should be thoroughly blended together.
  • the blend compositions of the Examples and Comparative Experiments are prepared by compounding the various components together.
  • the blends are injection molded to prepare parts for the property evaluations.
  • a Buss Ko-Kneader compounding machine, model MDK-46, is used to prepare the blends under the following conditions: the temperature profile is 160°C - 240°C - 250°C - 240°C - 160°C; the dosing speed is 30 rpm; and the throughput is 20 kg/hour at 204 rpm.
  • Molding of blends is carried out on a Klockner Ferromatic KF-60 machine to produce plaques and other test parts under the following conditions: the temperature profile is 250°C - 255°C - 260°C - 270°C; the mold temperature is 75°C; the injection speed is 30 mm/s; and the cooling time is 30 s. All formulations include a colorant system which is 1.7 parts by weight of a carbon black, Taxa 2319, unless otherwise indicated. Other materials employed are as follows:
  • ABS-M is a mass polymerized ABS containing 15 percent acrylonitrile and 12 percent polybutadiene;
  • Calibre ® polycarbonate resins are products of The Dow Chemical Company
  • Magnum ® 3453 and 3154 are commercially available mass ABS polymers produced by The Dow Chemical Company;
  • Magnum ® 3416HH is a high heat ABS available from The Dow Chemical Company
  • Dylark ® 232 is a rubber modified styrene/maleic anhydride copolymer produced by The Atlantic Richfield Company;
  • Igetabond ® 2B is a product of The Sumitomo Chemical Company
  • ABS-E is an emulsion polymerized SAN grafted polybutadiene with a 48 percent rubber content
  • Tyril® styrene acrylonitrile resins are a product of The Dow Chemical Company.
  • Paraloid ® 2B is a product of Rohm and Haas.
  • compositions given in weight parts, and relevant property data are as follows:
  • Example 1 shows that the desired low gloss property is achieved while keeping a formulation of significantly higher flow performance than Comparative Experiment A as measured via the melt flow rate.
  • the other thermal and mechanical properties of the blend Example 1 are improved or essentially maintained compared to that of Comparative Experiment A.
  • compositions given in weight parts, and relevant property data are presented in Table 1.
  • Examples 2-7 illustrate a range of relevant composition ratios and different Component (A) types, including Example 5, which is based on a branched polycarbonate.
  • Comparative Experiments B and E without Component (C) exhibit high gloss.
  • Comparative Experiment C shows that addition of Component (C) to a formulation based only on mass ABS shows no significant gloss reduction.
  • Comparative Experiment D is a formulation which only includes emulsion ABS as a component, and shows low gloss in combination with a major decrease in flow behavior.
  • Examples 8-10 illustrate the broad applicability of a range of different comonomers in combination with monovinylidene aromatic monomers, which are optionally rubber-modified, and comprise Component (B).
  • Comparative Experiment F shows that poor gloss and flow is observed for compositions low in Component (A).
  • ABS-E 1 10.0 10.0 10.0 10.0 13.3 10.0 10.0 12.5 10.0 - - 18.7 19.3 20.0
  • Tyril ® 114 # 7.5 7.5 7.5 7.5 10.0 - 7.5 - 7.5 - 14J 14.5 15.3 lgetabond ® 2B @ 3.0 3.0 3.0 3.0 6.0 3.0 3.0 3.0 3.0 - 3.0 3.0 - 3.0

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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)
  • Graft Or Block Polymers (AREA)

Abstract

Compositions mélangées de polymères thermoplastiques présentant une brillance limitée associée à des caractéristiques améliorées de traitement, ainsi qu'à des propriétés physiques optimisées. Lesdites compositions comprennent: un polymère de polycarbonate; des niveaux bas d'un copolymère contenant des groupes époxy; au moins un copolymère aromatique de monovinylidène, dont la teneur en caoutchouc est modifiée et qui est produit au moyen d'un procédé en masse; au moins un copolymère aromatique de monovinylidène, dont la teneur en caoutchouc est modifiée et qui est produit au moyen d'un procédé d'émulsion; et, éventuellement, des copolymères aromatiques de monovinylidène supplémentaires.
EP94913386A 1993-04-08 1994-04-07 Compositions polymeres melangees presentant une brillance limitee Ceased EP0693095A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US4554693A 1993-04-08 1993-04-08
PCT/US1994/003854 WO1994024210A1 (fr) 1993-04-08 1994-04-07 Compositions polymeres melangees presentant une brillance limitee
US45546 1998-03-20

Publications (1)

Publication Number Publication Date
EP0693095A1 true EP0693095A1 (fr) 1996-01-24

Family

ID=21938534

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94913386A Ceased EP0693095A1 (fr) 1993-04-08 1994-04-07 Compositions polymeres melangees presentant une brillance limitee

Country Status (5)

Country Link
EP (1) EP0693095A1 (fr)
JP (1) JPH08508783A (fr)
KR (1) KR960701953A (fr)
CA (1) CA2159351A1 (fr)
WO (1) WO1994024210A1 (fr)

Families Citing this family (12)

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Publication number Priority date Publication date Assignee Title
ES2112612T3 (es) * 1994-11-21 1998-04-01 Gen Electric Composiciones de copolimeros de compuestos alfa-alquil vinilaromaticos-cianuro de vinilo modificadas en su resistencia al impacto.
JP2002105299A (ja) * 2000-09-29 2002-04-10 Asahi Kasei Corp ポリカーボネート系難燃樹脂組成物
KR100376279B1 (ko) * 2000-11-06 2003-03-17 금호케미칼 주식회사 성형성이 개선된 내충격, 내열 저광택성 수지조성물
JP4679011B2 (ja) * 2001-09-27 2011-04-27 三菱エンジニアリングプラスチックス株式会社 ポリカーボネート樹脂組成物
US6849687B2 (en) 2002-08-01 2005-02-01 Bayer Polymers Llc Thermoplastic composition having low gloss appearance
DE102005058836A1 (de) 2005-12-09 2007-06-14 Bayer Materialscience Ag Polycarbonat-Formmassen
US8222351B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions
US8222350B2 (en) 2007-02-12 2012-07-17 Sabic Innovative Plastics Ip B.V. Low gloss polycarbonate compositions
CN101469120B (zh) * 2007-12-25 2012-10-17 上海普利特复合材料股份有限公司 一种低光泽、高抗冲、高流动聚碳酸酯组合物
KR101453772B1 (ko) 2010-10-22 2014-10-21 제일모직 주식회사 폴리카보네이트 수지 조성물 및 이를 이용한 성형품
KR102337560B1 (ko) * 2018-04-30 2021-12-10 롯데첨단소재(주) 열가소성 수지 조성물 및 이를 포함하는 성형품
WO2019212222A1 (fr) * 2018-04-30 2019-11-07 롯데첨단소재(주) Composition de résine thermoplastique et article moulé comprenant celle-ci

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US4444950A (en) * 1982-03-15 1984-04-24 Sumitomo Naugatuck Co., Ltd. Thermoplastic resin composition
US4526926A (en) * 1983-04-22 1985-07-02 The Dow Chemical Company Low gloss carbonate polymer blends
DE3615608A1 (de) * 1986-05-09 1987-11-12 Basf Ag Thermoplastische formmasse auf basis von polycarbonat, 2 pfropfmischpolymerisaten unterschiedlicher pfropfgrundlage (asa + aes) und vinylaromat/an enthaltenden copolymerisaten
WO1991013119A1 (fr) * 1990-02-21 1991-09-05 Exxon Chemical Limited Polyester thermoplastique ayant des caracteristiques d'impact ameliorees.
JP2955944B2 (ja) * 1990-03-29 1999-10-04 三菱レイヨン株式会社 疲労特性が改良された熱可塑性樹脂組成物
DE4122871A1 (de) * 1990-11-29 1992-06-04 Bayer Ag Abs-formmassen

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Also Published As

Publication number Publication date
JPH08508783A (ja) 1996-09-17
KR960701953A (ko) 1996-03-28
WO1994024210A1 (fr) 1994-10-27
CA2159351A1 (fr) 1994-10-27

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