EP0462185A4 - Molding compositions comprising carbonate polymer, rubber modified vinyl aromatic-nitrile graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions - Google Patents

Molding compositions comprising carbonate polymer, rubber modified vinyl aromatic-nitrile graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions

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Publication number
EP0462185A4
EP0462185A4 EP19900904582 EP90904582A EP0462185A4 EP 0462185 A4 EP0462185 A4 EP 0462185A4 EP 19900904582 EP19900904582 EP 19900904582 EP 90904582 A EP90904582 A EP 90904582A EP 0462185 A4 EP0462185 A4 EP 0462185A4
Authority
EP
European Patent Office
Prior art keywords
polymer
graft copolymer
weight
rubber
percent
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.)
Withdrawn
Application number
EP19900904582
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English (en)
Other versions
EP0462185A1 (fr
Inventor
Michael K. Laughner
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
Priority claimed from US07/411,278 external-priority patent/US5068285A/en
Priority claimed from US07/411,279 external-priority patent/US5008330A/en
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0462185A1 publication Critical patent/EP0462185A1/fr
Publication of EP0462185A4 publication Critical patent/EP0462185A4/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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
    • 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
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates

Definitions

  • This invention relates to thermoplastic resin compositions and more particularly relates to improved blends of carbonate polymers, core/shell graft copolymers and rubber modified vinyl aromatic- acrylonitrile graft copolymers where the rubber is other than a conjugated diene polymer and a method of using the compositions.
  • More specific examples of this invention include molding compositions comprising a blend of (1) one or more carbonate polymer with (2) one or more graft copolymer of vinyl aromatic-nitrile copolymer onto one or more rubbery polymer of ethylene-propylene- nonconjugated diene monomer (EPDM) , which includes an EPDM-vinyl aromatic hydrocarbon copolymer rubber; or onto one or more rubbery polymer of al yl acrylate(s), which include an alkyl acrylate-vinyl aromatic hydrocarbon copolymer rubber; or onto both of these types of rubbers and (3) one or more core/shell graft copolymer having as a core a rubbery polymer of alkyl acrylate or butadiene, including copolymers thereof such as butadiene-vinyl aromatic hydrocarbon or butadiene- vinyl aromatic hydrocarbon-alkyl acrylate copolymers, with optionally a second inner shell phase of a polymer of vinyl aromatic hydrocarbon monomer and an outer shell of
  • the graft copolymers of component (2) above are commonly referred to as AES resins where an EPDM-type polymer rubber is used or as ASA resins where an alkyl acrylate-type polymer rubber is used.
  • AES resins where an EPDM-type polymer rubber is used
  • ASA resins where an alkyl acrylate-type polymer rubber is used.
  • graft copolymers of component (3) above are often referred to as MBS rubbers or resins when they are a butadiene rubber core grafted with a polymer of methyl methacrylate and styrene or as butyl acrylate core/shell 1C - rubbers when a butyl acrylate rubber core is grafted with an alkyl acrylate polymer.
  • a tube or parison of the heat softened thermoplastic blend may be extruded vertically downward into a mold. The extrudate is then pressed unto the mold surfaces with a
  • pressurized gas flow usually air or inert gas
  • the successful molding of a given thermoplastic resin is dependent upon a number of factors, including the characteristics and physical properties of the heat softened resin.
  • the length and diameter of the tube and the quantity of material forming the tube are limiting factors in determining the size and wall thickness of the object that can be molded by this process.
  • the fluidity of the melt obtained from polycarbonate blends, or the lack of melt strength as well as the paucity of extrudate swelling, serve to limit blow molding applications to relatively small, thin walled parts.
  • the present invention is directed to a moldable thermoplastic blend composition
  • a moldable thermoplastic blend composition comprising:
  • a further aspect of the present invention is a process of preparing molded articles using the above composition.
  • the articles produced and/or molded by using the compositions of the invention are useful as automotive components, bottles, tool housings and the like.
  • Figures 1 and 2 are transmission electron micrograph (TEM) photographs of Experimental Compositions 1 and 4 showing that the blends of polycarbonate (PC) and the rubber modified vinyl aromatic-nitrile graft copolymer surprisingly have the MBS rubber (small black spheres) located at the interface of the dark gray polycarbonate phase with the lighter gray, vinyl aromatic-nitrile copolymer phase and in polycarbonate phase.
  • the photographs show the location of the rubbery impact modifier in the vinyl aromatic-nitrile copolymer (SAN) resin phase, as would be expected.
  • SAN vinyl aromatic-nitrile copolymer
  • the carbonate polymers employed in the present invention are advantageously the known aromatic carbonate polymers such as the trityl diol carbonates described in U.S. Patent Nos. 3,036,036; 3,036,037; 3,036,038 and 3,036,039; polycarbonates of bis(ar- hydroxyphenyl) -alkylidenes (often called bisphenol-A type diols) including their aromatically and aliphatically substituted derivatives such as disclosed in U.S. Patent Nos. 2,999,835; 3,028,365 and 3,334,154; and carbonate polymers derived from other aromatic diols such as described in U.S. Patent No. 3,169,121.
  • aromatic carbonate polymers such as the trityl diol carbonates described in U.S. Patent Nos. 3,036,036; 3,036,037; 3,036,038 and 3,036,039
  • polycarbonates of bis(ar- hydroxyphenyl) -alkylidenes of bis(ar
  • the polycarbonate may be derived from (1) two or more different dihydric phenols or (2) a dihydric phenol and a glycol or a hydroxy- or acid-terminated polyester or a dibasic acid in the event a carbonate copolymer or interpolymer rather than a homopolymer is desired. Also suitable for the practice of this invention are blends of any one of the above carbonate polymers. Also included in the term "carbonate polymer" are the ester/carbonate copolymers of the types described in U.S. Patent Nos.
  • the branched chain polycarbonates used in this invention are prepared by reacting a dihydric phenol with phosgene in the presence of a trihydric and/or tetrahydric phenol, as shown in U.S. Patent No. 3,544,514.
  • the rubber modified vinyl aromatic-nitrile graft copolymer(s) used in the compositions of the present invention are generally characterized as having a dispersed elastomeric phase and a rigid thermoplastic matrix phase and are typically prepared by means of an emulsion, mass or suspension polymerization process.
  • the rubber is selected from the known rubbery polymers other than the conjugated diene-type rubbers.
  • the preferred rubber materials for preparing the rubber modified vinyl aromatic-nitrile graft copolymers for use according to the present invention have a Tg less than 0°C, more preferably less than -20°C.
  • Examples of these types types of rubbers are well known and include the rubbery polymers of ethylene-propylene- nonconjugated diene monomer or alkyl acrylate(s).
  • suitable graft copolymers include acrylonitrile/EPDM(rubber)/styrene graft copolymers (AES resins) and acrylonitrile/styrene/acrylate(rubber) graft copolymers (ASA resins).
  • AES resins acrylonitrile/EPDM(rubber)/styrene graft copolymers
  • ASA resins acrylonitrile/styrene/acrylate(rubber) graft copolymers
  • the rubber modified vinyl aromatic-nitrile graft copolymer component for use according to the present invention can also advantageously be a blend or combination of AES and ASA resins.
  • AES resins may be characterized as an ethylene- propylene-nonconjugated diene (EPDM) polymer rubber
  • EPDM-type rubber materials suitable for the preparation of AES-type resins are well known and m m. commercially available.
  • EPDM-type rubber is typically employed in an AES resin in amounts of from 5 to 40 percent by weight, preferably from 10 to 30 percent by weight with the balance typically being a vinyl aromatic-nitrile copolymer containing from 10 to 40,
  • AES resins are commercially available from The Dow Chemical Company, for example as R0VELTM 300 brand resin and are further described in U.S. Patent Nos. 4,202,948 and 3,642,950.
  • ASA resins may be characterized as an alkyl (meth)acrylate polymer rubber grafted with and dispersed in a matrix thermoplastic resin which matrix resin is a vinyl aromatic-nitrile copolymer.
  • alkyl methacrylate polymer rubber grafted with and dispersed in a matrix thermoplastic resin which matrix resin is a vinyl aromatic-nitrile copolymer.
  • (meth)acrylate polymer rubber is meant rubbery polymers of alkyl acrylate where alkyl is a C- j to C Q hydrocarbyl radical or alkyl methacrylates where alkyl is a Cg to C 2 hydrocarbyl radical, including copolymers with other monomers, such as for example, acrylonitrile, methacrylonitrile, styrene, ⁇ -methylstyrene, and the like.
  • Acrylate rubber materials suitable for use in the preparation of ASA-type resins are well known and are typically prepared by an emulsion process where additional amounts of a rigid alkyl (meth)acrylate or vinyl aromatic-nitrile polymer can also advantageously be grafted thereto while still in the emulsion.
  • a grafted rubber concentrate obtained in such a process usually contains in excess of 40 weight percent of acrylate rubber and is then typically combined with
  • Acrylate-type rubber is typically employed in _.,- an ASA resin in amounts of from 5 to 40 percent by weight, preferably from 10 to 30 percent by weight with the balance typically being a vinyl aromatic-nitrile copolymer containing from 10 to 40, preferably from 15 to 30 percent by weight nitrile monomer residue.
  • ASA resin in amounts of from 5 to 40 percent by weight, preferably from 10 to 30 percent by weight with the balance typically being a vinyl aromatic-nitrile copolymer containing from 10 to 40, preferably from 15 to 30 percent by weight nitrile monomer residue.
  • 20 Acrylonitrile-styrene-acrylate rubber graft copolymers suitable for use in the blend compositions according to the present invention are commercially available and well known from U.S. Patent No. 3,944,631.
  • Suitable rubber modified vinyl aromatic-nitrile graft copolymer resins can be prepared by grafting a styrene-acrylonitrile (SAN) copolymer onto the desired rubber substrate in the form of a latex.
  • SAN styrene-acrylonitrile
  • the rubber elastomeric component is grafted with SAN copolymer and
  • the forming styrene-acrylonitrile (SAN) copolymer advantageously forms both grafted polymer onto the rubber and all or part of the balance of the matrix -i t -; polymer for the graft copolymer component.
  • SAN styrene-acrylonitrile
  • the rubber content of the rubber-modified vinyl aromatic-nitrile thermoplastic graft copolymer resin used in this invention is not more than 40 percent by 0 weight.
  • the rubber content of this component is at least 5 percent by weight, more preferably at least 10 percent by weight and preferably not more than 30 percent by weight, more preferably not more than 25 percent by weight.
  • This aspect of the graft copolymer 25 together with the flexibility of varying the molecular weight of the respective components, the degree of grafting, and rubber particle size and morphology are important, as are the precise vinyl aromatic and nitrile monomer contents, in obtaining desirable properties and
  • the rubber-modified vinyl aromatic- nitrile thermoplastic graft copolymer resin used in this invention should contain 10 to 40 percent by weight nitrile monomer based on total weight rubber-modified vinyl aromatic-nitrile thermoplastic graft copolymer resin, more preferably 15 to 35 weight percent. It has also been found that within these ranges further improved properties are obtained if the nitrile content of this component is maintained at levels greater than 18 percent by weight. This achieves sufficient polarity and an appropriate solubility parameter in the vinyl aromatic-nitrile copolymer phase to facilitate the location of the core/shell graft copolymer into the carbonate polymer phase and its interface with the ABS- type polymer.
  • thermoplastic vinyl aromatic-nitrile copolymer can be manufactured from nothing other than nitrile and vinyl aromatic monomers, or other monomers can be substituted (partially) or mixed in with them. Although alteration of the monomer mix yields a variation in the properties of the composite, usually it does not, nor is it intended to, cause a variation in the fundamental substrate-graft-matrix structure which is characteristic of rubber-modified thermoplastic vinyl aromatic-nitrile copolymers. However, the monomer mix (especially the nitrile monomer) does influence the solubility parameter of the thermoplastic SAN phase and can be used to direct or place the core/shell graft copolymer component in the carbonate polymer when the three are blended.
  • the preferred core/shell grafted copolymers have a Tg less than 0°C and a rubber content greater than 40 percent. They are generally obtained by polymerizing certain monomers in the presence of an alkyl (meth)acrylate or diene polymer rubber core.
  • diene polymer rubber as suitable for use as the core rubber is meant homopolymers of conjugated dienes having 4 to 8 carbon atoms such as butadiene, isoprene, piperylene, chloroprene, and copolymers of such dienes with less than 50 weight percent, preferably less than 20 weight percent, more preferably less than 10 weight percent other monomers, such as for example, acrylonitrile, methacrylonitrile, butyl acrylate, methyl methacrylate, styrene, ⁇ -methylstyrene, and the like.
  • alkyl (meth)acrylate polymer rubber as suitable for use as the core rubber is.
  • alkyl acrylate where alkyl is a C-
  • the rubber core may be at least partially crosslinked, and is preferably a latex polymer.
  • Preferred alkyl (meth)acrylate polymer rubbers include the rubber polymers based on butyl acrylate.
  • certain monomers are grafted onto the rubber core to form one or more grafted shell and/or small amounts of ungrafted matrix polymer.
  • a variety of monomers may be used for this grafting purpose, such as: vinyl aromatic compounds such as vinyl toluene, alpha- methyl styrene, halogenated styrene, naphthalene; nitriles such as acrylonitrile, methacrylonitrile or alpha-haloge ⁇ ated acrylonitrile; C- j to Cg alkyl acrylates such as methacrylate, ethylacrylate or hexyl acrylate; C-- to Cg alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, glycidyl methacrylate or hexyl methacrylate; unsaturated carboxylic acids such as an acrylic or methacrylic acid, including derivatives of such acids such as anhydrides; or a mixture of
  • the grafting monomers may be added to the reaction mixture simultaneously or in sequence, and, when added in sequence, layers, shells or wart-like appendages can be built up around the substrate latex, or core.
  • the monomers can be added in various ratios to each other.
  • Suitable grafted copolymers of the core/shell type are a methylmethacrylate/buta- diene/styrene grafted copolymer (MBS rubber), and a ⁇ butyl acrylate core-rigid methyl methacrylate thermoplastic shell copolymer.
  • An MBS-type rubber contains a substrate latex or core which is made by polymerizing a conjugated diene, or by copolymerizing a conjugated diene with a mono- olefin or polar vinyl compound, such as styrene, acrylonitrile or methyl methacrylate.
  • the substrate latex is typically made up of 50 to 100 percent conjugated diene and up to 50 percent of one or more additional mono-olefin or polar vinyl compound.
  • One or more of the above-listed suitable grafting monomers is graft polymerized to the substrate latex.
  • a typical weight ratio for an MBS rubber is 60 to 80 parts by weight substrate latex, 10 to 20 parts by weight first grafting monomer and 10 to 20 parts by weight second grafting monomer.
  • a preferred formulation of an MBS rubber is one having a core built up from about 71 parts of butadiene, about 3 parts of styrene, about 4 parts of methyl methacrylate and about 1 part of divinyl benzene; a second inner shell phase of about 11 parts of styrene; and an outer shell phase of about 11 parts of methyl methacrylate and about 0.1 part of 1,3-butylene glycol dimethacrylate, where the parts are by weight.
  • a product having substantially such content is available commercially from Rohm and Haas Company as ParalpidTM EXL 3607 core-shell MBS polymer.
  • the MBS rubber and methods for making same, as described above, are discussed in greater detail in U.S. Patent Nos. 3,243,481, 3,287,443, 3,509,237, 3,657,391, 3,660,535, 4,180,494, 4,221,833, 4,239,863 and 4,617,345.
  • compositions may also contain other ingredients such as UV and antioxidant stabilizers, fillers such as talc, reinforcement agents and such as mica or glass fibers, ignition resistant additives, pigments, dyes, antistatic agents, mold release additives, and the like.
  • UV and antioxidant stabilizers such as UV and antioxidant stabilizers
  • fillers such as talc
  • reinforcement agents such as mica or glass fibers
  • ignition resistant additives such as pigments, dyes, antistatic agents, mold release additives, and the like.
  • a linear polycarbonate (CalibreTM 300-10, Dow Chemical Company) was mixed with 700 parts by weight acrylonitrile-EPDM-styrene (AES) copolymer, 2 parts by weight epoxidized soybean oil (Plas ChekTM 775 from the Ferro Company), and 4 parts by weight IrganoxTM 1076 antioxidant (from Ciba Geigy) .
  • AES acrylonitrile-EPDM-styrene
  • Plas ChekTM 775 from the Ferro Company
  • IrganoxTM 1076 antioxidant from Ciba Geigy
  • the mixture was uniformly blended together in a laboratory tumbler.
  • the blend was introduced into a 30 millimeter (mm) Werner-Pfleiderer melt extruder with heating set points of 270°C.
  • the extrudate was pelletized and dried.
  • the pellets were fed to a 70 ton Arburg injection molding machine to mold test bars of . 12.6 centimeter (cm) x 2.25 cm with a thickness of 3.175 mm.
  • the moldings were subjected to tests to determine their blow moldability (R* value) and 0.025 millimeter (10 mil) notched Izod.
  • blowmoldability was determined by a method generally as described in U.S. Patent No. 4,652,602.
  • blowmoldable resins need to have two properties, reasonably low viscosity in the extrusion annulus as the parison is extruded (moderate shear conditions) and sufficient melt strength and higher viscosity to allow a suspended part to be formed (low shear conditions).
  • a value for blowmoldability, R* is defined as the ratio of viscosities at shear rates of 0.1 and 100 reciprocal seconds at a processing temperature that has experimentally been determined to be sufficient to form a reasonable parison or calculated to be the temperature at which the material viscosity is 20,000 poise at a shear rate of 100 reciprocal seconds. According to this method the R* values for this and the other Experimental compositions prepared below are determined.
  • PC is a randomly branched polycarbonate with a 3 MFR 0 commercially available from The Dow Chemical Company in the CalibreTM 600 series;
  • Para 3607 is ParaloidTM 3607 methylmethacrylate-styrene-butadiene (MBS) core/shell graft copolymer from Rohm and Haas having as a core a rubbery polymer of butadiene with an inner shell of a 5 styrene polymer and an outer shell of a methylmethacrylate polymer, containing greater than 70 percent rubber by weight and having a Tg of about -70°C;
  • Para 3330 is ParaloidTM 3330 core/shell graft copolymer from Rohm and Haas having as a core a rubbery 0 polymer of butyl acrylate with an outer shell of methylmethacrylate graft copolymer, containing greater than 70 percent rubber by weight and having a Tg of .
  • AES is an acrylonitrile-EPDM-styrene r- copolymer commercially available from The Dow Chemical Company as RovelTM F-300 containing about 23 percent by weight of an EPDM rubber and 20 percent by weight acrylonitrile.
  • compositions according to the present invention may be useful for injection molding, blow molding or thermoforming applications.
  • Izod J_ refers to notched Izod impact resistance values measured according to ASTM D-256 in joules/meter perpendicular to the direction of polymer flow at the given temperatures and "Izod II” refers to values measured parallel to the direction of polymer flow.
  • R* refers, as mentioned above, to a viscosity ratio which gives a measure of blowmoldability, higher values indicating better blowmoldability.
  • Control Experiment 1 is an example of a PC/AES composition not in accordance with the present invention.
  • Experiment 1 illustrates that higher R* vales and better low temperature izod impact values are obtained over Control 1 when MBS is added and preferentially located in the polycarbonate phase and/or interface with the vinyl aromatic-nitrile copolymer matrix of the AES resin, as can be seen in Figure 1.
  • Experiment 2 shows an even larger increase in R* values can be obtained by utilizing a branched polycarbonate in. the blend while Experiment 3 shows other core/shell graft copolymer rubbers, like a butyl acrylate rubber based graft copolymer, may also be used to obtain high R* values and high impact properties.
  • Blends and molded articles were prepared and tested according to the procedures of Control 1 and the AES Experiments above. The composition of each blend is given in Table 3 below and the test results are given in Table 4 below.
  • ASA refers to an acrylonitrile-styrene- acrylate graft copolymer rubber containing 15 percent by weight acrylate rubber and at least 20 percent by weight acrylonitrile.
  • Control Experiment 2 is an example of a PC/ASA composition not in accordance with the present invention.
  • Experiment 4 illustrates that higher R* Table 4

Abstract

Des carbonates polymères (PC) tels que des carbonates polymères à ramifications aléatoires, des carbonates polymères linéaires et des mélanges de ceux-ci, sont mélangés à des copolymères greffés de nitrile aromatique et de vinyle modifié au caoutchouc, le caoutchouc n'étant pas un diène conjugué. On ajoute comme modificateur d'impact un caoutchouc de type MBS. Les modificateurs d'impact en MBS sont situées à l'interface entre la phase du carbonate polymère et la phase du copolymère de nitrile aromatique et de vinyle ou dans la phase du carbonate polymère, ce qui permet d'obtenir une élasticité plus élevée de fusion et un meilleur moulage par soufflage.
EP19900904582 1989-03-08 1990-03-07 Molding compositions comprising carbonate polymer, rubber modified vinyl aromatic-nitrile graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions Withdrawn EP0462185A4 (en)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
US32066789A 1989-03-08 1989-03-08
US32068089A 1989-03-08 1989-03-08
US320680 1989-03-08
US320667 1989-03-08
US411278 1989-09-22
US07/411,278 US5068285A (en) 1989-03-08 1989-09-22 Molding compositions with acrylonitrile-styrene-acrylate rubber copolymers
US07/411,279 US5008330A (en) 1989-03-08 1989-09-22 Molding compositions with acrylonitrile-EPDM-styrene copolymers
US411279 1989-09-22

Publications (2)

Publication Number Publication Date
EP0462185A1 EP0462185A1 (fr) 1991-12-27
EP0462185A4 true EP0462185A4 (en) 1992-08-19

Family

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EP19900904582 Withdrawn EP0462185A4 (en) 1989-03-08 1990-03-07 Molding compositions comprising carbonate polymer, rubber modified vinyl aromatic-nitrile graft copolymer and methyl(meth)acrylate-butadiene-styrene graft copolymer and blow molding and thermoforming processes using such compositions

Country Status (7)

Country Link
EP (1) EP0462185A4 (fr)
JP (1) JPH04505628A (fr)
KR (1) KR920701360A (fr)
AU (1) AU5187490A (fr)
BR (1) BR9007201A (fr)
CA (1) CA2047667A1 (fr)
WO (1) WO1990010674A1 (fr)

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DE3939046A1 (de) * 1989-11-25 1991-05-29 Basf Ag Thermoplastische formmassen mit hoher kaeltezaehigkeit
ES2184028T3 (es) * 1996-02-02 2003-04-01 Gen Electric Composiciones de policarbonato/poliester modificadas al impacto con elevada resistencia a la intemperie.
DE602005022494D1 (de) 2004-11-22 2010-09-02 Arkema Inc Schlagzäh modifizierte thermoplastische harzzusammensetzung
EP2325257A1 (fr) * 2009-11-19 2011-05-25 DSM IP Assets B.V. Procédé de fabrication d'un article moulé

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DE3149812A1 (de) * 1981-12-16 1983-07-21 Basf Ag, 6700 Ludwigshafen Thermoplastische formmassen
EP0216065A1 (fr) * 1985-07-26 1987-04-01 ECP ENICHEM POLIMERI S.r.l. Mélanges à base de polymères vinyliques aromatiques ayant une grande ténacité et une grande résistance au choc
EP0379039A1 (fr) * 1989-01-10 1990-07-25 ENICHEM S.p.A. Mélanges à base de copolymères de styrène ayant des caractéristiques mécaniques modifiées

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US4677162A (en) * 1983-04-15 1987-06-30 Mobay Corporation Polycarbonate blends having low gloss
JPS61261349A (ja) * 1985-05-15 1986-11-19 Mitsubishi Gas Chem Co Inc 熱可塑性樹脂組成物
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US3541049A (en) * 1969-08-21 1970-11-17 Mobay Chemical Corp Cyanuric chloride branched polycarbonates
DE3149812A1 (de) * 1981-12-16 1983-07-21 Basf Ag, 6700 Ludwigshafen Thermoplastische formmassen
EP0216065A1 (fr) * 1985-07-26 1987-04-01 ECP ENICHEM POLIMERI S.r.l. Mélanges à base de polymères vinyliques aromatiques ayant une grande ténacité et une grande résistance au choc
EP0379039A1 (fr) * 1989-01-10 1990-07-25 ENICHEM S.p.A. Mélanges à base de copolymères de styrène ayant des caractéristiques mécaniques modifiées

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Title
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See also references of WO9010674A1 *

Also Published As

Publication number Publication date
KR920701360A (ko) 1992-08-11
WO1990010674A1 (fr) 1990-09-20
JPH04505628A (ja) 1992-10-01
CA2047667A1 (fr) 1990-09-09
AU5187490A (en) 1990-10-09
EP0462185A1 (fr) 1991-12-27
BR9007201A (pt) 1992-02-18

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