EP1341848A1 - Polycarbonate compositions - Google Patents

Polycarbonate compositions

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Publication number
EP1341848A1
EP1341848A1 EP01991755A EP01991755A EP1341848A1 EP 1341848 A1 EP1341848 A1 EP 1341848A1 EP 01991755 A EP01991755 A EP 01991755A EP 01991755 A EP01991755 A EP 01991755A EP 1341848 A1 EP1341848 A1 EP 1341848A1
Authority
EP
European Patent Office
Prior art keywords
polycarbonate composition
weight
polycarbonate
composition according
parts
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.)
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Application number
EP01991755A
Other languages
German (de)
French (fr)
Inventor
Thomas Eckel
Andreas Seidel
Bernd Keller
Dieter Wittmann
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.)
Covestro Deutschland AG
Original Assignee
Bayer AG
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Filing date
Publication date
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Publication of EP1341848A1 publication Critical patent/EP1341848A1/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Withdrawn legal-status Critical Current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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the invention relates to impact-modified, flame-retardant polycarbonate compositions with improved notched impact strength in the low-temperature range.
  • EP-A 0 640 655 describes molding compositions made from aromatic polycarbonate, styrene-containing copolymers and graft polymers which can be flame-retarded with monomeric and / or oligomeric organic phosphorus compounds.
  • EP-A 0 363 608 discloses flame-retardant polymer mixtures made from aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric organic phosphates as flame retardant additives.
  • flame-retardant polycarbonate compositions for applications, for example in the vehicle sector, requires a combination of properties of high mechanical strength even in the low-temperature range and excellent flame-resistance. These applications often include safety-relevant parts that can be subjected to high impact or shock loads.
  • the invention is therefore based on the object of impact-modified and at the same time flame-resistant to provide adverse polycarbonate compositions with improved mechanical properties in the low temperature range.
  • compositions which have a special ratio of rubber-containing fraction in the graft polymer to rubber-free fraction of ninyl (co) polymer in the composition.
  • Such compositions preferably have an impact strength of greater than about 20 k / J m 2 , preferably greater than about 25 k / J m 2 , measured according to ISO 180 1A at -20 ° C.
  • the Aii requirements N-0 according to the UL 94 N test are met by the polycarbonate composition according to the invention with a thickness of the test specimen ⁇ 3.2 mm, preferably ⁇ 1.6 mm. This means that a test specimen made from the polycarbonate compositions according to the invention does not exceed 10
  • test specimens do not show a total flame time of more than 50 seconds when exposed twice to each test set; they do not contain any specimens that burn completely up to the holding hammer attached to the upper end of the specimen; they have no samples which ignite the cotton wool arranged below the sample by burning drops or particles.
  • the desired property profile is achieved with polycarbonate compositions which
  • Part B a to the rubber-free part K of vinyl (co) polymer in the polycarbonate composition is greater than 1; is preferably greater than 1.5, particularly preferably greater than 2 and in particular greater than 2.5.
  • the rubber-free portion K is composed of the rubber-free portion
  • the polycarbonate composition according to the invention has a heat resistance according to Vicat B 120 greater than about 100 ° C.
  • compositions according to the invention preferably contain
  • Aromatic polycarbonates and / or aromatic polyester carbonates (component A) which are suitable according to the invention are known or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the production of aromatic polyester carbonates, for example
  • Aromatic polycarbonates can be prepared by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface method, optionally using chain terminators, for example monophenols and optionally using functional or more than non-functional branching agents , for example triphenols or tetraphenols.
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
  • B each C 1 -C 4 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
  • R ⁇ and R> individually selectable for each oil, independently of one another hydrogen or Cj to Cg-alkyl, preferably hydrogen, methyl or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X, Rß and R ⁇ are simultaneously alkyl.
  • Preferred diphenols are hyclroquinone, resorcinol, dihydroxydiphenols, bis-
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxypheny ⁇ ) cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-hydroxy ⁇ henyl ) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred.
  • the diphenols can be used individually or as any mixtures. The diphenols are known from the literature or can be obtained by processes known from the literature
  • Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) -phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert.- Octylphenol, p-dodecylphenol and 2- (3,5-di- methylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol.
  • the amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.
  • thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured for example by means of an ultracentrifuge or by scattered light measurement) from 10,000 to 200,000, preferably 15,000 to 80,000.
  • thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than non-functional compounds, for example those with three and more phenolic groups.
  • copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
  • copolycarbonates according to component A according to the invention 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known, for example, from US 3,419,634 and can be produced by processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxane is described in DE-OS 33 34 782.
  • preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of those other than those mentioned as preferred or particularly preferred
  • Diphenols especially 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenylemer-4,4 "-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
  • a carbonic acid halide preferably phosgene, is additionally used as a bifunctional acid derivative in the production of polyester carbonates.
  • the chain terminators for the production of the aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by d to C 2 -alkyl groups or by halogen atoms, and aliphatic C 2 to C 2 - Monocarboxylic acid chlorides into consideration.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenols in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates can also contain built-in aromatic hydroxycarboxylic acids. They can be linear or branched in a known manner (DE-OS 2 940 024 and DE-OS 3 007 934).
  • 3- or merirfunctional carboxylic acid chlorides such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 can be used as branching agents up to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or 3- or polyfunctional phenols, such as
  • Phloroglucin 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2,4,4-dimefhyl-2,4-6-tri- (4-hydroxyphenyl) -heptane, 1, 3, 5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis [4,4- bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, tetra- (4-hydroxyphenyl) methane, 2,6-bis (2-hydroxy-5-methyl-benzyl) ) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetra- (4- [4-hydroxy- phenyl-isopropyl] phenoxy) methane,
  • the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and
  • Both the ester and carbonate content of the aromatic polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ rel ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution) 25 ° C).
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture. They can be contained in the composition in an amount of 40 to 99, preferably 60 to 98.5 parts by weight.
  • Component B comprises one or more graft polymers of
  • Bl 5 to 95 preferably 30 to 90 wt .-%, of at least one vinyl monomer B.2 95 to 5, preferably 70 to 10% by weight of one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C.
  • the graft base B.2 generally has an average particle size (dso value) of 0.05 to 10 ⁇ m, preferably 0.1 to 5 ⁇ m, particularly preferably 0.2 to 1 ⁇ m.
  • Monomers B.l are preferably mixtures of
  • vinyl aromatics and / or core-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene
  • -C-C 8 alkyl esters such as methyl methacrylate, ethyl meth - acrylate
  • B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and lnides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
  • vinyl cyanides unsaturated nitriles such as acrylonitrile and methacrylonitrile
  • acrylic acid (C 1 -C 8 ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and lnides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-
  • Preferred monomers B.l.l are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B.l.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B.l.l styrene and B.l.2 acrylonitrile.
  • Graft bases B.2 suitable for the graft polymers B are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
  • Preferred graft bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to B1 and B1), with the proviso that the glass transition temperature of the component B.2 is below ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -10 ° C. Pure polybutadiene rubber is particularly preferred.
  • Particularly preferred polymers B are, for example, ABS polymers (emulsion, bulk and suspension ABS), such as those used e.g. in DE-OS 2 035 390
  • the gel percentage of the. Graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
  • the graft copolymers B are obtained by radical polymerization, e.g. prepared by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
  • Particularly suitable graft rubbers are also ABS polymers that pass through
  • Redox initiation with an initiator system made of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • the graft monomers are not necessarily grafted completely onto the graft base in the grafting reaction,
  • Graft polymers B are also understood to mean those products which are obtained by (co) polymerizing the graft monomers in the presence of the graft base and are also obtained in the working up.
  • the rubber-containing fraction B a (expressed in parts by weight) of component B for the
  • the ratio Z is the insoluble component of the graft polymer merisats.
  • the rubber-free portion K results from the copolymer (B ⁇ ) obtained in the graft polymerization, which is soluble, and the copolymer (C), which can additionally be added to the mixture as component C).
  • the rubber-free portion K of the copolymer is the sum of the amount Bj and C (in parts by weight).
  • the ratio Z is B a / K.
  • the rubber-free fraction in the graft polymer is determined by extracting the soluble fraction with the aid of a suitable solvent such as, for example, methylene chloride, acetone, methyl ethyl ketone, dimemylfoimamide, dimethyl acetate or mixtures of 2 or more of these solvents. After generally known workup e.g. Precipitation, you get the soluble portion in the graft polymer. The proportion of the insoluble rubber-containing components can then be calculated from this.
  • a suitable solvent such as, for example, methylene chloride, acetone, methyl ethyl ketone, dimemylfoimamide, dimethyl acetate or mixtures of 2 or more of these solvents.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include Ct to C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen CrCs alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
  • Monomers with more than one polymerizable double bond can be copolymerized for crosslinking.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as emylene glycol dimethacrylate, allyl - methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, emylene glycol dimethacrylate, diallyl phthalate and hetero- cyclic compounds which have at least three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahy ⁇ ro-s-friazine and triallylbenzenes.
  • the amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base B.2. In the case of cyclic crosslinking monomers with at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which can be used for preparing the graft base B.2 addition to Acrylklareestern optionally are, for example, acrylonitrile, styrene, ⁇ -methylstyrene, ide Acryla, vinyl-Cr C ö alkyl ethers, methyl methacrylate, .Butadien , Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • graft bases according to B.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
  • the gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and ⁇ , Georg Thieme-Verlag, Stuttgart 1977).
  • the graft polymers can in the composition according to the invention in one
  • Amount from 0.5 to 60, preferably 1 to 40 and most preferably 2 up to 25 parts by weight can be used. Mixtures of different graft polymers can also be present.
  • Component C comprises one or more thermoplastic vinyl (co) polymers C.l and / or polyalkylene terephthalates C.2.
  • Suitable vinyl (co) polymers C.I. polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles),
  • Cll 50 to 99 preferably 60 to 80 parts by weight of vinyl aromatics and / or nuclear-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) alkyl esters such as methyl methacrylate, ethyl methacrylate), and
  • Nitriles such as acrylonitrile and methaeryl nitrile and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide).
  • C 1 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide).
  • the vinyl (co) polymers C.l are resin-like, thermoplastic and rubber-free.
  • the copolymer of C.I. 1 styrene and C.1.2 acrylonitrile is particularly preferred.
  • the (co) polymers according to C.l are known and can be radicalized
  • the (co) polymers preferably have average molecular weights Mw. (Weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • the polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol -l, 4-residues.
  • the preferred polyalkylene terephthalates can contain up to
  • the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g. Residues of propanediol-1,3,2-ethylpropanediol-1,3, neopentylglycol,
  • Pentanediol-1 5, hexanediol-1,6, cyclohexane-dimethanol-1,4,3-ethylpentanediol-2,4,2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,2,2 Ethylhexanediol-1, 3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, l, 4-di- (ß-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (4-ß-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane
  • the polyalkylene terephthalates can be branched by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, for example according to DE-A 1 900270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and
  • polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
  • Polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.
  • the polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (see e.g. Kunststoff-Handbuch, Volume Vm, p. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973).
  • the vinyl (co) polymers or polyalkylene terephthalates can be present in the composition according to the invention in amounts of 0 to 45, preferably 1 to 30 and particularly preferably 2 to 25 parts by weight.
  • Phosphorus-containing flame retardants (D) in the sense of the invention are preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonatamines and phosphazenes, mixtures of several components selected from one or different of these groups also being able to be used as flame retardants.
  • Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.
  • Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IN)
  • Rl, R ⁇ , R3 and R ⁇ independently of one another in each case optionally halogenated C 1 -C 6 -alkyl, each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine, C5-Cg- Cycloalkyl, C to C20-rl or C7 to Ci2-aralkyl,
  • n independently of one another, 0 or 1
  • X is a mono- or polynuclear aromatic radical with 6 to 30 C atoms, or a linear or branched aliphatic radical with 2 to 30 C atoms, which can be OH-substituted and can contain up to 8 ether bonds.
  • R 1 , R 2 , R 3 and R 4 independently of one another are C to C4-alkyl, phenyl, naphthyl or phenyl -CC-C4-alkyl.
  • the aromatic groups R 1 , R 2 , R 3 and R 4 can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C to C4 alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in the formula (IN) preferably denotes a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (I).
  • n in the formula (IN), independently of one another, can be 0 or 1, preferably n is 1.
  • q stands for values from 0 to 30.
  • Components of the formula (IN) can be used in mixtures, preferably number-average q values of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6.
  • X particularly preferably stands for
  • X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol.
  • X is particularly preferably derived from bisphenol A.
  • the use of oligomeric phosphoric acid esters of the formula (TV), which are derived from bisphenol A, is particularly advantageous since the compositions equipped with this phosphorus compound have a particularly high resistance to stress cracking and hydrolysis and a particularly low tendency to form deposits in injection molding processing. Furthermore, these flame retardants can achieve a particularly high heat resistance.
  • Monophosphorus compounds of the formula (IN) are, in particular, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromobroyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl isophosphate, tris ) phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphate,
  • Phenylphosphonic acid diethyl ester triphenylphosphine oxide or tricresylphosphine oxide.
  • the phosphorus compounds according to component C formula (IN) are known (cf., for example, EP-A 363 608, EP-A 640 655) or can be prepared analogously by known methods (for example Ullmann's Encyclopedia of Industrial Chemistry, vol. 18, p . 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
  • the mean q values can be determined by using a suitable method
  • GC Gas Chromatography
  • HPLC High Pressure Liquid Chromatography
  • GPC Gel Permeation Chromatography
  • Phosphonatamines are preferably compounds of the formula (V) A 3 - - y yN ⁇ Bl y (V)
  • Rl 1 and R 2 independently of one another for unsubstituted or substituted
  • Rl3 and Rl4 independently of one another for unsubstituted or substituted C ⁇ to Cjo-alkyl or unsubstituted or substituted Cß to C ⁇ o ⁇
  • Rl3 and Rl4 together represent unsubstituted or substituted C3 to C ⁇ Q alkylene
  • the numerical values mean 0, 1 or 2 and ßl independently represents hydrogen, optionally halogenated C2 to Cg-alkyl, unsubstituted or substituted Cg to Cio-aryl.
  • ßl preferably independently represents hydrogen, ethyl, n- or iso-propyl, which may be substituted by halogen, unsubstituted or by
  • Alkyl in RÜ, R1 ⁇ 5 R13 and R14 s en independently preferably for methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
  • Substituted alkyl in R 3 and R 4 independently preferably represent halogen-substituted C 1 -C 10 -alkyl, in particular mono- or di-substituted methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
  • Cg to cyryl in R ⁇ , R ⁇ , R ⁇ and R 4 independently preferably represents phenyl, naphthyl or binaphthyl, especially o-phenyl, o-naphthyl, o-binaphthyl, which by halogen (generally one, two - or triple) can be substituted.
  • R13 and R14 together with the oxygen atoms to which they are directly attached and the phosphorus atom can form an Rmg structure.
  • Rl 1, Rl2 5 R13 and R 4 have the meanings given above.
  • Compounds of the formulas (Va-2) and (Va-1) are particularly preferred.
  • the preparation of the phosphonate amines is described, for example, in US Pat. No. 5,844,028.
  • Phosphazenes are compounds of the formulas (Via) and (Nlb)
  • R is in each case identical or different and for amino, in each case optionally halogenated, preferably halogenated with fluorine to Cg-alkyl, or Ci to Cg-alkoxy, in each case optionally with alkyl, preferably Ci to C4-alkyl, and / or halogen, preferably chlorine and / or bromine, substituted
  • C5 to Cö-cycloalkyl C to C20 aryl, preferably phenyl or naphthyl, Cß to C20 aryloxy, preferably phenoxy, naphthyloxy, or C7 to C12 aralkyl, preferably phenyl-C ⁇ -C4-alkyl,
  • Phenoxyphosphazene is preferred.
  • the phosphazenes can be used alone or as a mixture.
  • the radical R can always be the same or 2 or more radicals in the formulas (Ia) and (Ib) can be different.
  • Phosphazenes and their preparation are described for example in EP-A 728 811, DE-A 1 961668 and WO 97/40092.
  • the flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants.
  • the phosphorus-containing flame retardant can be used in an amount of 0.1 to 30, preferably 1 to 25 and most preferably 2 to 20 parts by weight in the composition according to the invention.
  • the flame retardants according to component D are often used in combination with so-called anti-dripping agents, which reduce the tendency of the material to burn in the event of a fire.
  • Compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers may be mentioned here as examples. These can also be used in the compositions according to the invention.
  • Fluorinated polyolefins are preferably used as anti-dripping agents.
  • the fluorinated polyolefins are generally present in the mixture in an amount of 0.01 to 3, preferably 0.05 to 1.5 parts by weight.
  • Fluorinated polyolefins are known and are described, for example, in EP-A 0 640 655. They are sold under the Teflon ® brand, for example Teflon 30N by DuPont.
  • the fluorinated polyolefins can be used both in pure form and in the form of a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of the graft polymers (component B) or with an emulsion of a copolymer, preferably based on styrene / acrylonitrile, the fluorinated -
  • the polyolefin is mixed as an emulsion with an emulsion of the graft polymer or of the copolymer and then coagulated.
  • the fluorinated polyolefins can be used as a precompound with the graft polymer (component B) or a copolymer, preferably based on styrene / acrylonitrile.
  • the fluorinated polyolefins are mixed as a powder with a powder or granulate of the graft polymer or copolymer and are compounded in the melt generally at temperatures from 200 to 330 ° C. in conventional units such as internal kneaders, extruders or twin-screw screws.
  • the fluorinated polyolefins can also be used in the form of a masterbatch which is prepared by emulsion polymerization of at least one monoethylenically unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin.
  • Preferred monomer components are styrene, acrylonitrile and mixtures thereof. After acidic precipitation and subsequent drying, the polymer is used as a free-flowing powder.
  • the coagulates, precompounds or masterbatches usually have solids contents of fluorinated polyolefin of 5 to 95% by weight, preferably 7 to 60% by weight.
  • Component F comprises very finely divided inorganic powders, which may only be added in up to an amount, so that the claimed impact strength is retained.
  • Suitable very finely divided inorganic powders F preferably consist of at least one polar compound of one or more metals of the 1st to 5th main group or 1st to 8th subgroup of the periodic table, preferably the 2nd to 5th main group or 4th to 8th subgroup, particularly preferably the 3rd to 5th
  • Main group or 4th to 8th subgroup or from compounds of these metals with at least one element selected from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.
  • Preferred compounds are, for example, oxides, hydroxides, water-containing
  • the very finely divided inorganic powders preferably consist of oxides, phosphates, hydroxides, preferably of TiO 2 , SiO 2 , SnO 2 , ZnO, ZnS, boehmite, ZrO 2 , Al 2 O 3 ,
  • nanoscale particles can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
  • Hydrated aluminum oxides for example boehmite or TiO 2 , are particularly preferred.
  • the average particle diameters of the nanoparticles are less than or equal to 200 ⁇ m, preferably less than or equal to 150 nm, in particular 1 to 100 nm.
  • Particle size and particle diameter always means the mean particle diameter d 50 , determined by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z. and Z. Polymers 250 (1972), pp. 782-796.
  • the inorganic powder is incorporated into the thermoplastic molding composition in amounts of 0.5 to 40, preferably 1 to 25, particularly preferably 2 to 15% by weight, based on the thermoplastic material.
  • the inorganic compounds can be present as powders, pastes, brine dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions.
  • the powders can be incorporated into the thermoplastic molding compositions by customary processes, for example by directly kneading or extruding molding compositions and the very finely divided inorganic powders.
  • Preferred methods are the preparation of a master batch, e.g. in flame retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-precipitation of a thermoplastic component and the very finely divided inorganic powders, e.g. by co-precipitation of an aqueous emulsion and the finely divided inorganic powders, optionally in the form of dispersions, suspensions, pastes or sols of the finely divided inorganic materials.
  • the molding compositions according to the invention can contain at least one of the customary additives, such as lubricants and mold release agents, for example pentaethylthritol tetrastearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials different from component F), and also dyes and pigments.
  • Preferred reinforcing materials are glass fibers.
  • Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc and titanium dioxide.
  • the molding compositions according to the invention can contain up to 35% by weight, based on the
  • Total molding compound another, optionally synergistic flame retardant contain.
  • Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins and inorganic hydroxide compounds such as are exemplified as further flame retardants
  • inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon oxide and tin oxide as well as siloxane compounds.
  • the fillers and reinforcing materials and additional flame retardants may only be added to the molding composition according to the invention in such quantities that it does not fall below the required notched impact strength value.
  • compositions according to the invention are prepared by mixing the respective constituents in a known manner and melt-compounding and melt-extruding them at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws.
  • the individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
  • thermoplastic molding compositions according to the invention are suitable on account of their excellent flame resistance, in particular the short afterburn time, and their good mechanical properties in the low-temperature range and their high heat resistance Dimensional stability for the production of moldings of all kinds, especially those with increased demands on mechanical properties in the low temperature range, such as in the automotive sector. Due to the heat resistance and theological properties, processing temperatures of> 240 ° C are preferred.
  • the molding compositions according to the invention can be used to produce moldings of any kind.
  • moldings can be produced by injection molding.
  • the compositions are also suitable for the following applications: household appliances, monitors, printers, copiers or
  • Cover plates for the construction sector and parts for rail vehicles can also be used in the field of electrical engineering because they have very good electrical properties, interior components for vehicles, ships, buses, other motor vehicles and aircraft, hubcaps, housings for electrical equipment containing small transformers, housings for devices for disseminating information and
  • Another form of processing is the production of molded articles by deep drawing from previously produced sheets or foils.
  • Another object of the present invention is therefore also the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the molding compositions according to the invention.
  • the rubber-containing fraction B a is determined to be 80% by weight and the rubber-free fraction is determined to be 20% by weight (based on B).
  • Strol / -A-ylnitrile copolymer with a styrene / acrylonitrile weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).
  • Triphenyl phosphate Disflamoll TP ® from Bayer AG.
  • compositions are mixed on a 3-1 internal kneader.
  • the moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
  • the notched impact strength ai is determined in accordance with ISO 180/1 A.
  • the heat resistance according to Vicat B is determined in accordance with DIN 53 460 (ISO 306) on rods measuring 80 x 10 x 4 mm 3 .
  • the fire behavior of the samples was determined according to UL Subj. 94 V measured on rods measuring 127 x 12.7 x 1.6 mm, produced on an injection molding machine at 260 ° C.

Abstract

The invention relates to an impact-resistant modified polycarbonate composition containing a graft polymer and flame proofing agents. The ratio Z of the rubber-containing part Ba which is contained within the graft polymer (B), to the rubber-free part K of vinyl (co)polymer, is higher than 1 in the polycarbonate composition.

Description

Polycarbonat-ZusammensetzungenPolycarbonate compositions
Die Erfindung betrifft schlagzahmodifizierte, flammwidrige Polycarbonat-Zu- sammensetzungen mit verbesserter Kerbschlagzähigkeit im Tieftemperaturbereich.The invention relates to impact-modified, flame-retardant polycarbonate compositions with improved notched impact strength in the low-temperature range.
Flammwidrige Polycarbonal/ABS-Formmassen sind aus zahlreichen Anwendungen bekannt. Die EP-A 0 640 655 beschreibt Formmassen aus aromatischem Poly- carbonat, styrolhaltigem Copolymerisaten und Pfropfpolymerisaten, die mit mono- meren und/oder oligomeren organischen Phosphorverbindungen flammwidrig ausgerüstet werden können.Flame-retardant polycarbonate / ABS molding compositions are known from numerous applications. EP-A 0 640 655 describes molding compositions made from aromatic polycarbonate, styrene-containing copolymers and graft polymers which can be flame-retarded with monomeric and / or oligomeric organic phosphorus compounds.
Die EP-A 0 363 608 offenbart flammwidrige Polymermischungen aus aromatischem Polycarbonat, styrolhaltigem Copolymer oder Pfropfcopolymer sowie oligomeren organischen Phosphaten als Flammschutzadditive.EP-A 0 363 608 discloses flame-retardant polymer mixtures made from aromatic polycarbonate, styrene-containing copolymer or graft copolymer and oligomeric organic phosphates as flame retardant additives.
Die US 5 061 745 beschreibt Polymermischungen aus aromatischem Polycarbonat, ABS-Pfropfpolymerisat und/oder styrolhaltigem Copolymer und organischen Mono- phosphaten als Flammschutzadditive.US Pat. No. 5,061,745 describes polymer mixtures made from aromatic polycarbonate, ABS graft polymer and / or styrene-containing copolymer and organic monophosphates as flame retardant additives.
In keinem dieser Dokumente werden Formmassen mit guter Tieftemperaturzähigkeit beschrieben, die für Anwendungen im Fahrzeugbereich wie Kfz- oder Schienenfahrzeuge, im Flugzeugbau, Schiffbau und anderen Feldern geeignet wären.In none of these documents are molding compounds with good low-temperature toughness described that would be suitable for applications in the vehicle sector such as motor vehicles or rail vehicles, in aircraft construction, shipbuilding and other fields.
Der Einsatz flammwidriger Polycarbonat-Zusarnmensetzungen für Anwendungen, beispielsweise im Fahrzeugbereich, erfordert eine Eigenschaftskombination aus hoher mechanischer Festigkeit auch im Tieftemperaturbereich und exzellenter Flammwidrigkeit. Häufig umfassen diese Anwendungen sicherheitsrelevante Teile, die hohen Schlag- oder Stoßbeanspruchungen ausgesetzt sein können. Der Erfindung liegt somit die Aufgabe zugrunde, schlagzahmodifizierte und gleichzeitig flamm- widrige Polycarbonat-Zusarnmensetzungen mit verbesserten mechanischen Eigenschaften im Tieftemperaturbereich bereitzustellen.The use of flame-retardant polycarbonate compositions for applications, for example in the vehicle sector, requires a combination of properties of high mechanical strength even in the low-temperature range and excellent flame-resistance. These applications often include safety-relevant parts that can be subjected to high impact or shock loads. The invention is therefore based on the object of impact-modified and at the same time flame-resistant to provide adverse polycarbonate compositions with improved mechanical properties in the low temperature range.
Gelöst wird diese Aufgabe durch scUagzähmodifizierte, flammwidrige, Pfropfpoly- merisat enthaltende Polycarbonat-Zusammensetzungen, die ein spezielles Nerhältnis von kautschukhaltigem Anteil im Pfropfpolymerisat zu kautschukfreiem Anteil an Ninyl(co)polymerisat in der Zusammensetzung aufweisen. Solche Zusammensetzungen haben vorzugsweise eine Kerbschlagzähigkeit von größer als etwa 20 k/J m2, vorzugsweise größer als etwa 25 k/J m2, gemessen nach ISO 180 1A bei -20°C.This object is achieved by scuff-modified, flame-retardant, graft polymer-containing polycarbonate compositions which have a special ratio of rubber-containing fraction in the graft polymer to rubber-free fraction of ninyl (co) polymer in the composition. Such compositions preferably have an impact strength of greater than about 20 k / J m 2 , preferably greater than about 25 k / J m 2 , measured according to ISO 180 1A at -20 ° C.
Vorteilhaft ist, dass die Aiiforderungen N-0 gemäß UL 94 N Test durch die erfindungsgemäße Polycarbonat-Zusammensetzung bei einer Dicke des Probekörpers <3,2 mm, vorzugsweise <1,6 mm, erfüllt sind. Dies bedeutet, dass ein Probekörper aus den erfindungsgemäßen Polycarbonat-Zusammensetzungen nicht länger als 10It is advantageous that the Aii requirements N-0 according to the UL 94 N test are met by the polycarbonate composition according to the invention with a thickness of the test specimen <3.2 mm, preferably <1.6 mm. This means that a test specimen made from the polycarbonate compositions according to the invention does not exceed 10
Sekunden nach Einwirkung einer Testflamme brennen darf; die Probekörper zeigen keine Gesamtflammzeit von mehr als 50 Sekunden bei der zweimaligen Flammeinwirkung auf jeden Probesatz; sie enthalten keine Probekörper, die vollständig bis hinauf zu der am oberen Ende der Probe befestigten HalteWammer ab- brennen; sie weisen keine Proben auf, die die unterhalb der Probe angeordnete Watte durch brennende Tropfen oder Teilchen entzünden.Allowed to burn seconds after exposure to a test flame; the test specimens do not show a total flame time of more than 50 seconds when exposed twice to each test set; they do not contain any specimens that burn completely up to the holding hammer attached to the upper end of the specimen; they have no samples which ignite the cotton wool arranged below the sample by burning drops or particles.
Gemäß einer bevorzugten Ausführungsform der Erfindung wird das gewünschte Eigenschaftsbild mit Polycarbonat-Zusammensetzungen erreicht, dieAccording to a preferred embodiment of the invention, the desired property profile is achieved with polycarbonate compositions which
A) ein aromatisches Polycarbonat und/oder Polyestercarbonat,A) an aromatic polycarbonate and / or polyester carbonate,
B) einen Schlagzähmodifikator,B) an impact modifier,
C) gegebenenfalls ein thermoplastisches Homo- und/oder Copolymer und D) eine PhosphorverbindungC) optionally a thermoplastic homo- and / or copolymer and D) a phosphorus compound
enthalten,contain,
wobei das Verhältnis Z des in der Komponente B enthaltenen kautschukhaltigenwhere the ratio Z of the rubber-containing component B contained
Anteils Ba zu dem kautschukfreien Anteil K an Ninyl(co)polymerisat in der Polycarbonat-Zusammensetzung größer als 1; vorzugsweise größer als 1,5, besonders bevorzugt größer als 2 und insbesondere größer als 2,5 ist.Part B a to the rubber-free part K of vinyl (co) polymer in the polycarbonate composition is greater than 1; is preferably greater than 1.5, particularly preferably greater than 2 and in particular greater than 2.5.
Der kautschukfreie Anteil K setzt sich zusammen aus dem kautschukfreien Anteil anThe rubber-free portion K is composed of the rubber-free portion
Ninyl(co)polymerisat in der Komponente B und dem als Komponente C) gegebenenfalls zugesetzten Vinyl(co)polymerisat.Ninyl (co) polymer in component B and the vinyl (co) polymer optionally added as component C).
Gemäß einer weiteren bevorzugten Ausfuhrungsform weist die erfindungsgemäße Polycarbonat-Zusammensetzung eine Wärmeformbeständigkeit nach Vicat B 120 größer als etwa 100°C auf.According to a further preferred embodiment, the polycarbonate composition according to the invention has a heat resistance according to Vicat B 120 greater than about 100 ° C.
Die erfindungsgemäßen Zusammensetzungen enthalten bevorzugtThe compositions according to the invention preferably contain
A) 40 bis 99, vorzugsweise 60 bis 98,5, insbesondere 60 bis 95 Gew. -TeileA) 40 to 99, preferably 60 to 98.5, in particular 60 to 95 parts by weight
Polycarbonat und/oder Polyestercarbonat,Polycarbonate and / or polyester carbonate,
B) 1 bis 40, vorzugsweise 2 bis 25, insbesondere 3 bis 20 Gew.-Teile Schlagzähmodifikator,B) 1 to 40, preferably 2 to 25, in particular 3 to 20 parts by weight of impact modifier,
C) 0 bis 30, insbesondere 0 bis 25 Gew.-Teile Homo- und/oder Copolymer undC) 0 to 30, in particular 0 to 25 parts by weight of homo- and / or copolymer and
D) 0,5 bis 30, vorzugsweise 1 bis 25, insbesondere 3,5 bis 15 Gew.-Teile Phosphorverbindung. Alle Gewichtsteilangaben in der vorliegenden Anmeldung sind so normiert, dass die Summe der Gewichtsteile aller Komponenten in der Zusammensetzung 100 ergibt.D) 0.5 to 30, preferably 1 to 25, in particular 3.5 to 15 parts by weight of phosphorus compound. All parts by weight in the present application are standardized so that the sum of the parts by weight of all components in the composition is 100.
Die erfindungsgemäß geeigneten Komponenten der tieftemperaturzähen, flamrn- widrig ausgerüsteten Polycarbonat-Zusammensetzungen werden nachfolgend beispielhaft erläutert.The components of the low-temperature tough, flame-retardant polycarbonate compositions which are suitable according to the invention are explained below by way of example.
Komponente AComponent A
Erfindungsgemäß geeignete aromatische Polycarbonate und/oder aromatische Poly- estercarbonate (Komponente A) sind bekannt oder nach literaturbekannten Verfahren herstellbar (zur Herstellung aromatischer Polycarbonate siehe beispielsweise Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 sowie die DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; zur Herstellung aromatischer Polyestercarbonate z.B.Aromatic polycarbonates and / or aromatic polyester carbonates (component A) which are suitable according to the invention are known or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; for the production of aromatic polyester carbonates, for example
DE-OS 3 077 934).DE-OS 3 077 934).
Die Herstellung aromatischer Polycarbonate kann durch Umsetzen von Diphenolen mit Kohlensäurehalogeniden, vorzugsweise Phosgen, und/oder mit aromatischen Di- carbonsäuredihalogeniden, vorzugsweise Benzoldicarbonsäuredihalogeniden, nach dem Phasengrenzflächenverfahren, gegebenenfalls unter Verwendung von Kettenabbrechern, beispielsweise Monophenolen und gegebenenfalls unter Verwendung von funktionellen oder mehr als frifunktionellen Verzweigern, beispielsweise Tri- phenolen oder Tetraphenolen, erfolgen.Aromatic polycarbonates can be prepared by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface method, optionally using chain terminators, for example monophenols and optionally using functional or more than non-functional branching agents , for example triphenols or tetraphenols.
Diphenole zur Herstellung der aromatischen Polycarbonate und/oder aromatischen Polyestercarbonate sind vorzugsweise solche der Formel (I) Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
wobeiin which
eine Einfachbindung, C\ bis C5-Alkylen, C2 bis C5-Alkyliden, C5 bis C - Cycloalkyliden, -O-, -SO-, -CO-, -S-, -SO2-, Cg bis Ci2- rylen, an das weitere aromatische gegebenenfalls Heteroatome enthaltende Ringe kondensiert sein können,a single bond, C \ to C5 alkylene, C2 to C5 alkylidene, C5 to C - cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO 2 -, Cg to Ci2- rylene the further aromatic rings which may contain heteroatoms may be condensed,
oder ein Rest der Formel (II) oder (III)or a radical of the formula (II) or (III)
B jeweils C\ bis Ci2-Alkyl, vorzugsweise Methyl, Halogen, vorzugsweise Chlor und/oder BromB each C 1 -C 4 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
x jeweils unabhängig voneinander 0, 1 oder 2,x each independently of one another 0, 1 or 2,
p 1 oder 0 sind, und R^ und R > für jedes χl individuell wählbar, unabhängig voneinander Wasserstoff oder Cj bis Cg-Alkyl, vorzugsweise Wasserstoff, Methyl oder Ethyl,p are 1 or 0, and R ^ and R> individually selectable for each oil, independently of one another hydrogen or Cj to Cg-alkyl, preferably hydrogen, methyl or ethyl,
χl Kohlenstoffundχl carbon and
m eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5 bedeuten, mit der Maßgabe, dass an mindestens einem Atom X , Rß und R^ gleichzeitig Alkyl sind.m is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X, Rß and R ^ are simultaneously alkyl.
Bevorzugte Diphenole sind Hyclrochinon, Resorcin, Dihydroxydiphenole, Bis-Preferred diphenols are hyclroquinone, resorcinol, dihydroxydiphenols, bis-
(hydroxyphenyl)-Cι-C5-alkane, Bis-(hydroxyphenyl)-C5-C6-cycloalkane, Bis- (hydroxyphenyl)-ether, Bis-(hydroxyphenyl)-sulfoxide, Bis-(hydroxyphenyl)-ketone, Bis-(hydroxyphenyl)-sulfone und oc, -Bis-(hydroxyphenyl)-diisopropyl-benzole sowie deren kernbromierte und/oder kernchlorierte Derivate.(Hydroxyphenyl) -C-C5-alkanes, bis (hydroxyphenyl) -C5-C6-cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) ) -sulfones and oc, -Bis (hydroxyphenyl) -diisopropyl-benzenes and their core-brominated and / or core-chlorinated derivatives.
Besonders bevorzugte Diphenole sind 4,4'-Dihydroxydiphenyl, Bisphenol- A, 2,4- Bis(4-hydroxyphenyl)-2-methylbutan, 1 , 1 -Bis-(4-hydroxyphenyι)-cyclohexan, 1,1- Bis-(4-hydroxyphenyl)-3.3.5-trimethylcyclohexan, 4,4'-Dihydroxydiphenylsulfid, 4,4'-Dihydroxydiphenyl-sulfon sowie deren di- und tetrabromierten oder chlorierten Derivate wie 2,2-Bis(3-Chlor-4-hydroxyρhenyl)-propan, 2,2-Bis-(3,5-dichlor-4- hydroxyphenyl)-propan oder 2,2-Bis-(3,5-dibrom-4-hydroxyphenyl)-propan. Insbesondere bevorzugt ist 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol-A). Es können die Diphenole einzeln oder als beliebige Mischungen eingesetzt werden. Die Diphenole sind literaturbekannt oder nach literaturbekannten Verfahren erhältlich.Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyι) cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3.3.5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-hydroxyρhenyl ) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. 2,2-bis (4-hydroxyphenyl) propane (bisphenol-A) is particularly preferred. The diphenols can be used individually or as any mixtures. The diphenols are known from the literature or can be obtained by processes known from the literature.
Für die Herstellung der thermoplastischen, aromatischen Polycarbonate geeignete Kettenabbrecher sind beispielsweise Phenol, p-Chlorphenol, p-tert.-Butylphenol oder 2,4,6-Tribromphenol, aber auch langkettige Alkylphenole, wie 4-(l,3-Tetramethyl- butyl)-phenol gemäß DE-OS 2 842 005 oder Monoalkylphenol oder Dialkylphenole mit insgesamt 8 bis 20 C-Atomen in den Alkylsubstituenten, wie 3,5-di-tert.-Butyl- phenol, p-iso-Octylphenol, p-tert.-Octylphenol, p-Dodecylphenol und 2-(3,5-Di- methylheptyl)-phenol und 4-(3,5-Dimethylheptyl)-phenol. Die Menge an einzusetzenden Kettenabbrechern beträgt im allgemeinen zwischen 0,5 Mol-%, und 10 Mol-%, bezogen auf die Molsumme der jeweils eingesetzten Diphenole.Chain terminators suitable for the production of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethylbutyl) -phenol according to DE-OS 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert.- Octylphenol, p-dodecylphenol and 2- (3,5-di- methylheptyl) phenol and 4- (3,5-dimethylheptyl) phenol. The amount of chain terminators to be used is generally between 0.5 mol% and 10 mol%, based on the molar sum of the diphenols used in each case.
Die thermoplastischen, aromatischen Polycarbonate haben mittlere Gewichtsmittelmolekulargewichte (Mw, gemessen beispielsweise mittels Ultrazentrifuge oder durch Streulichtmessung) von 10.000 bis 200.000, vorzugsweise 15.000 bis 80.000.The thermoplastic, aromatic polycarbonates have average weight-average molecular weights (M w , measured for example by means of an ultracentrifuge or by scattered light measurement) from 10,000 to 200,000, preferably 15,000 to 80,000.
Die thermoplastischen, aromatischen Polycarbonate können in bekannter Weise ver- zweigt sein, und zwar vorzugsweise durch den Einbau von 0,05 bis 2,0 Mol-%, bezogen auf die Summe der eingesetzten Diphenole, an dreifunktionellen oder mehr als Irifunktionellen Verbindungen, beispielsweise solchen mit drei und mehr phenolischen Gruppen.The thermoplastic, aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than non-functional compounds, for example those with three and more phenolic groups.
Geeignet sind sowohl Homopolycarbonate als auch Copolycarbonate. Zur Herstellung erfϊndungsgemäßer Copolycarbonate gemäß Komponente A können auch 1 bis 25 Gew.-%, vorzugsweise 2,5 bis 25 Gew.-%, bezogen auf die Gesamtmenge an einzusetzenden Diphenolen, Polydiorganosiloxane mit Hydroxyaryloxy-Endgruppen eingesetzt werden. Diese sind beispielsweise aus der US 3 419 634 bekannt und nach literaturbekannten Verfahren herstellbar. Die Herstellung Polydiorganosiloxan enthaltender Copolycarbonate wird in der DE-OS 33 34 782 beschrieben.Both homopolycarbonates and copolycarbonates are suitable. For the production of copolycarbonates according to component A according to the invention, 1 to 25% by weight, preferably 2.5 to 25% by weight, based on the total amount of diphenols to be used, polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known, for example, from US 3,419,634 and can be produced by processes known from the literature. The preparation of copolycarbonates containing polydiorganosiloxane is described in DE-OS 33 34 782.
Bevorzugte Polycarbonate sind neben den Bisphenol-A-Homopolycarbonaten die Copolycarbonate von Bisphenol-A mit bis zu 15 Mol-%, bezogen auf die Mol- summen an Diphenolen, anderen als bevorzugt oder besonders bevorzugt genanntenIn addition to the bisphenol A homopolycarbonates, preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of those other than those mentioned as preferred or particularly preferred
Diphenolen, insbesondere 2,2-Bis(3,5-dibrom-4-hydroxyphenyl)-propan.Diphenols, especially 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
Aromatische Dicarbonsäuredihalogenide zur Herstellung von aromatischen Poly- estercarbonaten sind vorzugsweise die Disäuredichloride der Isophthalsäure, Tere- phthalsäure, Diphenylemer-4,4"-dicarbonsäure und der Naphthalin-2,6-dicarbonsäure. Besonders bevorzugt sind Gemische der Disäuredichloride der Isophthalsäure und der Terephthalsäure im Verhältnis zwischen 1 :20 und 20:1.Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenylemer-4,4 "-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid. Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20: 1 are particularly preferred.
Bei der Herstellung von Polyestercarbonaten wird zusätzlich ein Kohlensäure- halogenid, vorzugsweise Phosgen, als bifunktionelles Säurederivat mitverwendet.A carbonic acid halide, preferably phosgene, is additionally used as a bifunctional acid derivative in the production of polyester carbonates.
Als Kettenabbrecher für die Herstellung der aromatischen Polyestercarbonate kommen außer den bereits genannten Monophenolen noch deren Chlorkohlensäureester sowie die Säurechloride von aromatischen Monocarbonsäuren, die gegebe- nenfalls durch d bis C 2-Alkylgruppen oder durch Halogenatome substituiert sein können, sowie aliphatische C2 bis C 2-Monocarbonsäurechloride in Betracht.In addition to the monophenols already mentioned, the chain terminators for the production of the aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by d to C 2 -alkyl groups or by halogen atoms, and aliphatic C 2 to C 2 - Monocarboxylic acid chlorides into consideration.
Die Menge an Kettenabbrechern beträgt jeweils 0,1 bis 10 Mol-%, bezogen im Falle der phenolischen Kettenabbrecher auf Mole Diphenole und im Falle von Mono- carbonsäurechlorid-Kettenabbrecher auf Mole Dicarbonsäuredichloride.The amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenols in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichlorides in the case of monocarboxylic acid chloride chain terminators.
Die aromatischen Polyestercarbonate können auch aromatische Hydroxycarbon- säuren eingebaut enthalten. Sie können sowohl linear als auch in bekannter Weise verzweigt sein (DE-OS 2 940 024 und DE-OS 3 007 934).The aromatic polyester carbonates can also contain built-in aromatic hydroxycarboxylic acids. They can be linear or branched in a known manner (DE-OS 2 940 024 and DE-OS 3 007 934).
Als Verzweigungsmittel können beispielsweise 3- oder merirfunktionelle Carbonsäurechloride, wie Trimesinsäuretrichlorid, Cyanursäuretrichlorid, 3,3'-,4,4'-Benzo- phenon-tetracarbonsäuretetrachlorid, 1,4,5,8-Napthalintetracarbonsäuretetrachlorid oder Pyromellithsäuretetrachlorid, in Mengen von 0,01 bis 1,0 Mol-% (bezogen auf eingesetzte Dicarbonsäuredichloride) oder 3- oder mehrfunktionelle Phenole, wieFor example, 3- or merirfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3 '-, 4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 can be used as branching agents up to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or 3- or polyfunctional phenols, such as
Phloroglucin, 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hepten-2,4,4-Dimefhyl-2,4- 6-tri-(4-hydroxyphenyl)-heptan, 1 ,3 ,5-Tri-(4-hydroxyphenyl)-benzol, 1,1,1 -Tri-(4- hydroxyphenyl)-ethan, Tri-(4-hydroxyphenyl)-phenylmethan, 2,2-Bis [4,4-bis(4- hydroxyphenyl)-cyclohexyl]-propan, 2,4-Bis(4-hydroxyphenylisopropyl)-phenol, Tetra-(4-hydroxyphenyl)-methan, 2,6-Bis(2-hydroxy-5-methyl-benzyl)-4-methyl- phenol, 2-(4-Hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propan, Tetra-(4-[4-hydroxy- phenyl-isopropyl]-phenoxy)-methan, l,4-Bis[4,4'-dmy(n-oxvtri-phenyl)-methyl]- benzol, in Mengen von 0,01 bis 1,0 Mol-% bezogen auf eingesetzte Diphenole verwendet werden. Phenolische Verzweigungsmittel können mit den Diphenolen vorgelegt, Säurechlorid- Verzweigungsmittel können zusammen mit den Säuredi- Chloriden eingetragen werden.Phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2,4,4-dimefhyl-2,4-6-tri- (4-hydroxyphenyl) -heptane, 1, 3, 5-tri- (4-hydroxyphenyl) benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis [4,4- bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenylisopropyl) phenol, tetra- (4-hydroxyphenyl) methane, 2,6-bis (2-hydroxy-5-methyl-benzyl) ) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetra- (4- [4-hydroxy- phenyl-isopropyl] phenoxy) methane, 1,4-bis [4,4'-dmy (n-oxytriphenyl) methyl] benzene, in amounts of 0.01 to 1.0 mol% based on Diphenols used can be used. Phenolic branching agents can be introduced with the diphenols, acid chloride branching agents can be introduced together with the acid dichlorides.
In den thermoplastischen, aromatischen Polyestercarbonaten kann der Anteil an Carbonatstruktureinheiten beliebig variieren. Vorzugsweise beträgt der Anteil an Carbonatgruppen bis zu 100 Mol-%, insbesondere bis zu 80 Mol-%, besonders be- vorzugt bis zu 50 Mol-%, bezogen auf die Summe an Estergruppen undThe proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired. The proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and
Carbonatgruppen. Sowohl der Ester- als auch der Carbonatanteil der aromatischen Polyestercarbonate kann in Form von Blöcken oder statistisch verteilt im Polykon- densat vorliegen.Carbonate. Both the ester and carbonate content of the aromatic polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
Die relative Lösungsviskosität (ηrel) der aromatischen Polycarbonate und Polyestercarbonate liegt im Bereich 1,18 bis 1,4, vorzugsweise 1,20 bis 1,32 (gemessen an Lösungen von 0,5 g Polycarbonat oder Polyestercarbonat in 100 ml Methylenchlorid-Lösung bei 25°C).The relative solution viscosity (η rel ) of the aromatic polycarbonates and polyester carbonates is in the range from 1.18 to 1.4, preferably from 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution) 25 ° C).
Die thermoplastischen, aromatischen Polycarbonate und Polyestercarbonate können allein oder im beliebigen Gemisch eingesetzt werden. Sie können in der Zusammensetzung in einer Menge von 40 bis 99, vorzugsweise 60 bis 98,5, Gewichtsteilen enthalten sein.The thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture. They can be contained in the composition in an amount of 40 to 99, preferably 60 to 98.5 parts by weight.
Komponente BComponent B
Die Komponente B umfasst ein oder mehrere Pfropfpolymerisate vonComponent B comprises one or more graft polymers of
B.l 5 bis 95, vorzugsweise 30 bis 90 Gew.-%, wenigstens eines Vinylmono- meren auf B.2 95 bis 5, vorzugsweise 70 bis 10 Gew.-% einer oder mehrerer Pfropfgrundlagen mit Glasübergangstemperaturen < 10°C, vorzugsweise < 0°C, besonders bevorzugt < -20°C.Bl 5 to 95, preferably 30 to 90 wt .-%, of at least one vinyl monomer B.2 95 to 5, preferably 70 to 10% by weight of one or more graft bases with glass transition temperatures <10 ° C, preferably <0 ° C, particularly preferably <-20 ° C.
Die Pfropfgrundlage B.2 hat im allgemeinen eine mittlere Teilchengröße (dso-Wert) von 0,05 bis 10 μm, vorzugsweise 0,1 bis 5 μm, besonders bevorzugt 0,2 bis 1 μm.The graft base B.2 generally has an average particle size (dso value) of 0.05 to 10 μm, preferably 0.1 to 5 μm, particularly preferably 0.2 to 1 μm.
Monomere B.l sind vorzugsweise Gemische ausMonomers B.l are preferably mixtures of
B.l.l 50 bis 99 Gew. -Teilen Vinylaromaten und/oder kernsubstituierten Vinylaro- maten (wie Styrol, α-Methylstyrol, p-Methylstyrol, p-Chlorstyrol) und/oder Methacrylsäure-(Cι-C8)-Alkylester, wie Methylmethacrylat, Ethylmeth- acrylat), undBll 50 to 99 parts by weight of vinyl aromatics and / or core-substituted vinyl aromatics (such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (-C-C 8 ) alkyl esters, such as methyl methacrylate, ethyl meth - acrylate), and
B.1.2 1 bis 50 Gew. -Teilen Vinylcyanide (ungesättigte Nitrile wie Acrylnitril und Methacrylnitril) und/oder (Meth)Acrylsäure-(C1-C8)-Alkylester, wie Methylmethacrylat, n-Butylacrylat, t-Butylacrylat, und/oder Derivate (wie Anhydride und Lnide) ungesättigter Carbonsäuren, beispielsweise Maleinsäureanhydrid und N-Phenyl-Maleinimid.B.1.2 1 to 50 parts by weight of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and lnides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
Bevorzugte Monomere B.l.l sind ausgewählt aus mindestens einem der Monomere Styrol, α-Methylstyrol und Methylmethacrylat, bevorzugte Monomere B.l.2 sind ausgewählt aus mindestens einem der Monomere Acrylnitril, Maleinsäureanhydrid und Methylmethacrylat. Besonders bevorzugte Monomere sind B.l.l Styrol und B.l.2 Acrylnitril.Preferred monomers B.l.l are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, preferred monomers B.l.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B.l.l styrene and B.l.2 acrylonitrile.
Für die Pfropfpolymerisate B geeignete Pfropfgrundlagen B.2 sind beispielsweise Dienkautschuke, EP(D)M-Kautschuke, also solche auf Basis Ethylen/Propylen und gegebenenfalls Dien, Acrylat-, Polyurethan-, Silikon-, Chloropren und Ethylen/Vinylacetat-Kautschuke. Bevorzugte Pfropfgrundlagen B.2 sind Dienkautschuke, beispielsweise auf Basis Butadien und Isopren, oder Gemische von Dienkautschuken oder Copolymerisate von Dienkautschuken oder deren Gemischen mit weiteren copoly erisierbaren Monomeren (z.B. gemäß B.l.l und B.l.2), mit der Maßgabe, dass die Glasüber- gangstemperatur der Komponente B.2 unterhalb < 10°C, vorzugsweise < 0°C, besonders bevorzugt < -10°C liegt. Besonders bevorzugt ist reiner Polybutadien- kautschuk.Graft bases B.2 suitable for the graft polymers B are, for example, diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers. Preferred graft bases B.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example according to B1 and B1), with the proviso that the glass transition temperature of the component B.2 is below <10 ° C, preferably <0 ° C, particularly preferably <-10 ° C. Pure polybutadiene rubber is particularly preferred.
Besonders bevorzugte Polymerisate B sind beispielsweise ABS-Polymerisate (Emul- sions-, Masse- und Suspensions-ABS), wie sie z.B. in der DE-OS 2 035 390Particularly preferred polymers B are, for example, ABS polymers (emulsion, bulk and suspension ABS), such as those used e.g. in DE-OS 2 035 390
(=US-PS 3 644 574) oder in der DE-OS 2 248 242 (=GB-PS 1 409 275) bzw. in Ulimanns, Enzyklopädie der Technischen Chemie, Bd. 19 (1980), S. 280 ff. beschrieben sind. Der Gelanteil der. Pfropfgrundlage B.2 beträgt mindestens 30 Gew.-%, vorzugsweise mindestens 40 Gew.-% (in Toluol gemessen).(= US-PS 3 644 574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ulimanns, Enzyklopadie der Technischen Chemie, vol. 19 (1980), p. 280 ff are. The gel percentage of the. Graft base B.2 is at least 30% by weight, preferably at least 40% by weight (measured in toluene).
Die Pfropfcopolymerisate B werden durch radikalische Polymerisation, z.B. durch Emulsions-, Suspensions-, Lösungs- oder Massepolymerisation, vorzugsweise durch Emulsions- oder Massepolymerisation hergestellt.The graft copolymers B are obtained by radical polymerization, e.g. prepared by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization.
Besonders geeignete Pfropfkautschuke sind auch ABS-Polymerisate, die durchParticularly suitable graft rubbers are also ABS polymers that pass through
Redox-Initiierung mit einem Initiatorsystem aus organischem Hydroperoxid und Ascorbinsäure gemäß US-P 4 937285 hergestellt werden.Redox initiation with an initiator system made of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
Da bei der Pfropfreaktion die Pfropfmonomeren bekanntlich nicht unbedingt voll- ständig auf die Pfropfgrundlage aufgepfropft werden, werden erfindungsgemäß unterAccording to the invention, since the graft monomers are not necessarily grafted completely onto the graft base in the grafting reaction,
Pfropfpolymerisaten B auch solche Produkte verstanden, die durch (Co)Polymeri- sation der Pfropfrnonomere in Gegenwart der Pfropfgrundlage gewonnen werden und bei der Aufarbeitung mit anfallen.Graft polymers B are also understood to mean those products which are obtained by (co) polymerizing the graft monomers in the presence of the graft base and are also obtained in the working up.
Der kautschukhaltige Anteil Ba (Angabe in Gew. -Teilen) der Komponente B für dieThe rubber-containing fraction B a (expressed in parts by weight) of component B for the
Bestimmung des Verhältnisses Z ist der nicht lösliche Bestandteil des Pfropfpoly- merisats. Der kautschukfreie Anteil K resultiert aus dem bei der Pfropfpolymerisation anfallenden Copolymerisat (B^), welches löslich ist, und dem Copolymerisat (C), welches als Komponente C) der Mischung zusätzlich zugesetzt werden kann. Der kautschukfreie Anteil K an Copolymerisat ist also die Summe aus der Menge Bj, und C (in Gew. -Teilen). Das Verhältnis Z ist Ba/K.Determining the ratio Z is the insoluble component of the graft polymer merisats. The rubber-free portion K results from the copolymer (B ^) obtained in the graft polymerization, which is soluble, and the copolymer (C), which can additionally be added to the mixture as component C). The rubber-free portion K of the copolymer is the sum of the amount Bj and C (in parts by weight). The ratio Z is B a / K.
Der kautschukfreie Anteil im Pfropfpolymerisat wird bestimmt, indem mit Hilfe eines geeigneten Lösungsmittels wie beispielsweise Methylenchlorid, Aceton, Methylethylketon, Dimemylfoimamid, Dimethylacetat oder Mischungen von 2 oder mehr dieser Lösungsmittel der lösliche Anteil extrahiert wird. Nach allgemein bekannter Aufarbeitung z.B. Fällung, erhält man den löslichen Anteil im Pfropfpolymerisat. Der Anteil der unlöslichen kautschukhaltigen Bestandteile lässt sich dann daraus berechnen.The rubber-free fraction in the graft polymer is determined by extracting the soluble fraction with the aid of a suitable solvent such as, for example, methylene chloride, acetone, methyl ethyl ketone, dimemylfoimamide, dimethyl acetate or mixtures of 2 or more of these solvents. After generally known workup e.g. Precipitation, you get the soluble portion in the graft polymer. The proportion of the insoluble rubber-containing components can then be calculated from this.
Geeignete Acrylatkautschuke gemäß B.2 der Polymerisate B sind vorzugsweise Polymerisate aus Acrylsäurealkylestem, gegebenenfalls mit bis zu 40 Gew.-%, bezogen auf B.2 anderen polymerisierbaren, ethylenisch ungesättigten Monomeren. Zu den bevorzugten polymerisierbaren Acrylsäureestern gehören Ct bis C8-Alkylester, beispielsweise Methyl-, Ethyl-, Butyl-, n-Octyl- und 2-Ethylhexylester; Halogenalkyl- ester, vorzugsweise Halogen-CrCs-alkylester, wie Chlorethylacrylat sowie Mischungen dieser Monomeren.Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers. The preferred polymerizable acrylic acid esters include Ct to C 8 alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halogen CrCs alkyl esters, such as chloroethyl acrylate and mixtures of these monomers.
Zur Vernetzung können Monomere mit mehr als einer polymerisierbaren Doppelbindung copolymerisiert werden. Bevorzugte Beispiele für vernetzende Monomere sind Ester ungesättigter Monocarbonsäuren mit 3 bis 8 C-Atomen und ungesättigter einwertiger Alkohole mit 3 bis 12 C-Atomen, oder gesättigter Polyole mit 2 bis 4 OH-Gruppen und 2 bis 20 C-Atomen, wie Emylenglykoldimethacrylat, Allyl- methacrylat; mehrfach ungesättigte heterocyclische Verbindungen, wie Trivinyl- und Triallylcyanurat; polvfunktionelle Vinylverbindungen, wie Di- und Trivinylbenzole; aber auch Triallylphosphat und Diallylphthalat. Bevorzugte vernetzende Monomere sind Allylmethacrylat, Emylenglykoldimethacrylat, Diallylphthalat und hetero- cyclische Verbindungen, die mindestens drei ethylenisch ungesättigte Gruppen aufweisen. Besonders bevorzugte vernetzende Monomere sind die cyclischen Monomere Triallylcyanurat, Triallylisocyanurat, Triacryloylhexahyαro-s-friazin, Triallylbenzole. Die Menge der vernetzten Monomere beträgt vorzugsweise 0,02 bis 5, insbesondere 0,05 bis 2 Gew.-%, bezogen auf die Pfropfgrundlage B.2. Bei cyclischen vernetzenden Mönomeren mit mindestens drei ethylenisch ungesättigten Gruppen ist es vorteilhaft, die Menge auf unter 1 Gew.-% der Pfropfgrundlage B.2 zu beschränken.Monomers with more than one polymerizable double bond can be copolymerized for crosslinking. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 C atoms and unsaturated monohydric alcohols with 3 to 12 C atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 C atoms, such as emylene glycol dimethacrylate, allyl - methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate. Preferred crosslinking monomers are allyl methacrylate, emylene glycol dimethacrylate, diallyl phthalate and hetero- cyclic compounds which have at least three ethylenically unsaturated groups. Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahyαro-s-friazine and triallylbenzenes. The amount of the crosslinked monomers is preferably 0.02 to 5, in particular 0.05 to 2% by weight, based on the graft base B.2. In the case of cyclic crosslinking monomers with at least three ethylenically unsaturated groups, it is advantageous to limit the amount to less than 1% by weight of the graft base B.2.
Bevorzugte "andere" polymerisierbare, ethylenisch ungesättigte Monomere, die neben den Acrylsäureestern gegebenenfalls zur Herstellung der Pfropfgrundlage B.2 dienen können, sind z.B. Acrylnitril, Styrol, α-Methylstyrol, Acryla ide, Vinyl-Cr Cö-alkylether, Methylmethacrylat, .Butadien. Bevorzugte Acrylatkautschuke als Pfropfgrundlage B.2 sind Emulsionspolymerisate, die einen Gelgehalt von min- destens 60 Gew.-% aufweisen.Preferred "other" polymerizable, ethylenically unsaturated monomers which can be used for preparing the graft base B.2 addition to Acrylsäureestern optionally are, for example, acrylonitrile, styrene, α-methylstyrene, ide Acryla, vinyl-Cr C ö alkyl ethers, methyl methacrylate, .Butadien , Preferred acrylate rubbers as graft base B.2 are emulsion polymers which have a gel content of at least 60% by weight.
Weitere geeignete Pfropfgrundlagen gemäß B.2 sind Silikonkautschuke mit pfropfaktiven Stellen, wie sie in den DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 und DE-OS 3 631 539 beschrieben werden.Further suitable graft bases according to B.2 are silicone rubbers with graft-active sites, as are described in DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and DE-OS 3 631 539.
Der Gelgehalt der Pfropfgrundlage B.2 wird bei 25°C in einem geeigneten Lösungsmittel bestimmt (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I und π, Georg Thieme-Verlag, Stuttgart 1977).The gel content of the graft base B.2 is determined at 25 ° C. in a suitable solvent (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and π, Georg Thieme-Verlag, Stuttgart 1977).
Die mittlere Teilchengröße d5o ist der Durchmesser, oberhalb und unterhalb dessen jeweils 50 Gew.-% der Teilchen liegen. Er kann mittels Ultrazentrifugenmessung (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796) bestimmt werden.The average particle size d 5 o of the diameter above and below which 50 wt .-% is of the particles lie. It can be determined by means of ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymer 250 (1972), 782-1796).
Die Pfropfpolymerisate können in der erfindungsgemäßen Zusammensetzung in einerThe graft polymers can in the composition according to the invention in one
Menge von 0,5 bis 60, vorzugsweise 1 bis 40 und in am meisten bevorzugter Weise 2 bis 25 Gewichtsteilen eingesetzt werden. Es können auch Mischungen verschiedener Pfropfpolymerisate vorliegen.Amount from 0.5 to 60, preferably 1 to 40 and most preferably 2 up to 25 parts by weight can be used. Mixtures of different graft polymers can also be present.
Komponente CComponent C
Die Komponente C umfasst ein oder mehrere thermoplastische Vinyl(Co)Poly- merisate C.l und/oder Polyalkylenterephthalate C.2.Component C comprises one or more thermoplastic vinyl (co) polymers C.l and / or polyalkylene terephthalates C.2.
Geeignet sind als Vinyl(Co)Polymerisate C.l Polymerisate von mindestens einem Monomeren aus der Gruppe der Vinylaromaten, Vinylcyanide (ungesättigte Nitrile),Suitable vinyl (co) polymers C.I. polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles),
(Meth)Acrylsäure-(C1-C8)-Alkylester, ungesättigte Carbonsäuren sowie Derivate (wie Anhydride und Imide) ungesättigter Carbonsäuren. Insbesondere geeignet sind (Co)Polymerisate aus(Meth) acrylic acid (C 1 -C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. (Co) polymers of are particularly suitable
C.l.l 50 bis 99, vorzugsweise 60 bis 80 Gew. -Teilen Vinylaromaten und/oder kernsubstituierten Vinylaromaten wie Styrol, α-Methylstyrol, p-Methyl- styrol, p-Chlorstyrol) und/oder Methacrylsäure-(C1-C8)-Alkylester, wie Methylmethacrylat, Ethylmethacrylat), undCll 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or nuclear-substituted vinyl aromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) alkyl esters such as methyl methacrylate, ethyl methacrylate), and
C.l.2 1 bis 50, vorzugsweise 20 bis 40 Gew. -Teilen Vinylcyanide (ungesättigteC.l.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated
Nitrile) wie Acryl-nitril und Methaerylnitril und/oder (Meth)Acryl-säure- (C1-C8)-Alkylester, wie Methylmeth-acrylat, n-Butylacrylat, t-Butylacrylat, und/oder ungesättigte Carbonsäuren, wie Maleinsäure, und/oder Derivate, wie Anhydride und Imide, ungesättigter Carbonsäuren, beispielsweise Maleinsäureanhydrid und N-Phenylmaleinimid).Nitriles) such as acrylonitrile and methaeryl nitrile and / or (meth) acrylic acid (C 1 -C 8 ) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or unsaturated carboxylic acids, such as maleic acid, and / or derivatives, such as anhydrides and imides, unsaturated carboxylic acids, for example maleic anhydride and N-phenylmaleimide).
Die Vinyl(co)polymerisate C.l sind harzartig, thermoplastisch und kautschukfrei. Besonders bevorzugt ist das Copolymerisat aus C.l.l Styrol und C.1.2 Acrylnitril.The vinyl (co) polymers C.l are resin-like, thermoplastic and rubber-free. The copolymer of C.I. 1 styrene and C.1.2 acrylonitrile is particularly preferred.
Die (Co)Polymerisate gemäß C.l sind bekannt und lassen sich durch radikalischeThe (co) polymers according to C.l are known and can be radicalized
Polymerisation, insbesondere durch Emulsions-, Suspensions-, Lösungs- oder Masse- polymerisation herstellen. Die (Co)Polymerisate besitzen vorzugsweise mittlere Molekulargewichte Mw. (Gewichtsmittel, ermittelt durch Lichtstreuung oder Sedimentation) zwischen 15.000 und 200.000.Polymerization, especially by emulsion, suspension, solution or bulk produce polymerization. The (co) polymers preferably have average molecular weights Mw. (Weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
Die Polyalkylenterephthalate der Komponente C.2 sind Reaktionsprodukte aus aromatischen Dicarbonsäuren oder ihren reaktionsfähigen Derivaten, wie Dimethyl- estern oder Anhydriden, und aliphatischen, cycloaliphatischen oder araliphatischen Diolen sowie Mischungen dieser Reaktionsprodukte.The polyalkylene terephthalates of component C.2 are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
Bevorzugte Polyalkylenterephthalate enthalten mindestens 80 Gew.-%, vorzugsweise mindestens 90 Gew.-%, bezogen auf die Dicarbonsäurekomponente Terephthalsäure- reste und mindestens 80 Gew.-%, vorzugsweise mindestens 90 Mol-%, bezogen auf die Diolkomponente Ethylenglykol- und/oder Butandiol-l,4-Reste.Preferred polyalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component of terephthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol -l, 4-residues.
Die bevorzugten Polyalkylenterephthalate können neben Terephthalsäureresten bis zuIn addition to terephthalic acid residues, the preferred polyalkylene terephthalates can contain up to
20 Mol-%, vorzugsweise bis zu 10 Mol-%, Reste anderer aromatischer oder cycloali- phatischer Dicarbonsäuren mit 8 bis 14 C-Atomen oder aliphatischer Dicarbonsäuren mit 4 bis 12 C-Atomen enthalten, wie z.B. Reste von Phthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbonsäure, Bernsteinsäure, Adipin- säure, Sebacinsäure, Azelainsäure, Cyclohexandiessigsäure.Contain 20 mol%, preferably up to 10 mol%, of residues of other aromatic or cycloaliphatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as e.g. Residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
Die bevorzugten Polyalkylenterephthalate können neben Ethylenglykol- bzw. Butan- diol-l,4-Resten bis zu 20 Mol-%, vorzugsweise bis zu 10 Mol-%, andere aliphatische Diole mit 3 bis 12 C-Atomen oder cycloaliphatische Diole mit 6 bis 21 C-Atomen enthalten, z.B. Reste von Propandiol-1,3, 2-Ethylpropandiol-l,3, Neopentylglykol,In addition to ethylene glycol or butanediol 1,4-residues, the preferred polyalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 Contain carbon atoms, e.g. Residues of propanediol-1,3,2-ethylpropanediol-1,3, neopentylglycol,
Pentandiol-1,5, Hexandiol-1,6, Cyclohexan-dimethanol-1,4, 3-Ethylpentandiol-2,4, 2-Methylρentandiol-2,4, 2,2,4-Trimethylpentandiol-l,3, 2-Ethylhexandiol-l,3, 2,2- Diethylpropandiol-1,3, Hexandiol-2,5, l,4-Di-(ß-hydroxyethoxy)-benzol, 2,2-Bis-(4- hydroxycyclohexyl)-propan, 2,4-Dihydroxy- 1,1,3,3 -tetramethyl-cyclobutan, 2,2-Bis- (4-ß-hydroxyethoxy-phenyl)-propan und 2,2-Bis-(4-hydroxypropoxyphenyl)-propanPentanediol-1,5, hexanediol-1,6, cyclohexane-dimethanol-1,4,3-ethylpentanediol-2,4,2-methylpentanediol-2,4,2,2,4-trimethylpentanediol-1,2,2 Ethylhexanediol-1, 3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, l, 4-di- (ß-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis (4-ß-hydroxyethoxy-phenyl) propane and 2,2-bis (4-hydroxypropoxyphenyl) propane
(DE-A 2 407 674, 2407 776, 2 715 932). Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4- wertiger Alkohole oder 3- oder 4-basischer Carbonsäuren, z.B. gemäß DE-A 1 900270 und US-PS 3 692 744, verzweigt werden. Beispiele bevorzugter Verzwei- gungsmittel sind Trimesinsäure, Trimellithsäure, Trimethylolethan und -propan und(DE-A 2 407 674, 2407 776, 2 715 932). The polyalkylene terephthalates can be branched by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, for example according to DE-A 1 900270 and US Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane and
Pentaeiythrit.Pentaeiythrit.
Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäure und deren reaktionsfähigen Derivaten (z.B. deren Dialkylestern) und Ethylenglykol und/oder Butandiol-1,4 hergestellt worden sind, und Mischungen dieser Polyalkylenterephthalate.Particularly preferred are polyalkylene terephthalates which have been produced solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.
Mischungen von Polyalkylenterephthalaten enthalten 1 bis 50 Gew.-%, vorzugsweise 1 bis 30 Gew.-%, Polyethylenterephthalat und 50 bis 99 Gew.-%, vorzugsweise 70 bis 99 Gew.-%, Polybutylenterephthalat.Mixtures of polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.
Die vorzugsweise verwendeten Polyalkylenterephthalate besitzen im allgemeinen eine Grenzviskosität von 0,4 bis 1,5 dl/g, vorzugsweise 0,5 bis 1,2 dl/g, gemessen in Phenol/o-Dichlorbenzol (1:1 Gewichtsteile) bei 25°C im Ubbelohde-Viskosimeter.The polyalkylene terephthalates preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
Die Polyalkylenterephthalate lassen sich nach bekannten Methoden herstellen (s. z.B. Kunststoff-Handbuch, Band Vm, S. 695 ff., Carl-Hanser-Verlag, München 1973).The polyalkylene terephthalates can be prepared by known methods (see e.g. Kunststoff-Handbuch, Volume Vm, p. 695 ff., Carl-Hanser-Verlag, Munich 1973).
Die Vinyl(co)polymerisate oder Polyalkylenterephtalate können in Mengen von 0 bis 45, vorzugsweise 1 bis 30 und besonders bevorzugt 2 bis 25 Gewichtsteilen in der erfindungsgemäßen Zusammensetzung enthalten sein.The vinyl (co) polymers or polyalkylene terephthalates can be present in the composition according to the invention in amounts of 0 to 45, preferably 1 to 30 and particularly preferably 2 to 25 parts by weight.
Komponente DComponent D
Phosphorhaltige Flammschutzmittel (D) im erfindungsgemäßen Sinne sind bevorzugt ausgewählt aus den Gruppen der Mono- und oligomeren Phosphor- und Phosphon- säureester, Phosphonatamine und Phosphazene, wobei auch Mischungen von mehreren Komponenten ausgewählt aus einer oder verschiedenen dieser Gruppen als Flammschutzmittel zum Einsatz kommen können. Auch andere hier nicht speziell erwähnte halogenfreie Phosphorverbindungen können alleine oder in beliebiger Kombination mit anderen halogenfreien Phosphorverbindungen eingesetzt werden.Phosphorus-containing flame retardants (D) in the sense of the invention are preferably selected from the groups of the mono- and oligomeric phosphorus and phosphonic acid esters, phosphonatamines and phosphazenes, mixtures of several components selected from one or different of these groups also being able to be used as flame retardants. Other halogen-free phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other halogen-free phosphorus compounds.
Bevorzugte Mono- und oligomere Phosphor- bzw. Phosphonsäureester sind Phosphorverbindungen der allgemeinen Formel (IN)Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IN)
worm worm
Rl, R^, R3 und R^, unabhängig voneinander jeweils gegebenenfalls halogeniertes C\ bis Cg-Alkyl, jeweils gegebenenfalls durch Alkyl, vorzugsweise C\ bis C4- Alkyl, und/oder Halogen, vorzugsweise Chlor, Brom, substituiertes C5 bis Cg-Cycloalkyl, C bis C20- r l oder C7 bis Ci2-Aralkyl,Rl, R ^, R3 and R ^, independently of one another in each case optionally halogenated C 1 -C 6 -alkyl, each optionally substituted by alkyl, preferably C 1 -C 4 -alkyl, and / or halogen, preferably chlorine, bromine, C5-Cg- Cycloalkyl, C to C20-rl or C7 to Ci2-aralkyl,
n unabhängig voneinander, 0 oder 1n independently of one another, 0 or 1
0 bis 30 und0 to 30 and
X einen ein- oder mehrkernigen aromatischen Rest mit 6 bis 30 C-Atomen, oder einen linearen oder verzweigten aliphatischen Rest mit 2 bis 30 C-Atomen, der OH-substituiert sein und bis zu 8 Etherbindungen enthalten kann, bedeuten. Bevorzugt stehen R1, R2, R3 und R4 unabhängig voneinander für C bis C4-Alkyl, Phenyl, Naphthyl oder Phenyl-Cι-C4-alkyl. Die aromatischen Gruppen R1, R2, R3 und R4 können ihrerseits mit Halogen- und/oder Alkylgruppen, vorzugsweise Chlor, Brom und/oder C bis C4-Alkyl substituiert sein. Besonders bevorzugte Aryl-Reste sind Kresyl, Phenyl, Xylenyl, Propylphenyl oder Butylphenyl sowie die entsprechenden bromierten und chlorierten Derivate davon.X is a mono- or polynuclear aromatic radical with 6 to 30 C atoms, or a linear or branched aliphatic radical with 2 to 30 C atoms, which can be OH-substituted and can contain up to 8 ether bonds. Preferably R 1 , R 2 , R 3 and R 4 independently of one another are C to C4-alkyl, phenyl, naphthyl or phenyl -CC-C4-alkyl. The aromatic groups R 1 , R 2 , R 3 and R 4 can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C to C4 alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
X in der Formel (IN) bedeutet bevorzugt einen ein- oder mehrkernigen aromatischen Rest mit 6 bis 30 C-Atomen. Dieser leitet sich bevorzugt von Diphenolen der Formel (I) ab.X in the formula (IN) preferably denotes a mono- or polynuclear aromatic radical having 6 to 30 carbon atoms. This is preferably derived from diphenols of the formula (I).
n in der Formel (IN) kann, unabhängig voneinander, 0 oder 1 sein, vorzugsweise ist n gleich 1.n in the formula (IN), independently of one another, can be 0 or 1, preferably n is 1.
q steht für Werte von 0 bis 30. Bei Einsatz von Mischungen verschiedenerq stands for values from 0 to 30. When using mixtures of different
Komponenten der Formel (IN) können Mischungen vorzugsweise zahlen- gemittelte q- Werte von 0,3 bis 20, besonders bevorzugt 0,5 bis 10, insbesondere 0,5 bis 6 verwendet werden.Components of the formula (IN) can be used in mixtures, preferably number-average q values of 0.3 to 20, particularly preferably 0.5 to 10, in particular 0.5 to 6.
X steht besonders bevorzugt fürX particularly preferably stands for
oder deren chlorierte oder bromierte Derivate, insbesondere leitet sich X von Resorcin, Hydrochinon, Bisphenol A oder Diphenylphenol ab. Besonders bevorzugt leitet sich X von Bisphenol A ab. Der Einsatz von oligomeren Phosphorsäureestern der Formel (TV), die sich vom Bisphenol A ableiten, ist besonders vorteilhaft, da die mit dieser Phosphorverbindung ausgerüsteten Zusammensetzungen eine besonders hohe Spannungsriss- und Hydrolysebeständigkeit sowie eine besonders geringe Neigung zur Belagsbildung bei der Spritzgussverarbeitung aufweisen. Des weiteren lässt sich mit diesen Flammschutzmitteln eine besonders hohe Wärmeformbeständigkeit erzielen.or their chlorinated or brominated derivatives, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. X is particularly preferably derived from bisphenol A. The use of oligomeric phosphoric acid esters of the formula (TV), which are derived from bisphenol A, is particularly advantageous since the compositions equipped with this phosphorus compound have a particularly high resistance to stress cracking and hydrolysis and a particularly low tendency to form deposits in injection molding processing. Furthermore, these flame retardants can achieve a particularly high heat resistance.
Als erfindungsgemäße Komponente C können Monophosphate (q=O), Oligophos- phate (q=l-30) oder Mischungen aus Mono- und Oligophosphaten eingesetzt werden.Monophosphates (q = O), oligophosphates (q = 1-30) or mixtures of mono- and oligophosphates can be used as component C according to the invention.
Monophosphorverbindungen der Formel (IN) sind insbesondere Tributylphosphat, Tris-(2-chlorethyl)-phosphat, Tris-(2,3 -dibromprobyl)-phosphat, Triphenylphosphat, Trikresylphosphat, Diphenylkresylphosphat, Diphenyloctylphosphat, Diphenyl-2- ethylkresylphosphat, Tri-(isopropylphenyl)-phosphat, halogensubstituierte Arylphos- phate, Methylphosphonsäuredimethylester, Methylphosphensäurediphenylester,Monophosphorus compounds of the formula (IN) are, in particular, tributyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromobroyl) phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl isophosphate, tris ) phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphate,
Phenylphosphonsäurediethylester, Triphenylphosphinoxid oder Trikresylphosphin- oxid.Phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide.
Die Phosphorverbindungen gemäß Komponente C Formel (IN) sind bekannt (vgl. z.B. EP-A 363 608, EP-A 640 655) oder lassen sich nach bekannten Methoden in analoger Weise herstellen (z.B. Ullmanns Enzyklopädie der technischen Chemie, Bd. 18, S. 301 ff. 1979; Houben-Weyl, Methoden der organischen Chemie, Bd. 12/1, S. 43; Beilstein Bd. 6, S. 177).The phosphorus compounds according to component C formula (IN) are known (cf., for example, EP-A 363 608, EP-A 640 655) or can be prepared analogously by known methods (for example Ullmann's Encyclopedia of Industrial Chemistry, vol. 18, p . 301 ff. 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
Die mittleren q- Werte können bestimmt werden, indem mittels geeigneter MethodeThe mean q values can be determined by using a suitable method
(Gaschromatographie (GC), High Pressure Liquid Chromatography (HPLC), Gelpermeationschromatographie (GPC)) die Zusammensetzung der Phosphat-Mischung (Molekulargewichtsverteilung) bestimmt wird und daraus die Mittelwerte für q berechnet werden.(Gas Chromatography (GC), High Pressure Liquid Chromatography (HPLC), Gel Permeation Chromatography (GPC)) the composition of the phosphate mixture (molecular weight distribution) is determined and from this the mean values for q are calculated.
Phosphonatamine sind vorzugsweise Verbindungen der Formel (V) A3- -yy-N ^Bl y (V)Phosphonatamines are preferably compounds of the formula (V) A 3 - - y yN ^ Bl y (V)
in welcherin which
A für einen Rest der Formel (Na)A for a radical of the formula (Na)
oder (Nb) or (Nb)
steht,stands,
Rl 1 und R 2 unabhängig voneinander für unsubstituiertes oder substituiertesRl 1 and R 2 independently of one another for unsubstituted or substituted
Cj-Cio-Alkyl oder für unsubstituiertes oder substituiertes Cg bis Cjo-Aryl, stehen,Cj-Cio-alkyl or represent unsubstituted or substituted Cg to Cjo-aryl,
Rl3 und Rl4 unabhängig voneinander für unsubstituiertes oder substituiertes C\ bis Cjo-Alkyl oder unsubstituiertes oder substituiertes Cß bis Cιo~Rl3 and Rl4 independently of one another for unsubstituted or substituted C \ to Cjo-alkyl or unsubstituted or substituted Cß to Cιo ~
Aryl stehen oderAryl stand or
Rl3 und Rl4 zusammen für unsubstituiertes oder substituiertes C3 bis C\Q- Alkylen stehen,Rl3 and Rl4 together represent unsubstituted or substituted C3 to C \ Q alkylene,
die Zahlenwerte 0, 1 oder 2 bedeuten und ßl unabhängig für Wasserstoff, gegebenenfalls halogeniertes C2 bis Cg-Alkyl, unsubstituiertes oder substituiertes Cg bis Cio-Aryl steht.the numerical values mean 0, 1 or 2 and ßl independently represents hydrogen, optionally halogenated C2 to Cg-alkyl, unsubstituted or substituted Cg to Cio-aryl.
ßl steht vorzugsweise unabhängig für Wasserstoff, für Ethyl, n- oder iso-Propyl, welche durch Halogen substituiert sein können, unsubstituiertes oder durchßl preferably independently represents hydrogen, ethyl, n- or iso-propyl, which may be substituted by halogen, unsubstituted or by
C\ bis C4-Alkyl und/oder Halogen substituiertes C bis Cio-Aryl, insbesondere Phenyl oder Naphthyl.C \ to C4-alkyl and / or halogen-substituted C to Cio-aryl, especially phenyl or naphthyl.
Alkyl in RÜ, R1^5 R13 nd R14 s en unabhängig vorzugsweise für Methyl, Ethyl, n-Propyl, iso-Propyl, n-, iso-, sek. oder tert.-Butyl, Pentyl oder Hexyl.Alkyl in RÜ, R1 ^ 5 R13 and R14 s en independently preferably for methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
Substituiertes Alkyl in R 3 und R 4 steht unabhängig vorzugsweise für durch Halogen substituiertes C\ bis Cio-Alkyl, insbesondere für ein- oder zweifach substituiertes Methyl, Ethyl, n-Propyl, iso-Propyl, n-, iso-, sek. oder tert.-Butyl, Pentyl oder Hexyl.Substituted alkyl in R 3 and R 4 independently preferably represent halogen-substituted C 1 -C 10 -alkyl, in particular mono- or di-substituted methyl, ethyl, n-propyl, iso-propyl, n-, iso-, sec. or tert-butyl, pentyl or hexyl.
Cg bis Cio- ryl steht in R^, R^, R^ und R 4 unabhängig vorzugsweise für Phenyl, Naphthyl oder Binaphthyl, insbesondere o-Phenyl, o-Naphthyl, o-Binaphthyl, welche durch Halogen (im allgemeinen ein-, zwei- oder dreifach) substituiert sein können.Cg to cyryl in R ^, R ^, R ^ and R 4 independently preferably represents phenyl, naphthyl or binaphthyl, especially o-phenyl, o-naphthyl, o-binaphthyl, which by halogen (generally one, two - or triple) can be substituted.
Rl3 und Rl4 können zusammen mit den Sauerstoffatomen, an die sie direkt gebunden sind, und dem Phosphoratom eine Rmgstruktur bilden.R13 and R14 together with the oxygen atoms to which they are directly attached and the phosphorus atom can form an Rmg structure.
Beispielhaft und vorzugsweise werden genannt: 5,5,5',5ς,5„,5„-Hexamethyl- tris(l,3,2-dioxaphosphorin- -methan)amino-2,2',2,,-trioxid der Formel (Va-1)Examples and preferably mentioned are: 5,5,5 ', 5 ς , 5 ", 5" -hexamethyl-tris (l, 3,2-dioxaphosphorine-methane) amino-2,2', 2 ,, - trioxide Formula (Va-1)
l,3,2-Dioxaphosphorinan-2-methanamin, N-butyl-N[(5,5-dimethyl-l,3,2-dioxaphos- phorman-2-yl)methyl]-5,5-dimefhyl-, P,2-dioxide; 1 ,3,2-Dioxaphosphorinane-2- methanamin, N-[[5,,5-mme yl-l,3,2-dioxaphosphorman-2-yl)methyl]-5,5-dimethyl- N-phenyl-, P,2-dioxid; l,3,2-Dioxaphosphorinan-2-memanamin, N,N-dibutyl-5,5- dimethyl-, 2-oxid, l,3,2-Dioxaphosphorinan-2-memanimin, N-[(5,5-dimethyl-l,3,2- dioxaphosphorinan-2-yl)methyl]-N-ethyl-555-dimethyl-, P,2-dioxid, 1 ,3,2-Dioxa- phosphorinan-2-methanamin, N-butyl-N-[(5,5-dichloromethyl-l,3,2-dioxaphosphori- nan-2-yl)-methyl]-5,5-di-chloromethyl-, P,2-dioxid, l,3,2-Dioxaphosphorinan-2- methanamin, N-[(5,5-di-cUoromemyl-l,3,2-dioxoaphosphorinan-2-yl)methyl]-5,5- di-chloromethyl-N-phenyl-, P,2-dioxid; 1 ,3,2-Dioxaphosphorinan-2-methanamin, N,N-di-(4-chlorobuιyl)-5,5-dimethyl-2-oxide; l,3,2-Dioxaphosphorinan-2-methan- imin, N-[(5,5-dimethyl-l,3,2-dioxaphosphorman-2-yl)meman]-N-(2-chloroethyl)- 5,5-di(chloromethyl)-, P2-dioxid. l, 3,2-dioxaphosphorinan-2-methanamine, N-butyl-N [(5,5-dimethyl-l, 3,2-dioxaphosphorman-2-yl) methyl] -5,5-dimefhyl-, P , 2-dioxide; 1, 3,2-dioxaphosphorinane-2-methanamine, N - [[5, 5-mme yl-l, 3,2-dioxaphosphorman-2-yl) methyl] -5,5-dimethyl-N-phenyl-, P, 2-dioxide; l, 3,2-dioxaphosphorinan-2-memanamine, N, N-dibutyl-5,5-dimethyl-, 2-oxide, l, 3,2-dioxaphosphorinan-2-memanimine, N - [(5,5-dimethyl -l, 3,2-dioxaphosphorinan-2-yl) methyl] -N-ethyl-5 5 5-dimethyl-, P, 2-dioxide, 1, 3,2-dioxa-phosphorinan-2-methanamine, N-butyl -N - [(5,5-dichloromethyl-l, 3,2-dioxaphosphori- nan-2-yl) methyl] -5,5-di-chloromethyl-, P, 2-dioxide, l, 3,2- Dioxaphosphorinan-2-methanamine, N - [(5,5-di-Cuoromemyl-l, 3,2-dioxoaphosphorinan-2-yl) methyl] -5,5-di-chloromethyl-N-phenyl-, P, 2- dioxide; 1, 3,2-dioxaphosphorinan-2-methanamine, N, N-di- (4-chlorobuιyl) -5,5-dimethyl-2-oxide; l, 3,2-dioxaphosphorinan-2-methane-imine, N - [(5,5-dimethyl-l, 3,2-dioxaphosphorman-2-yl) meman] -N- (2-chloroethyl) - 5.5 -di (chloromethyl) -, P2-dioxide.
Bevorzugt sind weiterhin:Also preferred are:
Verbindungen der Formel (Va-2) oder (Va-3)Compounds of formula (Va-2) or (Va-3)
wobeiin which
Rl 1, Rl25 R13 nd R 4 die oben angegebenen Bedeutungen haben. Besonders bevorzugt sind Verbindungen der Formel (Va-2) und (Va-1). Die Herstellung der Phosphonatamine ist beispielsweise in US-PS 5 844 028 beschrieben.Rl 1, Rl2 5 R13 and R 4 have the meanings given above. Compounds of the formulas (Va-2) and (Va-1) are particularly preferred. The preparation of the phosphonate amines is described, for example, in US Pat. No. 5,844,028.
Phosphazene sind Verbindungen der Formeln (Via) und (Nlb)Phosphazenes are compounds of the formulas (Via) and (Nlb)
worm worm
R jeweils gleich oder verschieden ist und für Amino, jeweils gegebenenfalls halogeniertes, vorzugsweise mit Fluor halogeniertes bis Cg-Alkyl, oder Ci bis Cg-Alkoxy, jeweils gegebenenfalls durch Alkyl, vorzugsweise Ci bis C4- Alkyl, und/oder Halogen, vorzugsweise Chlor und/oder Brom, substituiertesR is in each case identical or different and for amino, in each case optionally halogenated, preferably halogenated with fluorine to Cg-alkyl, or Ci to Cg-alkoxy, in each case optionally with alkyl, preferably Ci to C4-alkyl, and / or halogen, preferably chlorine and / or bromine, substituted
C5 bis Cö-Cycloalkyl, C bis C20-Aryl, vorzugsweise Phenyl oder Naphthyl, Cß bis C20-Aryloxy, vorzugsweise Phenoxy, Naphthyloxy, oder C7 bis C12- Aralkyl, vorzugsweise Phenyl-Cι-C4-alkyl, steht,C5 to Cö-cycloalkyl, C to C20 aryl, preferably phenyl or naphthyl, Cß to C20 aryloxy, preferably phenoxy, naphthyloxy, or C7 to C12 aralkyl, preferably phenyl-Cι-C4-alkyl,
für 0 oder eine Zahl von 1 bis 15, vorzugsweise für eine Zahl von 1 bis 10 steht. Beispielhaft seien Propoxyphosphazen, Phenoxyphosphazen, Methylphenoxy- phosphazen, Aminophosphazen und Fluoralkylphosphazene genannt. Bevorzugt ist Phenoxyphosphazen.represents 0 or a number from 1 to 15, preferably a number from 1 to 10. Examples include propoxyphosphazen, phenoxyphosphazen, methylphenoxyphosphazen, aminophosphazen and fluoroalkylphosphazenes. Phenoxyphosphazene is preferred.
Die Phosphazene können allein oder als Mischung eingesetzt werden. Der Rest R kann immer gleich sein oder 2 oder mehr Reste in den Formeln (Ia) und (Ib) können verschieden sein. Phosphazene und deren Herstellung sind beispielsweise in EP-A 728 811, DE-A 1 961668 und WO 97/40092 beschrieben.The phosphazenes can be used alone or as a mixture. The radical R can always be the same or 2 or more radicals in the formulas (Ia) and (Ib) can be different. Phosphazenes and their preparation are described for example in EP-A 728 811, DE-A 1 961668 and WO 97/40092.
Die Flammschutzmittel können allein oder in beliebiger Mischung untereinander oder in Mischung mit anderen Flammschutzmitteln eingesetzt werden. Das Phosphor enthaltende Flammschutzmittel kann in einer Menge von 0,1 bis 30, vorzugsweise 1 bis 25 und in am meisten bevorzugter Weise 2 bis 20 Gewichtsteilen in der erfindungsgemäßen Zusammensetzung eingesetzt werden.The flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants. The phosphorus-containing flame retardant can be used in an amount of 0.1 to 30, preferably 1 to 25 and most preferably 2 to 20 parts by weight in the composition according to the invention.
Komponente EComponent E
Die Flammschutzmittel entsprechend Komponente D werden oft in Kombination mit sogenannten Antidrippingrnitteln verwendet, welche die Neigung des Materials zum brennenden Abtropfen im Brandfall verringern. Beispielhaft seien hier Verbindungen der Substanzklassen der fluorierten Polyolefine, der Silikone sowie Aramidfasern genannt. Diese können auch in den erfindungsgemäßen Zusammensetzungen zum Einsatz kommen. Bevorzugt werden fluorierte Polyolefine als Antidrippingmittel eingesetzt. Die fluorierten Polyolefine sind im allgemeinen in einer Menge von 0,01 bis 3, vorzugsweise 0,05 bis 1,5 Gew. -Teilen in der Mischung enthalten.The flame retardants according to component D are often used in combination with so-called anti-dripping agents, which reduce the tendency of the material to burn in the event of a fire. Compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers may be mentioned here as examples. These can also be used in the compositions according to the invention. Fluorinated polyolefins are preferably used as anti-dripping agents. The fluorinated polyolefins are generally present in the mixture in an amount of 0.01 to 3, preferably 0.05 to 1.5 parts by weight.
Fluorierte Polyolefine sind bekannt und beispielsweise in der EP-A 0 640 655 beschrieben. Sie werden unter der Marke Teflon® beispielsweise Teflon 30N von DuPont vertrieben. Die fluorierten Polyolefine können sowohl in reiner Form als auch in Form einer koagulierten Mischung von Emulsionen der fluorierten Polyolefine mit Emulsionen der Pfropfpolymerisate (Komponente B) oder mit einer Emulsion eines Copolymeri- sats, vorzugsweise auf Styrol/Acrylnitril-Basis eingesetzt werden, wobei das fluorier- te Polyolefin als Emulsion mit einer Emulsion des Pfropfpolymerisats oder des Co- polymerisats gemischt und anschließend koaguliert wird.Fluorinated polyolefins are known and are described, for example, in EP-A 0 640 655. They are sold under the Teflon ® brand, for example Teflon 30N by DuPont. The fluorinated polyolefins can be used both in pure form and in the form of a coagulated mixture of emulsions of the fluorinated polyolefins with emulsions of the graft polymers (component B) or with an emulsion of a copolymer, preferably based on styrene / acrylonitrile, the fluorinated - The polyolefin is mixed as an emulsion with an emulsion of the graft polymer or of the copolymer and then coagulated.
Weiterhin können die fluorierten Polyolefine als Präcompound mit dem Pfropfpolymerisat (Komponente B) oder einem Copolymerisat, vorzugsweise auf Styrol/Acryl- nitril-Basis, eingesetzt werden. Die fluorierten Polyolefine werden als Pulver mit einem Pulver oder Granulat des Pfropfpolymerisats oder Copolymerisats vermischt und in der Schmelze im allgemeinen bei Temperaturen von 200 bis 330°C in üblichen Aggregaten wie Innenknetern, Extrudern oder Doppelwellenschnecken com- poundiert.Furthermore, the fluorinated polyolefins can be used as a precompound with the graft polymer (component B) or a copolymer, preferably based on styrene / acrylonitrile. The fluorinated polyolefins are mixed as a powder with a powder or granulate of the graft polymer or copolymer and are compounded in the melt generally at temperatures from 200 to 330 ° C. in conventional units such as internal kneaders, extruders or twin-screw screws.
Die fluorierten Polyolefine können auch in Form eines Masterbatches eingesetzt werden, der durch Emulsionspolymerisation mindestens eines monoethylenisch ungesättigten Monomers in Gegenwart einer wässrigen Dispersion des fluorierten Polyolefins hergestellt wird. Bevorzugte Monomerkomponenten sind Styrol, Acryl- nitril und deren Gemische. Das Polymerisat wird nach saurer Fällung und nachfolgender Trocknung als rieselfähiges Pulver eingesetzt.The fluorinated polyolefins can also be used in the form of a masterbatch which is prepared by emulsion polymerization of at least one monoethylenically unsaturated monomer in the presence of an aqueous dispersion of the fluorinated polyolefin. Preferred monomer components are styrene, acrylonitrile and mixtures thereof. After acidic precipitation and subsequent drying, the polymer is used as a free-flowing powder.
Die Koagulate, Präcompounds oder Masterbatches besitzen üblicherweise Feststoffgehalte an fluoriertem Polyolefin von 5 bis 95 Gew.-%, vorzugsweise 7 bis 60 Gew.-%.The coagulates, precompounds or masterbatches usually have solids contents of fluorinated polyolefin of 5 to 95% by weight, preferably 7 to 60% by weight.
Komponente FComponent F
Die Komponente F umfasst feinstteilige anorganische Pulver, die nur in bis zu einer Menge zugesetzt werden dürfen, so dass die beanspruchte Kerbschlagzähigkeit erhalten bleibt. Geeignete feinstteilige anorganische Pulver F bestehen vorzugsweise aus wenigstens einer polaren Verbindung von einem oder mehreren Metallen der 1. bis 5. Hauptgruppe oder 1. bis 8. Nebengruppe des Periodensystems, bevorzugt der 2. bis 5. Hauptgruppe oder 4. bis 8. Nebengruppe, besonders bevorzugt der 3. bis 5.Component F comprises very finely divided inorganic powders, which may only be added in up to an amount, so that the claimed impact strength is retained. Suitable very finely divided inorganic powders F preferably consist of at least one polar compound of one or more metals of the 1st to 5th main group or 1st to 8th subgroup of the periodic table, preferably the 2nd to 5th main group or 4th to 8th subgroup, particularly preferably the 3rd to 5th
Hauptgruppe oder 4. bis 8. Nebengruppe, oder aus Verbindungen dieser Metalle mit wenigstens einem Element ausgewählt aus Sauerstoff, Wasserstoff, Schwefel, Phosphor, Bor, Kohlenstoff, Stickstoff oder Silicium.Main group or 4th to 8th subgroup, or from compounds of these metals with at least one element selected from oxygen, hydrogen, sulfur, phosphorus, boron, carbon, nitrogen or silicon.
Bevorzugte Verbindungen sind beispielsweise Oxide, Hydroxide, wasserhaltigePreferred compounds are, for example, oxides, hydroxides, water-containing
Oxide, Sulfate, Sulfite, Sulfide, Carbonate, Carbide, Nitrate, Nitrite, Nitride, Borate, Silikate, Phosphate, Hydride, Phosphite oder Phosphonate.Oxides, sulfates, sulfites, sulfides, carbonates, carbides, nitrates, nitrites, nitrides, borates, silicates, phosphates, hydrides, phosphites or phosphonates.
Bevorzugt bestehen die feinstteiligen anorganischen Pulver aus Oxiden, Phosphaten, Hydroxiden, vorzugsweise aus TiO2, SiO2, SnO2, ZnO, ZnS, Böhmit, ZrO2, Al2O3,The very finely divided inorganic powders preferably consist of oxides, phosphates, hydroxides, preferably of TiO 2 , SiO 2 , SnO 2 , ZnO, ZnS, boehmite, ZrO 2 , Al 2 O 3 ,
Aluminiumphosphate, Eisenoxide, ferner TiN, WC, AIO(OH), SB2O3 Eisenoxide, NaSO4, Vanadianoxide, Zinkborat, Silikate wie AI-Silikate, Mg-Silikate, ein-, zwei-, dreidimensionale Silikate. Mischungen und dotierte Verbindungen sind ebenfalls verwendbar.Aluminum phosphates, iron oxides, also TiN, WC, AIO (OH), SB 2 O 3 iron oxides, NaSO 4 , vanadian oxides, zinc borate, silicates such as Al silicates, Mg silicates, one-, two-, three-dimensional silicates. Mixtures and doped compounds can also be used.
Des weiteren können diese nanoskaligen Partikel mit organischen Molekülen oberflächenmodifiziert sein, um eine bessere Verträglichkeit mit den Polymeren zu erzielen. Auf diese Weise lassen sich hydrophobe oder hydrophile Oberflächen erzeugen.Furthermore, these nanoscale particles can be surface-modified with organic molecules in order to achieve better compatibility with the polymers. In this way, hydrophobic or hydrophilic surfaces can be created.
Besonders bevorzugt sind hydrathaltige Aluminiumoxide, z.B. Böhmit oder TiO2.Hydrated aluminum oxides, for example boehmite or TiO 2 , are particularly preferred.
Die durchschnittlichen Teilchendurchmesser der Nanopartikel sind kleiner gleich 200 um, bevorzugt kleiner gleich 150 nm, insbesondere 1 bis 100 nm. Teilchengröße und Teilchendurchmesser bedeutet immer den mittleren Teilchen- durchmesser d50, ermittelt durch Ultrazentrifugenmessungen nach W. Scholtan et al., Kolloid-Z. und Z. Polymere 250 (1972), S. 782-796.The average particle diameters of the nanoparticles are less than or equal to 200 μm, preferably less than or equal to 150 nm, in particular 1 to 100 nm. Particle size and particle diameter always means the mean particle diameter d 50 , determined by ultracentrifuge measurements according to W. Scholtan et al., Kolloid-Z. and Z. Polymers 250 (1972), pp. 782-796.
Das anorganische Pulver wird in Mengen von 0,5 bis 40, vorzugsweise 1 bis 25, besonders bevorzugt von 2 bis 15 Gew.-%, bezogen auf das thermoplastische Material in die thermoplastische Formmasse eingearbeitet.The inorganic powder is incorporated into the thermoplastic molding composition in amounts of 0.5 to 40, preferably 1 to 25, particularly preferably 2 to 15% by weight, based on the thermoplastic material.
Die anorganischen Verbindungen können als Pulver, Pasten, Sole Dispersionen oder Suspensionen vorliegen. Durch Ausfällen können aus Dispersionen, Sole oder Suspensionen Pulver erhalten werden.The inorganic compounds can be present as powders, pastes, brine dispersions or suspensions. Precipitation can be used to obtain powders from dispersions, brine or suspensions.
Die Pulver können nach üblichen Verfahren in die thermoplastischen Formmassen eingearbeitet werden, beispielsweise durch direktes Kneten oder Extrudieren von Formmassen und den feinstteiligen anorganischen Pulvern. Bevorzugte Verfahren stellen die Herstellung eines Masterbatch, z.B. in Flammschutzadditiven und wenigstens einer Komponente der erfindungsgemäßen Formmassen in Monomeren oder Lösungsmitteln, oder die Cofallung von einer thermoplastischen Komponente und den feinstteiligen anorganischen Pulvern, z.B. durch Cofallung einer wäßrigen Emulsion und den feinstteiligen anorganischen Pulvern dar, gegebenenfalls in Form von Dispersionen, Suspensionen, Pasten oder Solen der feinstteiligen anorganischen Materialien.The powders can be incorporated into the thermoplastic molding compositions by customary processes, for example by directly kneading or extruding molding compositions and the very finely divided inorganic powders. Preferred methods are the preparation of a master batch, e.g. in flame retardant additives and at least one component of the molding compositions according to the invention in monomers or solvents, or the co-precipitation of a thermoplastic component and the very finely divided inorganic powders, e.g. by co-precipitation of an aqueous emulsion and the finely divided inorganic powders, optionally in the form of dispersions, suspensions, pastes or sols of the finely divided inorganic materials.
Weitere BestandteileOther components
Die erfindungsgemäßen Formmassen können wenigstens eines der üblichen Additive, wie Gleit- und Entformungsmittel, beispielsweise Pentaeiythrittetrastearat, Nukleiermittel, Antistatika, Stabilisatoren, Füll- und Verstärkungsstoffe verschieden von Komponente F), sowie Farbstoffe und Pigmente enthalten. Bevorzugte Verstärkungsstoffe sind Glasfasern. Bevorzugte Füllstoffe, die auch verstärkend wirken können, sind Glaskugeln, Glimmer, Silikate, Quarz, Talkum und Titandioxid.The molding compositions according to the invention can contain at least one of the customary additives, such as lubricants and mold release agents, for example pentaethylthritol tetrastearate, nucleating agents, antistatic agents, stabilizers, fillers and reinforcing materials different from component F), and also dyes and pigments. Preferred reinforcing materials are glass fibers. Preferred fillers, which can also have a reinforcing effect, are glass balls, mica, silicates, quartz, talc and titanium dioxide.
Die erfindungsgemäßen Formmassen können bis zu 35 Gew.-%, bezogen auf dieThe molding compositions according to the invention can contain up to 35% by weight, based on the
Gesamt-Formmasse, eines weiteren, gegebenenfalls synergistisch wirkenden Flammschutzmittels enthalten. Beispielhaft werden als weitere Flarr ischutzmittel organische Halogenverbindungen wie Decabrombisphenylether, Tetrabrombisphenol, anorganische Halogenverbindungen wie Ammoniumbromid, Stickstoffverbindungen, wie Melamin, Melaminformaldehyd-Harze, anorganische Hydroxidverbindungen wieTotal molding compound, another, optionally synergistic flame retardant contain. Organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins and inorganic hydroxide compounds such as are exemplified as further flame retardants
Mg-, Al-Hydroxid, anorganische Verbindungen wie Antimonoxide, Bariummetaborat, Hydroxoantimonat, Zirkonoxid, Zirkonhydroxid, Molybdenoxid, Ammonium- molybdat, Zinkborat, Ammoniumborat, Bariummetaborat, Talk, Silikat, Siliziumoxid und Zinnoxid sowie Siloxanverbindungen genannt.Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon oxide and tin oxide as well as siloxane compounds.
Die Füll- und Verstärkungsstoffe sowie zusätzliche Flammschutzmittel dürfen nur in solchen Mengen der erfindungsgemäßen Formmasse zugesetzt werden, dass diese den geforderten Kerbschlagzähigkeitswert nicht unterschreitet.The fillers and reinforcing materials and additional flame retardants may only be added to the molding composition according to the invention in such quantities that it does not fall below the required notched impact strength value.
Die erfindungsgemäßen Zusammensetzungen werden hergestellt, indem man die jeweiligen Bestandteile in bekannter Weise yermischt und bei Temperaturen von 200°C bis 300°C in üblichen Aggregaten wie Innenknetern, Extrudern und Doppelwellenschnecken schmelzcompoundiert und schmelzextrudiert.The compositions according to the invention are prepared by mixing the respective constituents in a known manner and melt-compounding and melt-extruding them at temperatures from 200 ° C. to 300 ° C. in conventional units such as internal kneaders, extruders and twin-screw screws.
Die Vermischung der einzelnen Bestandteile kann in bekannter Weise sowohl sukzessive als auch simultan erfolgen, und zwar sowohl bei etwa 20°C (Raumtemperatur) als auch bei höherer Temperatur.The individual constituents can be mixed in a known manner both successively and simultaneously, both at about 20 ° C. (room temperature) and at a higher temperature.
Die erfindungsgemäßen thermoplastischen Formmassen eignen sich aufgrund ihrer ausgezeichneten Flammfestigkeit, insbesondere der kurzen Nachbrennzeit, und ihrer guten mechanischen Eigenschaften im Tieftemperaturbereich und ihre hohe Wärme- formbeständigkeit zur Herstellung von Formkörpern jeglicher Art, insbesondere solchen mit erhöhten Anforderungen an mechanischen Eigenschaften im Tieftemperaturbereich wie etwa im Fahrzeugbereich. Aufgrund der Wärmeformbeständigkeit und Theologischen Eigenschaften sind Verarbeitungstemperaturen von >240°C be- vorzugt.The thermoplastic molding compositions according to the invention are suitable on account of their excellent flame resistance, in particular the short afterburn time, and their good mechanical properties in the low-temperature range and their high heat resistance Dimensional stability for the production of moldings of all kinds, especially those with increased demands on mechanical properties in the low temperature range, such as in the automotive sector. Due to the heat resistance and theological properties, processing temperatures of> 240 ° C are preferred.
Die erfindungsgemäßen Formmassen können zur Herstellung von Formkörpern jeder Art verwendet werden. Insbesondere können Formkörper durch Spritzguss hergestellt werden. Außer für Fahrzeug-Anwendungen sind die Zusammensetzungen noch für folgende Anwendungen geeignet: Haushaltsgeräte, Monitore, Drucker, Kopierer oderThe molding compositions according to the invention can be used to produce moldings of any kind. In particular, moldings can be produced by injection molding. In addition to vehicle applications, the compositions are also suitable for the following applications: household appliances, monitors, printers, copiers or
Abdeckplatten für den Bausektor und Teile für Schienenfahrzeuge. Sie sind außerdem auf dem Gebiet der Elekfrotechnik einsetzbar, weil sie sehr gute elektrische Eigenschaften haben, Innenausbauteile für ScWenenfahrzeuge, Schiffe, Busse, andere Kraftfahrzeuge und Luftfahrzeuge, Radkappen, Gehäuse von Kleintransformatoren enthaltenden Elektrogeräten, Gehäuse für Geräte zur Informationsverbreitung undCover plates for the construction sector and parts for rail vehicles. They can also be used in the field of electrical engineering because they have very good electrical properties, interior components for vehicles, ships, buses, other motor vehicles and aircraft, hubcaps, housings for electrical equipment containing small transformers, housings for devices for disseminating information and
-Übermittlung, flächige Wandelemente, Gehäuse für Sicherheitseinrichtungen, wärmeisolierte Transportbehältnisse, Vorrichtung zur Haltung oder Versorgung von Kleintieren, Abdeckgitter für Lüfteröffnungen, Formteile für Garten- und Gerätehäuser, Gehäuse für Gartengeräte.-Transmission, flat wall elements, housing for safety devices, heat-insulated transport containers, device for keeping or supplying small animals, cover grille for ventilation openings, molded parts for garden and tool sheds, housing for garden tools.
Eine weitere Form der Verarbeitung ist die Herstellung von Formkörpern durch Tiefziehen aus vorher hergestellten Platten oder Folien.Another form of processing is the production of molded articles by deep drawing from previously produced sheets or foils.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher auch die Verwendung der erfindungsgemäßen Formmassen zur Herstellung von Formkörpern jeglicher Art, vorzugsweise der oben genannten, sowie die Formkörper aus den erfindungsgemäßen Formmassen.Another object of the present invention is therefore also the use of the molding compositions according to the invention for the production of moldings of any kind, preferably those mentioned above, and the moldings from the molding compositions according to the invention.
Die folgenden Beispiele dienen der weiteren Erläuterung der Erfindung. BeispieleThe following examples serve to further explain the invention. Examples
Entsprechend den Angaben der Tabelle 1 werden fünf Polycarbonat-Zusammensetzungen hergestellt zu Prüfkörpern weiterverarbeitet und geprüft.According to the information in Table 1, five polycarbonate compositions are manufactured into test specimens and processed.
Komponente AIComponent AI
Lineares Polycarbonat auf Basis Bisphenol A mit einer relativen Lösungsviskosität von 1,272, gemessen in CH2C12 als Lösungsmittel bei 25°C und einer Konzentration von 0,5 g/100 ml.Linear polycarbonate based on bisphenol A with a relative solution viscosity of 1.272, measured in CH 2 C1 2 as solvent at 25 ° C and a concentration of 0.5 g / 100 ml.
Komponente A2Component A2
Verzweigtes Polycarbonat auf Basis von Bisphenol A mit einer relativen Lösungs- Viskosität von 1,34, gemessen in Methylenchlorid als Lösungsmittel bei 25°C und einer Konzentration von 0,5 g/ml.Branched polycarbonate based on bisphenol A with a relative solution viscosity of 1.34, measured in methylene chloride as solvent at 25 ° C and a concentration of 0.5 g / ml.
Komponente BComponent B
Pfropfrjolymerisat von 40 Gew.-Teilen eines Copolymerisats aus Styrol undGraft copolymer of 40 parts by weight of a copolymer of styrene and
Acrylnitril im Verhältnis von 72:28 auf 60 Gew.-Teile teilchenförmigen vernetzten Polybutadienkautschuk (mittlerer Teilchendurchmesser d5o = 0,32 μm), hergestellt durch Emulsionspolymerisation.Acrylonitrile particulate crosslinked in a ratio of 72:28 to 60 parts by weight of polybutadiene rubber (average particle diameter d 5 o = 0.32 m) made by emulsion polymerization.
Mittels Extraktion in Mefhylethylketon, anschließender Fällung und Trocknung wird der kautschukhaltige Anteil Ba zu 80 Gew.-% und der kautschukfreie Anteil zu 20 Gew.-% bestimmt (bezogen auf B). Komponente CBy extraction in methyl ethyl ketone, subsequent precipitation and drying, the rubber-containing fraction B a is determined to be 80% by weight and the rubber-free fraction is determined to be 20% by weight (based on B). Component C
St rol/-A-ylnitril-Copolymerisat mit einem Styrol/ Acrylnitril-Gewichtsverhältnis von 72:28 und einer Grenzviskosität von 0,55 dl/g (Messung in Dimethylformamid bei 20°C).Strol / -A-ylnitrile copolymer with a styrene / acrylonitrile weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).
Komponente DlComponent Dl
Triphenylphosphat, Disflamoll TP® der Bayer AG.Triphenyl phosphate, Disflamoll TP ® from Bayer AG.
Komponente D2Component D2
m-Phenylen-bis(di-phenylphosphat), Fyrolflex® der AKZO Nobel Chemicals GmbH.m-phenylene bis (di-phenyl phosphate), Fyrolflex ® from AKZO Nobel Chemicals GmbH.
Komponente D3Component D3
Bisphenol- A-basierendes Oligophosphat, Reofos B APP der Great Lakes Chem.Bisphenol A based oligophosphate, Reofos B APP from Great Lakes Chem.
Herstellung und Prüfung der erfindungsgemäßen FormmassenProduction and testing of the molding compositions according to the invention
Das Mischen der Komponenten der Zusammensetzungen erfolgt auf einem 3-1-Innen- kneter. Die Formkörper werden auf einer Spritzgießmaschine Typ Arburg 270 E bei 260°C hergestellt.The components of the compositions are mixed on a 3-1 internal kneader. The moldings are produced on an Arburg 270 E injection molding machine at 260 ° C.
Die Bestimmung der Kerbschlagzähigkeit ai- wird gemäß ISO 180/1 A durchgeführt.The notched impact strength ai is determined in accordance with ISO 180/1 A.
Die Bestimmung der Wärmeformbeständigkeit nach Vicat B erfolgt gemäß DIN 53 460 (ISO 306) an Stäben der Abmessung 80 x 10 x 4 mm3. Das Brandverhalten der Proben wurde nach UL-Subj. 94 V an Stäben der Abmessung 127 x 12,7 x 1,6 mm gemessen, hergestellt auf einer Spritzgußmaschine bei 260°C. The heat resistance according to Vicat B is determined in accordance with DIN 53 460 (ISO 306) on rods measuring 80 x 10 x 4 mm 3 . The fire behavior of the samples was determined according to UL Subj. 94 V measured on rods measuring 127 x 12.7 x 1.6 mm, produced on an injection molding machine at 260 ° C.
Die im unteren Teil der Tabelle dargestellten Ergebnisse zeigen, dass alle Proben die gewünschte Kerbschlagzähigkeit von größer als 20 kJ/m2 bei -20 °C, eine gute bis sehr gute Wärmeformbeständigkeit aufweisen und die geforderte Flammwidrigkeit V-O besitzen. The results shown in the lower part of the table show that all samples have the desired impact strength of greater than 20 kJ / m 2 at -20 ° C, have good to very good heat resistance and have the required flame retardancy VO.

Claims

Patentansprfiche Patentansprfiche
1. Schlagzahmodifizierte Pfropfpolymerisat und Flammschutzmittel enthaltende Polycarbonat-Zusammensetzung, wobei das Verhältms Z des im Pfropfpolymerisat (B) enthaltenen kautschukhaltigen Anteils Ba zu dem kautschukfreien Anteil K an Vinyl(co)polymerisat in der Polycarbonat- Zusammensetzung größer als 1 ist.1. Impact-modified graft polymer and flame retardant-containing polycarbonate composition, the ratio Z of the rubber-containing component B a contained in the graft polymer (B) to the rubber-free component K of vinyl (co) polymer in the polycarbonate composition being greater than 1.
2. Schlagzahmodifizierte, flammwidrige Pfropfpolymerisat enthaltende Poly- carbonat-Zusammensetzung mit einer Kerbschlagzähigkeit von größer als2. Impact-modified polycarbonate composition containing flame-retardant graft polymer with a notched impact strength of greater than
20 kJ/m2, gemessen nach ISO 180 1A bei -20°C.20 kJ / m 2 , measured according to ISO 180 1A at -20 ° C.
3. Polycarbonat-Zusammensetzung nach Anspruch 1 oder 2 die die Anforderungen V-0 gemäß UL 94 V bei einer Dicke des Probekörpers <3,2 mm erfüllt.3. Polycarbonate composition according to claim 1 or 2 which meets the requirements V-0 according to UL 94 V with a thickness of the test specimen <3.2 mm.
4. Polycarbonat-Zusammensetzung nach einem der Ansprüche 1 bis 3, enthaltend als Polycarbonat aromatisches Polycarbonat, aromatisches Polyestercarbonat oder ein Gemisch aus aromatischem Polycarbonat und Polyestercarbonat.4. Polycarbonate composition according to one of claims 1 to 3, containing as polycarbonate aromatic polycarbonate, aromatic polyester carbonate or a mixture of aromatic polycarbonate and polyester carbonate.
5. Polycarbonatzusammensetzung nach 4, worin das Polycarbonat und/oder Polyestercarbonat in einer Menge von 40 bis 99 Gew.-Teilen enthalten ist, wobei die Summe der Gewichtsteile aller Komponenten in der Zusammensetzung 100 ergibt.5. Polycarbonate composition according to 4, wherein the polycarbonate and / or polyester carbonate is contained in an amount of 40 to 99 parts by weight, the sum of the parts by weight of all components in the composition being 100.
6. Polycarbonat-Zusammensetzung nach einem der Ansprüche 1 bis 5, worin das Pfropfpolymerisat (B) aufgebaut ist aus6. Polycarbonate composition according to one of claims 1 to 5, wherein the graft polymer (B) is composed of
B.l) 5 bis 95 Gew.-% eines oder mehrerer Vinylmonomeren auf B.2) 95 bis 5 Gew.-% einer oder mehrerer Pfropfgrundlagen mit einer Glasumwandlungstemperatur <10°C.Bl) 5 to 95 wt .-% of one or more vinyl monomers B.2) 95 to 5 wt .-% of one or more graft bases with a glass transition temperature <10 ° C.
7. Polycarbonat-Zusammensetzung nach Anspruch 6, worin das Pfropfpoly- merisat in einer Menge von 1 bis 40 Gew.-Teilen enthalten ist.7. The polycarbonate composition according to claim 6, wherein the graft polymer is contained in an amount of 1 to 40 parts by weight.
8. Polycarbonat-Zusammensetzung nach Anspruch 7, enthaltend 2 bis 25 Gew.-Teile Pfropfpolymerisat.8. polycarbonate composition according to claim 7, containing 2 to 25 parts by weight of graft polymer.
9. Polycarbonat-Zusammensetzung nach einem der Ansprüche 3 bis 8, enthaltend mindestens ein thermoplastisches Polymer ausgewählt aus Vinyl(Co)- polymerisat und Polyalkylenterephthalat.9. Polycarbonate composition according to one of claims 3 to 8, containing at least one thermoplastic polymer selected from vinyl (co) polymer and polyalkylene terephthalate.
10. Polycarbonat-Zusammensetzung nach Anspruch 9, worin das thermo- plastische Polymer in einer Menge von bis zu 30 Gew.-Teilen in der Zusammensetzung enthalten ist.10. The polycarbonate composition of claim 9, wherein the thermoplastic polymer is contained in the composition in an amount of up to 30 parts by weight.
11. Polycarbonat-Zusammensetzung nach einem der Ansprüche 1 bis 10, worin eine Phosphorverbindung in einer Menge von 0,5 bis 30 Gewichtsteilen ent- halten ist.11. The polycarbonate composition according to any one of claims 1 to 10, wherein a phosphorus compound is contained in an amount of 0.5 to 30 parts by weight.
12. Polycarbonat-Zusammensetzung nach Anspruch 11, enthaltend 1 bis 25 Gew.-Teile Phosphorverbindung.12. Polycarbonate composition according to claim 11, containing 1 to 25 parts by weight of phosphorus compound.
13. Polycarbonat-Zusammensetzung nach einem der Ansprüche 1 bis 12, worin die Phosphorverbindung ein Oligophosphat ist.13. The polycarbonate composition according to any one of claims 1 to 12, wherein the phosphorus compound is an oligophosphate.
14. Polycarbonat-Zusammensetzung nach einem der Ansprüche 1 bis 13, worin fluorierte Polyolefine, organische Additive und/oder anorganische Teilchen wie Talk, Glimmer, Wollastonit, Quarz, Titandioxid und nanoskalige Verbindungen enthalten sind. 14. Polycarbonate composition according to any one of claims 1 to 13, wherein fluorinated polyolefins, organic additives and / or inorganic particles such as talc, mica, wollastonite, quartz, titanium dioxide and nanoscale compounds are contained.
15. Verwendung der Zusammensetzungen gemäß Anspruch 1 bis 14 zur Herstellung von Formkörpern.15. Use of the compositions according to claims 1 to 14 for the production of moldings.
16. Formkörper, enthaltend eine schlagzahmodifizierte Pfropfpolymerisat enthaltende Polycarbonat-Zusammensetzung nach einem der Ansprüche 1 bis 14.16. Shaped body containing an impact-modified graft polymer-containing polycarbonate composition according to any one of claims 1 to 14.
17. Formkörper nach Anspruch 16, dadurch gekennzeichnet, dass der Formkörper ein Teil eines Kraftfahrzeugs, Schienenfahrzeugs, Luftfahrzeugs oder Wasser- fahrzeugs ist. 17. Shaped body according to claim 16, characterized in that the shaped body is part of a motor vehicle, rail vehicle, aircraft or watercraft.
EP01991755A 2000-12-08 2001-11-26 Polycarbonate compositions Withdrawn EP1341848A1 (en)

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