EP1355988A1 - Polycarbonat-zusammensetzungen mit reduziertem eisengehalt - Google Patents

Polycarbonat-zusammensetzungen mit reduziertem eisengehalt

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Publication number
EP1355988A1
EP1355988A1 EP02711801A EP02711801A EP1355988A1 EP 1355988 A1 EP1355988 A1 EP 1355988A1 EP 02711801 A EP02711801 A EP 02711801A EP 02711801 A EP02711801 A EP 02711801A EP 1355988 A1 EP1355988 A1 EP 1355988A1
Authority
EP
European Patent Office
Prior art keywords
weight
polycarbonate composition
alkyl
acid
composition according
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
EP02711801A
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German (de)
English (en)
French (fr)
Inventor
Andreas Seidel
Thomas Eckel
Holger Warth
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 EP1355988A1 publication Critical patent/EP1355988A1/de
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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
    • 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
    • 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
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K7/00—Use of ingredients characterised by shape

Definitions

  • the invention relates to polycarbonate compositions (molding compositions) containing inorganic materials with improved mechanical properties and to moldings produced from the compositions.
  • polycarbonate compositions containing inorganic materials are known.
  • the inorganic materials are used, for example, as a reinforcing agent for increasing the rigidity and tensile strength
  • inorganic materials are typically used in concentrations of 0.5 to 30% by weight. Both mineral and artificially obtained materials are used.
  • WO 98/51737 discloses polycarbonate / ABS compositions (PC / ABS) which contain 1 to 15% by weight of a mineral filler such as talc or wollastonite. The use of the filler types and described in this document
  • the PC / ABS compositions of US Pat. No. 5,091,461 contain talc and non-calcined clay materials as inorganic fillers.
  • the types of talc used are characterized by a comparatively high iron content.
  • US-A 5 961 915 discloses amorphous thermoplastic compositions which are flame-retardant with phosphoric acid esters and glass flakes or Contain mica as an inorganic filler. Such fillers or reinforcing materials often have relatively high iron concentrations.
  • JP-A 11/199768 discloses flame-retardant PC / ABS compositions containing talc and phosphoric acid esters, different types of talc being used. This document does not indicate how far the different talc types affect the property profile of the blends achieved with them.
  • Particle geometry are added, but are distinguished by an improved toughness and / or low-temperature toughness level compared to the prior art.
  • inorganic material with anisotropic particle geometry-containing polycarbonate compositions (blends) with an iron content of less than about 100 ppm, preferably less than about 70 ppm and, according to a particularly preferred embodiment, less than about 50 ppm.
  • the invention furthermore relates to molded articles consisting of or containing these compositions.
  • Iron is typically introduced into polymeric compositions by polymers, fillers or reinforcing materials, and other additives.
  • iron salts are also used as process chemicals in certain polymer production processes, for example as a redox initiator or as an emulsion breaker in emulsion polymerization processes.
  • the iron is often not completely removed from the polymer in the course of the workup.
  • particles with anisotropic particle geometry are understood to mean those particles whose average so-called aspect ratio - ratio of the largest and smallest particle dimensions - is greater than 1, preferably greater than 2 and particularly preferably greater than about 5.
  • Such particles are, at least in the broadest sense, in the form of platelets or fibers.
  • Such materials include, for example, talc, other (alumino) silicates with a layer or fiber geometry such as bentonite, wollastonite, mica (mica), kaolin, hydrotalcite, hectorite, montmorillonite, and glass fibers, glass scales, carbon fibers and graphite.
  • compositions according to the invention can contain further polymeric constituents and customary additives.
  • Possible polymeric components are, for example, graft polymers of at least one vinyl monomer on one or more graft bases, thermoplastic vinyl (co) polymers, polyalkylene terephthalates, polyamides and other thermoplastic resins.
  • Possible polymer additives are mold release agents, stabilizers, antioxidants, flame retardants, dyes and pigments, antistatic agents, nucleating agents, anti-dripping agents and organic and other inorganic fillers and reinforcing materials.
  • Aromatic polycarbonates and / or aromatic polyester carbonates according to component A which are suitable according to the invention are known from the literature 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
  • aromatic polycarbonates takes place e.g. B. by implementing
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
  • B each C. to C ] 2 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
  • R 5 and R 6 can be selected individually for each X 1 , independently of one another hydrogen or C. to C, alkyl, preferably hydrogen, methyl or ethyl,
  • n is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C. -C 5 -alkanes, bis- (hydroxyphenyl) -C.-C 6 -cycloalkanes, bis- (hydroxyphenyl) ethers, bis- (hydroxyphenyl) sulfoxides, bis- (hydroxyphenyl) ketones, bis- (hy - Droxyphenyl) sulfones and ⁇ , ⁇ -bis (hydroxyphenyl) diisopropyl benzenes and their core-brominated and / or core-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol-A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) 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-hydroxyphenyl) 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.
  • thermoplastic, aromatic polycarbonates Suitable for the production of thermoplastic, aromatic polycarbonates
  • Chain terminators 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-A 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-dimethylheptyl) 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 scattered light measurement) of 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 trifunctional compounds, for example those with three and more phenolic groups.
  • copolycarbonates Both homopolycarbonates and copolycarbonates are suitable.
  • 1 to 25% by weight, preferably 2.5 to 25% by weight (based on the total amount of diphenols to be used) of polydiorganosiloxanes with hydroxyaryloxy end groups can also be used. These are known (for example US 3,419,634) or according to methods known from the literature can be produced.
  • the production of copolycarbonates containing polydiorganosiloxanes is described, for example, in DE-A 3 334 782.
  • preferred polycarbonates are the copolycarbonates of bisphenol-A with up to 15 mol%, based on the molar amounts of diphenols, of other diphenols mentioned as preferred or particularly preferred, in particular 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, diphenyl ether-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.
  • aromatic polyester carbonates In addition to the monophenols already mentioned, their 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 C 1 to C 22 -alkyl groups or by halogen atoms, and aliphatic C 2 to C 22 - 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 aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be linear or branched in a known manner (see also DE-A 2 940 024 and DE-A 3 007 934).
  • three or more functional 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, can be used as branching agents in amounts of 0 , 01 to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or multifunctional phenols, such as phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4 , 4-dimethyl-2,4-
  • 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 carbonate groups.
  • Both the ester and the carbonate content of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ re ⁇ ) 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 in terms of solutions of 0.5 g polycarbonate or polyester carbonate in 100 ml methylene chloride solution at 25 ° C).
  • thermoplastic, aromatic polycarbonates and polyester carbonates can be used alone or in any mixture. You can in the composition of the invention in an amount of preferably 5 to 95 parts by weight, particularly preferably 10 to 90 parts by weight and most preferably 20 to 80 parts by weight, very particularly preferably 45 to 80 parts by weight. Parts.
  • Component B comprises one or more graft polymers of
  • the graft base B.2 generally has an average particle size (d 50 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
  • 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 imides) of unsaturated carboxylic acids (for example maleic anhydride and N phenyl-maleimide).
  • C 1 -C 8 alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate
  • derivatives such as anhydrides and imides of unsaturated carboxylic acids (for example maleic anhydride and N phenyl-maleimide).
  • 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.1.2 acrylonitrile.
  • Graft bases B.2 suitable for the graft polymers B are, for example, diene rubbers, EP (D) M rubbers, ie 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, isoprene etc.) or mixtures of diene rubbers or copolymers of diene rubbers or their mixtures with other copolymerizable monomers (for example in accordance with B1 and B1), with the proviso that the glass transition temperature 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 e.g. ABS polymers (emulsion,
  • the gel fraction 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. by
  • Emulsion, suspension, solution or bulk polymerization preferably produced by emulsion or bulk polymerization.
  • Particularly suitable graft rubbers are also ABS polymers which, by redox initiation with an initiator system made of organic hydroperoxide and
  • Ascorbic acid can be prepared according to US Pat. No. 4,937,285.
  • graft polymers B are also understood according to the invention 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.
  • Suitable acrylate rubbers according to B.2 of the polymers B are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on B.2, of other polymerizable, ethylenically unsaturated monomers.
  • the preferred polymerizable acrylic acid esters include Cj-Cs alkyl esters, for example methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Halogen alkyl esters, preferably halogen -Cs 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 carbon atoms, such as ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds such as trivinyl and triallyl cyanate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least three ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers trialyll cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine 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.
  • 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, ⁇ -methyl styrene, acrylamides, vinyl CJ C ⁇ alkylether, methylmethacrylate, butadiene.
  • 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-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 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 II, Georg Thieme-Verlag, Stuttgart 1977).
  • the average particle size d 50 is the diameter above and below which 50% by weight 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).
  • Component B can in the composition according to the invention in a
  • 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),
  • the (co) polymers C.l are resin-like, thermoplastic and rubber-free.
  • the copolymer of C.1.1 styrene and C.1.2 acrylonitrile is particularly preferred.
  • the (co) polymers according to Cl are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights M w (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
  • 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.
  • the polyalkylene terephthalates can be prepared by incorporating relatively small amounts of trihydric or tetravalent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • 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 preferably used polyalkylene terephthalates 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 Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (e.g.
  • Component C can be contained in the composition according to the invention in an amount of preferably 0 to 50 parts by weight, particularly preferably up to 30 parts by weight and most preferably up to 20 parts by weight.
  • compositions can be made flame-retardant by adding suitable additives.
  • Halogen compounds in particular those based on chlorine and bromine and compounds containing phosphorus, may be mentioned as examples of flame retardants.
  • compositions preferably contain phosphorus-containing flame retardants from the groups of the mono- and oligomeric phosphoric and phosphonic acid esters,
  • Phosphonatamines and phosphazenes where mixtures of several components selected from one or different of these groups can also be used as flame retardants.
  • Other phosphorus compounds not specifically mentioned here can also be used alone or in any combination with other flame retardants.
  • Preferred mono- and oligomeric phosphoric or phosphonic acid esters are phosphorus compounds of the general formula (IV)
  • R 1 , R 2 , R 3 and R 4 independently of one another, in each case optionally halogenated C 1 to C 8 -alkyl, in each case optionally by alkyl, preferably C. to C 4 -alkyl, and / or halogen, preferably chlorine, bromine, substituted C 5 to C 6 cycloalkyl, C 6 to C 20 aryl or C ⁇ to C, 2 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 are each independently C j to C 4 - alkyl, phenyl, naphthyl or phenyl-C.-C 4 alkyl.
  • the aromatic groups R, R, R and R 4 can in turn be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C j to C 4 alkyl.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in the formula (TN) 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 (IV), 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 (IV) can be used in mixtures preferably having 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.
  • oligomeric phosphoric acid esters of the formula (IV), 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 during injection molding processing. Furthermore, these flame retardants can achieve a particularly high heat resistance.
  • Further preferred phosphorus-containing compounds are compounds of the formula (IVa)
  • R 1 , R 2 , R 3 and R 4 each independently of one another Ci to C 8 alkyl and / or C 5 to C 6 cycloalkyl, C 6 to C 10 optionally substituted by alkyl
  • n independently of one another 0 or 1
  • R 5 and R 6 are independently Cj to C 4 alkyl and
  • Y is Ci to C 7 alkylidene, Ci to C 7 alkylene, C 5 to C 2 cycloalkylene, C 5 to C 12 cycloalkylidene, -O-, -S-, -SO-, SO 2 or -CO- mean ,
  • 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, diphenyloctyl phosphate, diphenyl 2-ethyl, tri-phosphyl phosphate (isopropylphenyl) phosphate, halogen-substituted aryl phosphates, methylphosphonic acid dimethyl ester, methylphosphonic acid diphenyl ester, phenylphosphonic acid diethyl ester, triphenylphosphine oxide or tricresylphosphine oxide
  • the phosphorus compounds according to component D formula (IN) are known (cf. e.g. EP-A 0 363 608, EP-A 0 640 655) or can be prepared in an analogous manner by known methods (e.g. Ullmann's encyclopedia of industrial chemistry,
  • the mean q values can be determined by using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) to determine the composition of the phosphate mixture (molecular weight distribution) and from this the mean values for q be calculated.
  • a suitable method gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)
  • Phosphonatamines are preferably compounds of the formula (V)
  • R 11 and R 12 independently of one another represent unsubstituted or substituted C to C 10 alkyl or unsubstituted or substituted C 6 to C 1Q aryl,
  • R 13 and R 14 independently of one another for unsubstituted or substituted C.
  • R 13 and R 14 together represent unsubstituted or substituted C 3 to C 10 alkylene
  • y are the numerical values 0, 1 or 2 and
  • ß independently represents hydrogen, optionally halogenated C 2 to C 8 alkyl, unsubstituted or substituted C fi to C 10 aryl.
  • ⁇ preferably independently represents hydrogen, ethyl, n- or iso-propyl, which may be substituted by halogen, unsubstituted or substituted by C 1 -C 4 -alkyl and / or halogen-substituted C 6 to C IQ aryl, in particular phenyl or naphthyl.
  • Alkyl in R 11 , R 12 , R 13 and R 14 is independently preferably methyl, ethyl, n-propyl, isopropyl, n-, iso-, sec- or tert-butyl, pentyl or hexyl.
  • Substituted alkyl in R 11, R 12, R 13 and R 14 independently preferably halogen-substituted C j to C 10 alkyl, in particular mono- or disubstituted methyl, ethyl, n-propyl, iso-propyl, n- , iso-, sec- or tert-butyl, pentyl or hexyl.
  • C 6 to C 10 aryl in R 11 , R 12 , R 13 and R 14 independently independently preferably represent phenyl, naphthyl or binaphthyl, in particular o-phenyl, o-naphthyl, o-binaphthyl, which is replaced by halogen (generally a , two or three times) can be substituted.
  • R 13 and R 14 together with the oxygen atoms to which they are directly attached and the phosphorus atom can form a ring structure.
  • R 11 , R 12 , R 13 and R 14 have the meanings given above.
  • Phosphazenes are compounds of the formulas (Via) and (Vlb)
  • R is the same or different and represents amino, in each case optionally halogenated, preferably with fluorine halogenated C ⁇ to C 8 alkyl, or C to C 8 - alkoxy, each optionally substituted by alkyl, preferably C to C 4 - alkyl , and / or halogen, preferably chlorine and / or bromine, substituted C 5 to C 6 cycloalkyl, C 6 to C 2Q aryl, preferably phenyl or naphthyl,
  • k 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 particularly 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.
  • the flame retardants can be used alone or in any mixture with one another or in a mixture with other flame retardants.
  • Component D can be present in the composition according to the invention in an amount of preferably 0.5 to 20 parts by weight, particularly preferably 1 to 18 parts by weight and most preferably 2 to 15 parts by weight.
  • polycarbonate compositions contain the aforementioned inorganic materials with anisotropic particle geometry.
  • Inorganic materials with a flaky or flaky character are preferably used, such as talc, mica / clay layer minerals, montmorrilonite, the latter also in an organophilic form modified by ion exchange, kaolin and vermiculite.
  • the inorganic materials can be surface-treated, for example silanized, in order to ensure better polymer compatibility.
  • Talc is particularly preferred.
  • Talc is understood to mean a naturally occurring or synthetically produced talc.
  • Pure talc has the chemical composition 3MgO 4SiO 2 H 2 O and thus an MgO content of 31.9% by weight, an SiO 2 Content of 63.4% by weight and a content of chemically bound water of 4.8% by weight. It is a silicate with a layer structure.
  • Naturally occurring talc materials generally do not have the ideal composition listed above, since they are replaced by partial exchange of the
  • Magnesium are contaminated by other elements, by partial exchange of silicon, for example by aluminum and / or by adhesions with other minerals such as dolomite, magnesite and chlorite.
  • These contaminated natural talcum powders can also be used in the composition according to the invention, but preference is given to high purity talc types. These contain, for example, an MgO content of 28 to 35% by weight, preferably 30 to 33% by weight, particularly preferably 30.5 to 32% by weight and an SiO 2 content of 55 to 65% by weight , preferably 58 to 64% by weight, particularly preferably 60 to 62.5% by weight.
  • Preferred types of talc are further characterized by an Al 2 O 3 content of ⁇ 5% by weight, particularly preferably ⁇ 1% by weight, in particular of
  • the iron content of the talc should be as low as possible, for example ⁇ 0.5% by weight, in particular ⁇ 0.3% by weight, particularly preferably ⁇ 0.2% by weight.
  • talc in the form of finely ground types with an average largest particle size dso of ⁇ 10 ⁇ m, preferably ⁇ 5 ⁇ m, particularly preferably ⁇ 2.5 ⁇ m, very particularly preferably ⁇ 1.5 ⁇ m.
  • component E can be present in the composition according to the invention in an amount of preferably 0.1 to 30 parts by weight, particularly preferably 0.2 to 20 parts by weight and most preferably 0.5 to 15 parts by weight. Parts.
  • Component F is preferably 0.1 to 30 parts by weight, particularly preferably 0.2 to 20 parts by weight and most preferably 0.5 to 15 parts by weight.
  • 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 drip in the event of fire.
  • anti-dripping agents 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.
  • Fluorinated polyolefins are known and are described, for example, in EP-A 0 640 655. For example, they are marketed by DuPont under the Teflon ® 30N brand.
  • 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 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 generally compounded in the melt 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. The polymer becomes after acidic precipitation and subsequent
  • Drying 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 can be present in the composition according to the invention in an amount of preferably 0.05 to 5 parts by weight, particularly preferably 0.1 to 1 part by weight and most preferably 0.1 to 0.5 parts by weight. Parts may be included.
  • the molding compositions according to the invention can also contain at least one of the customary additives, such as lubricants and mold release agents, for example pentaerythritol tetra-stearate, nucleating agents, antistatic agents, stabilizers, and, in addition to the inorganic materials with the selected aspect ratio, inorganic materials with a different geometry such as further fillers and Reinforcing materials as well as dyes and pigments contain.
  • the customary additives such as lubricants and mold release agents, for example pentaerythritol tetra-stearate, nucleating agents, antistatic agents, stabilizers, and, in addition to the inorganic materials with the selected aspect ratio, inorganic materials with a different geometry such as further fillers and Reinforcing materials as well as dyes and pigments contain.
  • the molding compositions according to the invention can contain up to 35% by weight, based on the total molding composition, of a further flame retardant which may have a synergistic effect. contain protective agents.
  • a further flame retardant which may have a synergistic effect.
  • contain protective agents examples include organic halogen compounds such as decabromobisphenyl ether, tetrabromobisphenol, inorganic halogen compounds such as ammonium bromide, nitrogen compounds such as melamine, melamine formaldehyde resins, inorganic hydroxide compounds such as Mg, Al hydroxide, inorganic compounds such as antimony oxides, barium metaborate, hydroxoantimonate, zirconium oxide, zirconium hydroxide , Ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talc, silicate, silicon oxide and tin oxide, and siloxane compounds.
  • organic halogen compounds such as decabromobispheny
  • the molding compositions according to the invention are produced by the respective
  • 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.
  • the molding compositions according to the invention can be used to produce moldings of any kind. These can be made by injection molding, extrusion and blow molding. Another form of processing is the production of shaped bodies by deep drawing from previously produced plates or foils.
  • foam bodies are foils, profiles, housing parts of any kind, e.g. for household appliances such as juicers, coffee machines, mixers; for office machines like
  • the molding compositions according to the invention can furthermore be used, for example, for the production of the following moldings or moldings:
  • Molded parts for garden and tool sheds 16. Housing for garden tools.
  • Component C
  • Styrene / acrylonitrile copolymer with a styrene / acylmtril weight ratio of 72:28 and an intrinsic viscosity of 0.55 dl / g (measurement in dimethylformamide at 20 ° C).
  • Talc with an average particle diameter (d 5 o) according to the manufacturer's specification of 0.9 ⁇ m, a total iron content of 0.14% by weight and a content of acid-soluble iron of 0.11% by weight.
  • Talc with an average particle diameter (d 50 ) according to the manufacturer's specification of 1.2 ⁇ m, a total iron content of 0.06% by weight and a content of acid-soluble iron of 0.01% by weight.
  • Talc with an average particle diameter (dso) according to the manufacturer's specification of 1.2 ⁇ m, a total iron content of 0.98% by weight and an acid-soluble content
  • Talc with an average particle diameter (dso) according to the manufacturer's specification of 1.3 ⁇ m, a total iron content of 0.99% by weight and a content of acid-soluble iron of 0.03% by weight.
  • Talc with an average particle diameter (dso) according to the manufacturer's specification of 1.3 ⁇ m, a total iron content of 1.05% by weight and a content of acid-soluble iron of 0.03% by weight.
  • Talc with an average particle diameter (d 50 ) according to the manufacturer's specification of 2.1 ⁇ m, a total iron content of 0.07% by weight and a content of acid-soluble iron of 0.04% by weight.
  • Talc with an average particle diameter (d 5 o) according to the manufacturer's specification of 1.8 ⁇ m, a total iron content of 0.42% by weight and an acid-soluble content
  • Talc with an average particle diameter (d 50 ) according to the manufacturer's specification of 1.9 ⁇ m, a total iron content of 0.96% by weight and an acid-soluble iron content of 0.02% by weight.
  • Talc with an average particle diameter (d 5 o) according to the manufacturer's specification of 2.0 ⁇ m, a total iron content of 1.79% by weight and an acid-soluble iron content of 0.11% by weight.
  • Talc with an average particle diameter (d 50 ) according to the manufacturer's specification of 2.5 ⁇ m, a total iron content of 0.70% by weight and a content of acid-soluble iron of 0.05% by weight. All components El to El 2 are ground natural minerals with a talc content of> 96% by weight. According to the manufacturer, the Al 2 O 3 content of all types is ⁇ 1% by weight.
  • Tetrafluoroethylene polymer as a coagulated mixture of a SAN graft polymer emulsion according to component B mentioned above in water and a tetrafluoroethylene polymer emulsion in water.
  • the weight ratio of graft polymer B to the tetrafluoroethylene polymer in the mixture is 90% by weight
  • the tetrafluoroethylene polymer emulsion has a solids content of 60% by weight; the average particle diameter is between 0.05 and 0.5 ⁇ m.
  • the emulsion of the tetrafluoroethylene polymer (Teflon® 30 N from DuPont) is mixed with the emulsion of the SAN graft polymer B and stabilized with 1.8% by weight, based on polymer solids, of phenolic antioxidants. At 85 to 95 ° C the mixture is coagulated with an aqueous solution of MgSO 4 (Epsom salt) and acetic acid at pH 4 to 5, filtered and washed until practically free of electrolytes, then freed from the main amount of water by centrifugation and then at 100 ° C to a powder.
  • MgSO 4 Epsom salt
  • PTS Pentaerythritol tetrastearate
  • the iron content of inorganic material and molding materials containing inorganic material is determined by optical emission spectrometry with inductively coupled plasma (ICP-OES).
  • the material is subjected to a melt digestion using lithium metaborate as a flux, with 0.1 to 1 g of the material to be investigated being precisely weighed and mixed and mixed in a platinum crucible with 1.5 to 2.5 g of the flux Melt at 1000 ° C for 30 minutes. After cooling, the melt cake is taken up in 5 ml of nitric acid and dissolved with stirring. The solution is made up to 100 ml for examination using ICP-OES.
  • the notched impact strength aj ⁇ is determined in accordance with ISO 180/1 A.
  • the examples in columns 1 to V7 are samples with comparatively small amounts of the inorganic material
  • the examples in columns 5 and V8 are samples with larger amounts of the same
  • the examples in columns 6 to V10 relate to polycarbonate blends without flame retardants and without Teflon masterbatch.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Inorganic Insulating Materials (AREA)
EP02711801A 2001-01-25 2002-01-14 Polycarbonat-zusammensetzungen mit reduziertem eisengehalt Withdrawn EP1355988A1 (de)

Applications Claiming Priority (3)

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DE10103237 2001-01-25
DE10103237A DE10103237A1 (de) 2001-01-25 2001-01-25 Polycarbonat-Zusammensetzungen mit reduziertem Eisengehalt
PCT/EP2002/000257 WO2002059203A1 (de) 2001-01-25 2002-01-14 Polycarbonat-zusammensetzungen mit reduziertem eisengehalt

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JP2011012122A (ja) * 2009-06-30 2011-01-20 Asahi Kasei Chemicals Corp 難燃性に優れる熱可塑性樹脂組成物
JP2015500899A (ja) * 2011-11-30 2015-01-08 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ 高表面品質を有する成形品
KR101771729B1 (ko) * 2012-07-25 2017-08-25 삼성전기주식회사 적층형 인덕터 및 적층형 인덕터의 보호층 조성물
TWI674290B (zh) * 2013-09-11 2019-10-11 德商科思創德意志股份有限公司 具尺寸穩定性之聚碳酸酯－聚對酞酸伸烷基酯模塑料
TWI508994B (zh) * 2013-12-27 2015-11-21 Chi Mei Corp 聚碳酸酯組成物
CN105482426B (zh) * 2015-12-25 2017-05-31 金发科技股份有限公司 一种聚碳酸酯复合材料
CN105482425B (zh) * 2015-12-25 2017-03-22 金发科技股份有限公司 一种聚碳酸酯复合材料
TWI745364B (zh) * 2016-03-23 2021-11-11 德商科思創德意志股份有限公司 具改良之耐水解性之聚碳酸酯組成物
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US7030180B2 (en) 2006-04-18
BR0206757A (pt) 2004-02-17
CN1537145A (zh) 2004-10-13
CN1240776C (zh) 2006-02-08
CA2435564A1 (en) 2002-08-01
US20020132899A1 (en) 2002-09-19
RU2003125872A (ru) 2005-01-10
KR100842134B1 (ko) 2008-06-27
TWI304427B (en) 2008-12-21
JP2004520469A (ja) 2004-07-08
MXPA03006507A (es) 2004-04-21

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