WO2001066640A1 - Polycarbonat-formmassen mit pfropfkautschuk - Google Patents

Polycarbonat-formmassen mit pfropfkautschuk Download PDF

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Publication number
WO2001066640A1
WO2001066640A1 PCT/EP2001/002190 EP0102190W WO0166640A1 WO 2001066640 A1 WO2001066640 A1 WO 2001066640A1 EP 0102190 W EP0102190 W EP 0102190W WO 0166640 A1 WO0166640 A1 WO 0166640A1
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Prior art keywords
weight
parts
compositions according
polycarbonate compositions
acrylonitrile
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PCT/EP2001/002190
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German (de)
English (en)
French (fr)
Inventor
Herbert Eichenauer
Thomas Eckel
Holger Warth
Dieter Wittmann
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Bayer AG
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Bayer AG
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Priority claimed from DE2000136056 external-priority patent/DE10036056A1/de
Priority to MXPA02008732A priority Critical patent/MXPA02008732A/es
Priority to AU2001246480A priority patent/AU2001246480A1/en
Priority to JP2001565803A priority patent/JP5007010B2/ja
Priority to CA2402404A priority patent/CA2402404C/en
Application filed by Bayer AG filed Critical Bayer AG
Priority to BRPI0109053-4A priority patent/BR0109053B1/pt
Priority to ES01919350.7T priority patent/ES2428351T5/es
Priority to US10/220,769 priority patent/US6890979B2/en
Priority to HK03107358.8A priority patent/HK1054959B/xx
Priority to EP01919350.7A priority patent/EP1274795B2/de
Publication of WO2001066640A1 publication Critical patent/WO2001066640A1/de
Anticipated expiration legal-status Critical
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions 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
    • C08L51/04Compositions 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04Vinyl aromatic monomers and nitriles as the only monomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to thermoplastic polycarbonate / graft polymer molding compositions with improved mechanical properties (in particular impact resistance and elongation at break) and improved processing behavior (flow behavior).
  • the special graft rubbers according to the present invention are generally known (EP-A 745 624 and US-A 5 741 853). They are characterized by good toughness, workability and surface quality (gloss, color impression). It is generally mentioned that the graft rubbers can be used in thermoplastic resins such as aromatic polycarbonates, polyesters, polyamides, the proportion of the graft rubbers in the molding compositions preferably being 10 to 80, in particular 20 to 75,% by weight. There is no indication in the document of the advantageous properties of such molding compositions. EP-A 745 624 does not disclose the compositions according to the invention according to the present application.
  • DE-A 196 39 821 discloses polycarbonate-ABS mixtures, the ABS part of which consists of a mixture of graft polymers with different particle sizes and which are characterized by improved processing behavior.
  • the level of mechanical properties that can be achieved with such molding compositions, especially the combination of notched impact strength and elongation at break, is not sufficient for many applications.
  • the flame-retardant polycarbonate ABS molding compounds are also subject to increasingly higher mechanical properties.
  • organic phosphates such as oligophosphates as flame retardants for polycarbonate molding compositions
  • oligophosphates as flame retardants for polycarbonate molding compositions
  • problemsatic when used Such oligophosphates as flame retardants are always accompanied by a deterioration in the mechanical properties.
  • the object was therefore to provide polycarbonate / graft polymer (in particular of the ABS type) molding compositions with improved mechanical properties, in particular a combination of impact resistance and elongation at break and improved processing behavior.
  • Rubber bases in polycarbonate molding compositions that have the desired property profile.
  • the invention relates to a composition containing
  • the rubber latex (B2) has a particle diameter d 50 > 350 nm, preferably 380 to 450 nm, a width of the particle size distribution (measured as d od 10 from the integral Particle size distribution) from 50 to 500 nm, preferably from 100 to 400 nm, and a gel content> 70% by weight, preferably 75 to 90% by weight, and the difference in average particle diameter> 50 nm, preferably> 80 nm , particularly preferably> 100 nm,
  • thermoplastic, aromatic polycarbonates according to the invention
  • Component A are those based on the diphenols of the formula (I)
  • A is a single bond, -CC 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -S- or -SO 2 -,
  • p are 1 or 0
  • R and R, 9 independently of one another hydrogen, halogen, preferably chlorine or bromine, -CC 8 alkyl, C 5 -C 6 cycloalkyl, C 6 -C 0 aryl, preferably phenyl, and C 7 -C 2 aralkyl , preferably phenyl-C] -C -alkyl, in particular benzyl,
  • n is an integer of 4, 5, 6 or 7, preferably 4 or 5,
  • R 10 and R 11 can be selected individually for each Z, independently of one another hydrogen or CC 6 alkyl
  • ZR 10 and R n mean alkyl on at least one atom at the same time.
  • Suitable diphenols of formula (I) are e.g. Hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4th -hydorxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
  • Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane, 2,2-
  • Preferred diphenols of the formula (II) are l, l-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, l, l-bis (4-hydroxyphenyl-3,3,5-trimethylcyclohexane and l, l -Bis (4-hydroxyphenyl) -2,4,4-trimethyl-cyclopentane.
  • Polycarbonates suitable according to the invention are both homopolycarbonates and copolycarbonates.
  • Component A can also be a mixture of the thermoplastic polycarbonates defined above.
  • Polycarbonates can be made in a known manner from diphenols with phosgene by the phase interface method or with phosgene by the method in a homogeneous manner
  • the molecular weight can be adjusted in a known manner by an appropriate amount of known chain terminators.
  • Suitable chain terminators are e.g. Phenol, p-chlorophenol, p-tert-butylphenol or
  • 2,4,6-tribromophenol but also long-chain alkylphenols, such as 4- (1,3-tetramethyl- butyl) phenol according to DE-OS 2 842 005 (Le A 19 006) or monoalkylphenol or dialkylphenol with a total of 8 to 20 C atoms in the alkyl substituents according to German patent application P 3 506 472.2 (Le A 23 654), such as 3. 5-di-tert-butylphenol, p-iso-octylphenol), p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethyl-heptyl) -phenol and 4- (3,5- dimethyl-heptyl) phenol.
  • alkylphenols such as 4- (1,3-tetramethyl- butyl) phenol according to DE-OS 2 842 005 (Le A 19 006) or monoalkylphenol or dialkylphenol with a total of 8 to 20 C
  • the amount of chain terminators is generally between 0.5 and 10 mol%, based on the sum of the diphenols of the formulas (I) and / or (II) used in each case.
  • the polycarbonates A suitable according to the invention have average molecular weights (M w , weight average, measured for example by ultracentrifugation or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
  • the polycarbonates A suitable according to the invention can be branched in a known manner, preferably by incorporating 0.05 to 2 mol%, based on the sum of the diphenols used, of three or more than three-functional compounds, e.g. those with three or more than three phenolic groups.
  • preferred polycarbonates are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sum of diphenols, of 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane and the copolycarbonates of bisphenol A with up to 60 mol%, based on the molar sum of diphenols, 1, l-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane.
  • Preferred polycarbonates can also be copolycarbonates with polysiloxane structures.
  • Component B is
  • the weight ratio B1: B2, based on the respective solids content of the latices, is preferably 90:10 to 10:90, particularly preferably 60:40 to 30:70.
  • Suitable rubber latices are, for example and preferably selected from diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, dienes, and also acrylate rubbers. They generally have glass transition temperatures below 10 ° C., preferably 0 ° C., particularly preferably below -10 ° C. Diene rubbers are preferred. Particularly preferred are diene rubbers based on butadiene which, as comonomers, contain up to 50, preferably up to 30% by weight (based on the total amount of monomers used for rubber latex production), further monomers selected from the group consisting of isoprene,
  • Preferred comonomers are styrene, acrylonitrile or methyl (meth) acrylate or mixtures thereof.
  • Polybutadiene is particularly preferred.
  • the rubber patents B 1 and B2 can be prepared by emulsion polymerization of the corresponding monomers.
  • the graft polymerization is preferably carried out by adding monomers to the mixture of the butadiene polymer latices B1 and B2 in such a way that 55 to 90% by weight, preferably 60 to 80% by weight and particularly preferably 65 to 75% by weight within the first half of the monomer runtime. % of the monomers are metered in.
  • the butadiene polymer latices B1 and B2 can also be prepared by emulsifying finely divided butadiene polymers in aqueous media (cf. Japanese patent application JP-A 55 125 102).
  • the butadiene polymer latex B1 has an average particle diameter d 0
  • ⁇ 350 nm preferably 260 to 310 nm
  • a width of the particle size distribution (measured as d 90 -d ⁇ o from the integral particle size distribution) of 30 to 100 nm, preferably from 40 to 80 nm
  • a gel content ⁇ 70% by weight preferably 40 to 65% by weight.
  • the rubber latex B2 having an average particle diameter d 5 o> 350 nm, preferably 380 nm to 450, a particle size distribution width (measured as d 90 -d ⁇ o from the integral particle size distribution) of 50 to 500 nm, preferably nm from 100 to 400, and a gel content> 70% by weight, preferably 75 to 90% by weight.
  • the rubber latices according to the invention are distinguished by the fact that the difference in the average particle diameter is> 50 nm, preferably> 80 nm and particularly preferably l 100 nm.
  • the rubber latices very particularly preferably have a difference in the average particle diameter of 80 to
  • the mean particle diameter d 50 and the d 10 and d 9 o values can be determined by ultracentrifuge measurement (cf. W. Scholtan, H. Lange: Kolloid Z. and Z. Polymer 250, pp. 782 to 796 (1972 )), the values given for the gel content refer to the determination using the wire cage method in toluene (cf.
  • the gel contents of the rubber latices B1 and B2 can be adjusted in a manner known in principle by using suitable reaction conditions (e.g. high
  • the usual anionic emulsifiers such as alkyl sulfates, alkyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturated fatty acids and alkaline disproportionated or hydrogenated abietic or tall oil acids can be used as emulsifiers; emulsifiers with carboxyl groups (for example salts of C 1 -C 8) fatty acids, disproportionated
  • the graft polymerization can be carried out in such a way that the monomer mixture is continuously added to the mixture of the rubber latices B1 and B2 and polymerized.
  • the monomers used in this graft polymerization are preferably mixtures of styrene and acrylonitrile in a weight ratio of 90:10 to 50:50, particularly preferably in a weight ratio of 65:35 to 80:20, styrene and / or acrylonitrile in whole or in part can be replaced by copolymerizable monomers, preferably by ⁇ -methylstyrene, methyl methacrylate or N-phenylmaleimide.
  • molecular weight regulators can be used in the graft polymerization, preferably in amounts of 0.05 to 2% by weight, particularly preferably in amounts of 0.1 to 1% by weight (in each case based on the total amount of monomer in the
  • Suitable molecular weight regulators are, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, dimeric ⁇ -methylstyrene, terpinols.
  • the initiators are inorganic and organic peroxides, for example H 2 O, di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert-butyl hydroperoxide, p-menthane hydroperoxide, azo initiators such as azobisisobutyronitrile, inorganic persalts such as ammonium, sodium or potassium persulfate Potassium perphosphate, sodium perborate and redox systems, which are composed of a generally organic oxidizing agent and a reducing agent, with heavy metal ions also being present in the reaction medium (see H. Logemann in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1 , Pp. 263 to 297).
  • the reaction temperature is 25 ° C to 160 ° C, preferably 40 ° C to 90 ° C.
  • the above-mentioned compounds can be used as emulsifiers.
  • the graft polymerization is preferably carried out by adding monomers such that 55 to 90% by weight, preferably 60 to 80% by weight and particularly preferably 65 to 75% by weight of the total, within the first half of the total monomer metering time monomers to be used in the graft polymerization are metered in; the remaining
  • the monomer portion is metered in within the second half of the total monomer metering time.
  • thermoplastic resin component C
  • thermoplastic resin was itself produced by emulsion polymerization, the latices can be mixed and precipitated and worked up together. If the thermoplastic resin was produced by solution or bulk polymerization, the graft polymer must be washed by known methods, for example by spray drying or by adding salts and / or acids, washing the precipitated products and
  • thermoplastic resin preferably in granular form (preferably on multi-roll mills, mixing extruders or internal kneaders); this method is preferred.
  • Component C comprises one or more thermoplastic vinyl (co) polymers.
  • Suitable as vinyl (co) polymers C are polymers of at least one monomer from the group of the vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C] -C 8 ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides ) unsaturated carboxylic acids.
  • (Co) polymers of are particularly suitable Cl 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or nucleus-substituted vinyl aromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C 1 -C 8 ) alkyl esters such as eg methyl methacrylate, ethyl methacrylate), and
  • vinyl cyanides unsaturated nitriles
  • acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (d-C 8 ) alkyl esters such as methyl methacrylate, n-butyl acrylate, t -Butyl acrylate
  • unsaturated carboxylic acids such as maleic acid
  • derivatives such as anhydrides and imides
  • the (co) polymers C are resinous, thermoplastic and rubber-free.
  • copolymer of C.I. styrene and C. 2 acrylonitrile is particularly preferred.
  • Preferred vinyl resins are copolymers of styrene and acrylonitrile in a weight ratio of 90:10 to 50:50, it being possible for styrene and / or acrylonitrile to be replaced in whole or in part by ⁇ -methylstyrene and / or methyl methacrylate.
  • the (co) polymers according to C are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization (see, for example, DE-AS 2 420 385, DE-A 2 724 360).
  • the (co) polymers preferably have molecular weights M w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.
  • Flame retardants and optionally conventional additives such as lubricants, antistatic agents, mold release agents, nucleating agents or mixtures are suitable as component D to be used according to the invention. - 13 -
  • flame retardants are both halogen-containing and halogen-free compounds.
  • Suitable halogen compounds are organic chlorine and / or bromine compounds.
  • Halogen-containing flame retardants are, for example
  • Chlorinated and brominated diphenyls such as octachlorodiphenyl, decachlorodiphenyl, octabromodiphenyl, decabromodiphenyl.
  • Chlorinated and brominated diphenyl ethers such as octa and decachlorodiphenyl ether and octa and decabromodiphenyl ether.
  • Chlorinated and brominated phthalic anhydride and its derivatives such as phthalimides and bisphthalimides, e.g. Tetrachloro- and tetrabromophthalic anhydride, tetrachlor- and tetrabromophthalimide, N, N'-ethylene-bis-tetrachloro- and N, N'-ethylene-bis-tetrabromophthalimide, N-methyltetrachloro- and N-methyltetrabromophthalimide.
  • phthalimides and bisphthalimides e.g. Tetrachloro- and tetrabromophthalic anhydride, tetrachlor- and tetrabromophthalimide, N, N'-ethylene-bis-tetrachloro- and N, N'-ethylene-bis-tetrabromophthalimide, N-methyltetrachloro- and N-methyltetrabromophthalimide.
  • Chlorinated and brominated bisphenols such as 2,2-bis (3,5-di-chloro-4-hydroxyphenyl) propane and 2,2-bis (3,5-di-bromo-4-hydroxyphenyl) )-propane.
  • Bromine compounds are preferred over chlorine compounds.
  • Halogen-free flame retardants are preferred. - 14 -
  • All phosphorus compounds commonly used for this purpose are particularly suitable as flame retardants, in particular phosphine oxides and derivatives of acids of phosphorus and salts of acids and acid derivatives of phosphorus.
  • Derivatives (for example esters) of acids of phosphorus and their salts are preferred, acids of phosphorus, phosphoric acid, phosphonic acid, phosphinic acid, phosphorous acid, also in each case in dehydrated form, salts preferably being alkali metal, alkaline earth metal and ammonium salts of these acids and also whose derivatives (for example partially esterified acids) are included.
  • Particularly preferred phosphorus compounds are those of the formula (III)
  • R 12 , R 13 and R 14 independently of one another are an optionally halogenated C 1 -C 8 -alkyl or an optionally halogenated and / or alkylated C 5 - or C 6 - cycloalkyl or an optionally halogenated and / or alkylated and / or aralkylated C 6 - C 30 aryl
  • n and m are independently 0 or 1
  • halogenated C 1 -C 8 -alkyl radicals according to compounds of the formulas (III) and (IV) can be halogenated once or several times, linearly or branched.
  • alkyl radicals are chloroethyl, 2-chloropropyl, 2,3-dibromopropyl, butyl, methyl or octyl.
  • halogenated and / or alkylated C 5 - or C 6 -cycloalkyls are optionally mono- to multiply halogenated and / or alkylated C 5 - or C 6 -cycloalkyls, ie for example cyclopentyl, 0 cyclohexyl, 3,3,3-trimethylcyclohexyl and fully chlorinated cyclohexyl.
  • halogenated and / or alkylated and / or aralkylated C 6 -C 3 o-aryl radicals are optionally mono- or polynuclear, single or multiple halogenated and / or alkylated and / or aralkylated, for example chlorine-5 phenyl, bromophenyl, pentachlorophenyl, pentabromophenyl, phenyl, cresyl, isopropylphenyl, benzyl-substituted phenyl and naphthyl.
  • Phosphorus compounds of the formula (III) which can be used according to the invention are e.g. Tri-butyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, tri-phenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethyl cresyl phosphate, tri- (isopropyl-phenyl) phosphate, tris (p-benzylphenyl) phosphate, triphenylphosphine oxide, methanephosphonic acid dimethyl ester, methanephosphonic acid diphenyl ester and phenylphosphonic acid diethyl ester. 5
  • Suitable flame retardants are also oligomeric phosphorus compounds of the formula (IV) embedded image in which
  • R 15 , R 16 , R 17 , R 18 independently of one another dC 8 alkyl, preferably methyl, C 5 -C 6 cycloalkyl, C 6 -C 0 aryl, preferably phenyl, C 7 -C 2 aralkyl, preferably phenyl -C ⁇ -C -alkyl,
  • n independently of one another 0 or 1
  • X represents a mono- or polynuclear aromatic radical having 6 to 30 C atoms; preferably derived diphenols of the formula (I), in particular bisphenol A, hydroquinone or resorcinol.
  • N represents an average value between 1 and 5.
  • the molecular weight of the phosphorus compounds of the formula (IV) is generally less than 2000 g / mol, preferably less than 1000 g / mol. These are described, for example, in EP-A 0 363 608.
  • Preferred flame retardants are also mixtures of phosphorus compounds of the formula (III) and phosphorus compounds of the formula (IV).
  • the compositions according to the invention generally contain 0.5 to 25, preferably 2 to 20, in particular 3 to 15 parts by weight of phosphorus compounds (based on 100 parts by weight of total composition) as a flame retardant.
  • lubricants are hydrocarbons (e.g. paraffin oils, polyethylene waxes), alcohols (e.g. stearyl alcohol), carboxylic acids (e.g. lauric acid, palmitic acid, stearic acid), carboxylic acid amides (stearic acid amide, ethylenediamine bisstearyl amide), carboxylic acid esters (e.g. n-butyl stearate, stearyl Glycerol monostearate, glycerol tristearate, pentaerythritol tetrastearate); preferred lubricants are carboxylic acid amides and carboxylic acid esters.
  • hydrocarbons e.g. paraffin oils, polyethylene waxes
  • alcohols e.g. stearyl alcohol
  • carboxylic acids e.g. lauric acid, palmitic acid, stearic acid
  • carboxylic acid amides stearic acid amide, ethylenediamine bissteary
  • antistatic agents examples include cation-active compounds (for example quaternary ammonium, phosphonium or sulfonium salts), anion-active compounds (for example alkyl sulfonates, alkyl sulfates, alkyl phosphates, carboxylates in the form of alkali metal or alkaline earth metal salts), nonionic compounds (for example polyethylene glycol esters, poly ethylene glycol ethers, fatty acid esters, ethoxylated fatty amines); preferred antistatic agents are nonionic compounds.
  • cation-active compounds for example quaternary ammonium, phosphonium or sulfonium salts
  • anion-active compounds for example alkyl sulfonates, alkyl sulfates, alkyl phosphates, carboxylates in the form of alkali metal or alkaline earth metal salts
  • nonionic compounds for example polyethylene glycol esters, poly ethylene glycol ethers,
  • mold release agents are calcium stearate, zinc stearate, pentaerythritol tetrastearate; preferred mold release agent is pentaerythritol tetrastearate.
  • the polycarbonate / graft polymer molding compositions may contain fluorinated polyolefins in the case of specific flame retardant requirements. These are high molecular weight and have glass transition temperatures of above -30 ° C, usually above 100 ° C, fluorine contents, preferably from 65 to 76, in particular from 70 to
  • the fluorinated polyolefins have a density of 1.2 to 2.3 g / cm 3 .
  • Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers.
  • the fluorinated polyolefins are known (see “Vinyl and Related
  • compositions contain 0.01 to 1, preferably 0.05 to 0.6 parts by weight of fluorinated polyolefin (based on 100 parts by weight of the total composition).
  • the molding compositions according to the invention can also contain stabilizers, pigments, fillers and reinforcing materials.
  • Preferred fillers are glass balls, mica, silicates, quartz, talc, titanium dioxide or wollastonite.
  • Reinforcing materials are preferably glass or carbon fibers.
  • the molding compositions according to the invention containing components A to D and, if appropriate, other known additives such as stabilizers, dyes, pigments, fillers and reinforcing materials and / or nucleating agents, are prepared by mixing the respective constituents in a known manner and at temperatures of
  • the present invention thus also relates to a process for the production of thermoplastic molding compositions comprising components A to D and, if appropriate, stabilizers, dyes, pigments, fillers and reinforcing materials and / or nucleating agents, which is characterized in that components A to D and optionally stabilizers, dyes, pigments, flow agents, fillers and reinforcing materials and / or nucleating agents after mixing at temperatures of 200 to 330 ° C. in common units in melt-compounded or melt-extruded.
  • 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.
  • molding compositions of the present invention can be used to produce moldings of any type.
  • moldings can be produced by injection molding.
  • moldings that can be produced are: Housing parts of all types, for example for household appliances, such as juicers, coffee machines, mixers, for office machines, or cover plates for the construction sector and parts for the motor vehicle sector. She who- which is also used in the field of electrical engineering because they have very good electrical properties.
  • the molding compounds are particularly suitable for the production of thin-walled molded parts (e.g. data technology housing parts), where particularly high demands are placed on the impact strength, elongation at break and stress crack resistance of the plastics used.
  • thin-walled molded parts e.g. data technology housing parts
  • Another form of processing is the production of molded articles by blow molding or by deep drawing from previously produced sheets or foils.
  • A2 Polycarbonate based on bisphenol A with a relative solution viscosity of 1.20 measured in methylene chloride at 25 ° C and a concentration of
  • the graft latex After a 4-hour post-reaction time, the graft latex, after adding about 1.0 part by weight of a phenolic antioxidant, is coagulated with a magnesium sulfate / acetic acid mixture and, after washing with water, the resulting powder is dried at 70 ° C. in vacuo ,
  • E Fluorinated polyolefin: The tetrafluoroethylene polymer is used as a coagulated mixture of a graft polymer emulsion according to B1 in water and a tetrafluoroethylene polymer emulsion in water.
  • the weight ratio of graft polymer B1 to the tetrafluoroethylene polymer in the mixture is 90% by weight to 10% by weight.
  • the tetrafluoroethylene polymer emulsion has a solids content of 60% by weight, the particle size is between 50 and 500 nm.
  • the graft polymer emulsion has a solids content of 34% by weight. Mold release agent: pentaerythritol tetrastearate
  • 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 elongation at break is determined in accordance with ISO 527.
  • the MVR (melt volume flow rate) is determined according to ISO 1133.
  • the impact strength is determined according to IO 180 / 1A.
  • the fire behavior is according to UL Subj. 94 V measured on bars measuring 127x12.7x1.6 mm, produced on an injection molding machine at 260 ° C.
  • Table 2 Composition and properties of the molding compounds
  • Mold release agent 0.4 0.4 a k [kJ / m 2 ] 45 49
  • the molding compositions according to the invention which contain a special graft polymer, show marked improvements in properties with regard to notched impact strength and elongation at break.

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  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Graft Or Block Polymers (AREA)
PCT/EP2001/002190 2000-03-09 2001-02-27 Polycarbonat-formmassen mit pfropfkautschuk Ceased WO2001066640A1 (de)

Priority Applications (9)

Application Number Priority Date Filing Date Title
EP01919350.7A EP1274795B2 (de) 2000-03-09 2001-02-27 Polycarbonat-formmassen mit pfropfkautschuk
HK03107358.8A HK1054959B (en) 2000-03-09 2001-02-27 Polycarbonate molding materials containing graft rubber
AU2001246480A AU2001246480A1 (en) 2000-03-09 2001-02-27 Polycarbonate molding materials containing graft rubber
JP2001565803A JP5007010B2 (ja) 2000-03-09 2001-02-27 特定のグラフトゴムを有するポリカーボネート成形用組成物
CA2402404A CA2402404C (en) 2000-03-09 2001-02-27 Polycarbonate molding materials containing graft rubber
MXPA02008732A MXPA02008732A (es) 2000-03-09 2001-02-27 Masas de moldeo de policarbonato con caucho de injerto.
BRPI0109053-4A BR0109053B1 (pt) 2000-03-09 2001-02-27 composições de policarbonato, seu emprego, bem como corpos moldados, placas ou laminados e peças assim obtidas.
ES01919350.7T ES2428351T5 (es) 2000-03-09 2001-02-27 Masas de moldeo de policarbonato con caucho de injerto
US10/220,769 US6890979B2 (en) 2000-03-09 2001-02-27 Polycarbonate molding materials containing graft rubber

Applications Claiming Priority (4)

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DE10011544 2000-03-09
DE10011544.6 2000-03-09
DE2000136056 DE10036056A1 (de) 2000-07-25 2000-07-25 Polycarbonat-Formmassen mit speziellem Pfropfkautschuk
DE10036056.4 2000-07-25

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2537895A1 (en) 2011-06-20 2012-12-26 Styrolution (Jersey) Limited Impact modified polycarbonate compositions
WO2014122179A1 (de) * 2013-02-07 2014-08-14 Bayer Materialscience Ag Verfahren zur herstellung von abs-zusammensetzungen mit verbesserter oberfläche
WO2014122177A1 (de) * 2013-02-07 2014-08-14 Bayer Materialscience Ag Verfahren zur herstellung von abs-zusammensetzungen mit verbesserter oberfläche
WO2014122178A1 (de) * 2013-02-07 2014-08-14 Bayer Materialscience Ag Verfahren zur herstellung von abs-zusammensetzungen mit verbesserter oberfläche nach wärme-feucht-lagerung
EP2257590B1 (de) 2008-03-22 2015-04-29 Bayer Intellectual Property GmbH Schlagzähmodifizierte polycarbonat-zusammensetzungen mit einer guten kombination aus rohton, hydrolyse- und schmelzestabilität
EP3156452B1 (en) 2014-06-13 2019-01-23 Techno-UMG Co., Ltd. Thermoplastic resin composition and molded product thereof

Families Citing this family (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7514147B2 (en) * 2003-01-14 2009-04-07 Sabic Innovative Plastics Ip B.V. Formable thermoplastic multi-layer laminate, a formed multi-layer laminate, an article, and a method of making an article
KR20050106447A (ko) * 2003-02-21 2005-11-09 제너럴 일렉트릭 캄파니 내후성 다층 제품 및 그의 제조 방법
US7270882B2 (en) * 2003-02-21 2007-09-18 General Electric Company Weatherable multilayer articles and method for their preparation
US20050144309A1 (en) * 2003-12-16 2005-06-30 Intel Corporation, A Delaware Corporation Systems and methods for controlling congestion using a time-stamp
KR100650910B1 (ko) * 2004-10-13 2006-11-27 제일모직주식회사 난연성 열가소성 수지 조성물
KR100694456B1 (ko) * 2004-10-20 2007-03-12 주식회사 엘지화학 열가소성 수지 조성물 및 그의 제조방법
KR100645065B1 (ko) * 2005-06-23 2006-11-10 삼성전자주식회사 핀 전계 효과 트랜지스터와 이를 구비하는 비휘발성 메모리장치 및 그 형성 방법
WO2007078083A1 (en) * 2005-12-30 2007-07-12 Cheil Industries Inc. Flame retardant polycarbonate thermoplastic resin composition having good extrusion moldability and impact resistance
KR100722149B1 (ko) * 2005-12-30 2007-05-28 제일모직주식회사 압출가공성 및 내충격성이 우수한 난연성 폴리카보네이트계열가소성 수지 조성물
KR101114039B1 (ko) * 2007-02-05 2012-03-14 주식회사 엘지화학 기계적 물성, 내후성 및 저발연성이 우수한 열가소성 수지조성물 및 이로부터 제조된 고분자 수지 물품
KR100885819B1 (ko) * 2007-12-18 2009-02-26 제일모직주식회사 굴절률이 우수한 분지형 아크릴계 공중합체 및 그 제조방법
KR101004040B1 (ko) * 2007-12-18 2010-12-31 제일모직주식회사 상용성이 향상된 난연 내스크래치 열가소성 수지 조성물
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US8735490B2 (en) * 2009-12-30 2014-05-27 Cheil Industries Inc. Thermoplastic resin composition having improved impact strength and melt flow properties
US20110159293A1 (en) * 2009-12-31 2011-06-30 Cheil Industries Inc. Polycarbonate Resin Composition and Molded Product Using the Same
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EP2881408B1 (en) 2013-12-04 2017-09-20 Lotte Advanced Materials Co., Ltd. Styrene-based copolymer and thermoplastic resin composition including the same
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US9856371B2 (en) 2014-06-27 2018-01-02 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and low-gloss molded article made therefrom
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US9850333B2 (en) 2014-06-27 2017-12-26 Lotte Advanced Materials Co., Ltd. Copolymers and thermoplastic resin composition including the same
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KR101795132B1 (ko) * 2015-04-24 2017-11-08 롯데첨단소재(주) 폴리카보네이트 수지 조성물 및 이로부터 제조된 성형품
WO2019243107A1 (en) * 2018-06-20 2019-12-26 Ineos Styrolution Group Gmbh High heat resistant impact modified polycarbonate blend
CN114539755A (zh) * 2022-02-25 2022-05-27 金发科技股份有限公司 一种聚碳酸酯组合物及其制备方法和应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482451A2 (de) * 1990-10-24 1992-04-29 Bayer Ag Lichtalterungsbeständige, flammwidrige Polycarbonat-, Polyestercarbonat- oder Polyarylat-Formmassen
EP0745624A1 (de) 1995-06-02 1996-12-04 Bayer Ag ABS-Formmassen mit verbesserten Eigenschaften
EP0824451A1 (en) 1996-01-30 1998-02-25 HE HOLDINGS, INC. dba HUGHES ELECTRONICS Carbon fiber flocking for thermal management of compact missile electronics
US5883189A (en) 1996-11-28 1999-03-16 Bayer Ag Thermoplastic high-gloss moulding compositions of the abs type
US5883190A (en) 1996-11-28 1999-03-16 Bayer Ag Thermoplastic moulding compositions of the ABS type
US5969041A (en) 1996-07-08 1999-10-19 Bayer Ag High-impact ABS moulding compositions
WO2000000544A1 (de) 1998-06-26 2000-01-06 Bayer Aktiengesellschaft Flammwidrige polycarbonat-abs-formmassen
WO2000004067A1 (de) 1998-07-15 2000-01-27 Bayer Aktiengesellschaft Thermoplastische formmassen auf basis hochwirksamer pfropfkautschukkomponenten
DE19858731A1 (de) * 1998-12-18 2000-06-21 Bayer Ag Hochschlagzähe ABS-Formmassen

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3708913A1 (de) 1987-03-19 1988-09-29 Bayer Ag Verfahren zur herstellung kautschukreicher pfropfpolymerisate
US5204394A (en) 1988-09-22 1993-04-20 General Electric Company Polymer mixture having aromatic polycarbonate, styrene I containing copolymer and/or graft polymer and a flame-retardant, articles formed therefrom
TW386099B (en) 1995-07-26 2000-04-01 Gen Electric Flame resistant compositions of polycarbonate and monovinylidene aromatic compounds
SG69988A1 (en) 1995-11-01 2000-01-25 Gen Electric Flame retardant polycarbonate/graft blends exhibiting heat aging stability
DE19639821A1 (de) 1996-09-27 1998-04-02 Bayer Ag Polycarbonat-ABS-Mischungen mit feinteiligen Pfropfpolymerisaten
DE19734437A1 (de) 1997-08-08 1999-02-11 Clariant Gmbh Synergistische Flammschutzmittel-Kombination für Polymere

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0482451A2 (de) * 1990-10-24 1992-04-29 Bayer Ag Lichtalterungsbeständige, flammwidrige Polycarbonat-, Polyestercarbonat- oder Polyarylat-Formmassen
EP0745624A1 (de) 1995-06-02 1996-12-04 Bayer Ag ABS-Formmassen mit verbesserten Eigenschaften
EP0824451A1 (en) 1996-01-30 1998-02-25 HE HOLDINGS, INC. dba HUGHES ELECTRONICS Carbon fiber flocking for thermal management of compact missile electronics
US5969041A (en) 1996-07-08 1999-10-19 Bayer Ag High-impact ABS moulding compositions
US5883189A (en) 1996-11-28 1999-03-16 Bayer Ag Thermoplastic high-gloss moulding compositions of the abs type
US5883190A (en) 1996-11-28 1999-03-16 Bayer Ag Thermoplastic moulding compositions of the ABS type
WO2000000544A1 (de) 1998-06-26 2000-01-06 Bayer Aktiengesellschaft Flammwidrige polycarbonat-abs-formmassen
WO2000004067A1 (de) 1998-07-15 2000-01-27 Bayer Aktiengesellschaft Thermoplastische formmassen auf basis hochwirksamer pfropfkautschukkomponenten
DE19858731A1 (de) * 1998-12-18 2000-06-21 Bayer Ag Hochschlagzähe ABS-Formmassen

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2257590B1 (de) 2008-03-22 2015-04-29 Bayer Intellectual Property GmbH Schlagzähmodifizierte polycarbonat-zusammensetzungen mit einer guten kombination aus rohton, hydrolyse- und schmelzestabilität
EP2537895A1 (en) 2011-06-20 2012-12-26 Styrolution (Jersey) Limited Impact modified polycarbonate compositions
WO2014122179A1 (de) * 2013-02-07 2014-08-14 Bayer Materialscience Ag Verfahren zur herstellung von abs-zusammensetzungen mit verbesserter oberfläche
WO2014122177A1 (de) * 2013-02-07 2014-08-14 Bayer Materialscience Ag Verfahren zur herstellung von abs-zusammensetzungen mit verbesserter oberfläche
WO2014122178A1 (de) * 2013-02-07 2014-08-14 Bayer Materialscience Ag Verfahren zur herstellung von abs-zusammensetzungen mit verbesserter oberfläche nach wärme-feucht-lagerung
US9714324B2 (en) 2013-02-07 2017-07-25 Covestro Deutschland Ag Method for the production of ABS compositions having an improved surface following storage in a warm-humid environment
US9976029B2 (en) 2013-02-07 2018-05-22 Covestro Deutschland Ag Method for the production of ABS compositions having an improved surface
EP3156452B1 (en) 2014-06-13 2019-01-23 Techno-UMG Co., Ltd. Thermoplastic resin composition and molded product thereof

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EP1274795B1 (de) 2013-07-31
ES2428351T5 (es) 2018-01-02
EP1274795A1 (de) 2003-01-15
KR100769440B1 (ko) 2007-10-22
MXPA02008732A (es) 2003-04-14
JP5007010B2 (ja) 2012-08-22
KR20020079949A (ko) 2002-10-19
JP2003525991A (ja) 2003-09-02
JP2012097286A (ja) 2012-05-24
CA2402404A1 (en) 2001-09-13
AR027623A1 (es) 2003-04-02
CN1170882C (zh) 2004-10-13
AU2001246480A1 (en) 2001-09-17
US20030060565A1 (en) 2003-03-27
TWI301136B (en) 2008-09-21
BR0109053A (pt) 2003-06-03
EP1274795B2 (de) 2017-06-14
HK1054959A1 (en) 2003-12-19
CN1411490A (zh) 2003-04-16
CA2402404C (en) 2010-07-13
BR0109053B1 (pt) 2012-08-21
US6890979B2 (en) 2005-05-10
ES2428351T3 (es) 2013-11-07

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