EP1563009A1 - Matiere moulable polyamide, pieces moulees pouvant etre fabriquees a partir de cette matiere et utilisation de ladite matiere - Google Patents

Matiere moulable polyamide, pieces moulees pouvant etre fabriquees a partir de cette matiere et utilisation de ladite matiere

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Publication number
EP1563009A1
EP1563009A1 EP03778296A EP03778296A EP1563009A1 EP 1563009 A1 EP1563009 A1 EP 1563009A1 EP 03778296 A EP03778296 A EP 03778296A EP 03778296 A EP03778296 A EP 03778296A EP 1563009 A1 EP1563009 A1 EP 1563009A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
composition according
molding composition
polyamides
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP03778296A
Other languages
German (de)
English (en)
Inventor
Alwin Hermann Schwitzer
Manfred Hewel
Eduard Schmid
Ivano Laudonia
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.)
EMS Chemie AG
Original Assignee
EMS Chemie AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EMS Chemie AG filed Critical EMS Chemie AG
Publication of EP1563009A1 publication Critical patent/EP1563009A1/fr
Withdrawn legal-status Critical Current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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/36—Sulfonation; Sulfation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C08F222/08—Maleic anhydride with vinyl aromatic monomers
    • 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
    • C08K3/013—Fillers, pigments or reinforcing 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • 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
    • C08L51/06—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 homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Definitions

  • the invention relates to reinforced polyamide molding compositions with improved processing behavior, increased flowability and molded articles produced therefrom with improved surface quality and improved mechanical properties, in particular in the conditioned state after moisture absorption.
  • the molding compound according to the invention is suitable for the production of molded parts, in particular with large wall thicknesses, or other semi-finished or finished parts which, for example, can be produced by extrusion, extrusion blow molding, extrusion stretch blow molding, pultrusion, injection molding, micro injection molding, GIT injection molding, injection blowing or other shaping techniques.
  • Reinforced polyamides play an increasing role in the field of engineering construction materials in addition to high rigidity, toughness and heat resistance for use in the visible area, must show an optimal surface quality. Areas of application are interior and exterior parts in the automotive and other transport sectors, housing material for devices and apparatus for telecommunications, consumer electronics, household appliances, mechanical engineering, heating systems and fastening parts for installations. External parts that are exposed to the weather require additional stabilization in order to ensure the necessary function for several years.
  • reinforced polyamides is the exceptionally good bond between the polymer matrix and reinforcing materials. This enables high levels of reinforcement, which lead to highly rigid products, which can be easily processed in an injection molding process due to the low melt viscosity of polyamides.
  • EP 1 120 443 A2 describes transparent polyamide mixtures in which a branched polyamide component based on the transparent polyamide is used to improve the flow.
  • the resulting, unreinforced mixtures are stiffer but less impact-resistant than the purely transparent polyamides.
  • the branched polyamide is made using a polyamine dendrimer.
  • Transparent polyamides must be used as the basis of the mixtures and the mixtures must remain transparent.
  • EP 0 672 703 A1 also describes the structure of branched, star-shaped polyamides from linear polyamides with dendrimers as branching agents for improving the flow.
  • star-shaped polyamides from lac amen is described in EP 0 832 149 B1 by a two-stage process with a triazine derivative or a trifunctional amine as branching agent.
  • the resulting star-shaped (3 arms) polyamides show a ne reduction of melt and solution viscosity. Lactam polymerization with the branching agents also provides a mixture of low molecular weight, linear polyamides and branched polyamides.
  • H-shaped polyamides from lactaenes or aminocarboxylic acids with at least trifunctional amines (dendrimers) or trifunctional carboxylic acids as branching structures is known from DE 19 654 179 AI.
  • the H-shaped polyamides show improved flow behavior with good mechanical properties. This document only deals with the production of the branched polyamides and does not describe any reinforced molding compounds.
  • branched graft polyamides which can be used as an unreinforced blend component or as a hot melt adhesive, from diamines and dicarboxylic acids via precondensates which appear to crosslink or via a hydrolytic degradation of e.g. PA66 with polyamines as a branching structure are described in EP 1065 232 A2.
  • EP 1 065 236 A2 discloses hydrolysis-stable, low-viscosity, branched polyamides which are produced in a batch process from caprolactam and a polyamine.
  • the polyamides obtained are preferably used as unreinforced, solvent- and fuel-resistant molding compositions.
  • WO 0 068 298 describes the production of highly branched, hyperbranched, dendrimer-like polyamides (PA6) with short PA6 arms, from 2 -10 caprolactam units per arm, as an additive for improving the melt flow of reinforced, thermoplastic molding compositions.
  • PA6 dendrimer-like polyamides
  • the molding compositions produced in this way are characterized by a higher breaking stress and a higher Tg.
  • Reinforced polyamide molding compositions are also presented in EP 1099 727 A2. They consist of mixtures of thermoplastic polyamides with highly branched, so-called hyperbranched, polyetherimides, which are obtained by the polymerization of 1-oxazolines.
  • the molding compositions are characterized by improved flowability and a reduction in the crystalline content.
  • WO 0 196 474 describes the visual surface improvement of injection molded parts by mixing linear, partially crystalline polyamides with highly branched, polyamide 6, with short polyamide 6 arms, and reinforcing materials.
  • the molding compositions should have the smallest possible differences in the mechanical properties, the highest possible heat resistance and moderate processing temperatures.
  • branched, highly flowable graft polyamides which are derived from linear, semi-crystalline polyamides, to give linear semi-crystalline polyamides and amorphous polyamides, molding compositions which, with high reinforcement proportions, have a high stiffness, a high breaking stress, one show high impact strength even after absorption of moisture and have a high flowability of the melt or a low solution viscosity and molded articles produced therefrom have a high surface quality.
  • What is important in the case of the polyamide mixture A) is not only that it has a combination of a semicrystalline linear polyamide a) with a branched graft polyamide b), but that the graft polyamide b) has to meet special conditions.
  • the graft polyamide bl) is composed of a styrene-maleimide basic structural unit of the general formula 1
  • m stands for 1-5 and n stands for 3-15, the molar mass of the basic structural unit being between S00 and 9000 g / mol and that a polyamic acid chain was grafted onto position x.
  • a graft polyamide is basically known in the prior art. Reference is made to EP 0 409 115 B1 for this and to a related process for the production of such graft polyamides. Reference is expressly made to the disclosure content of this document. It is then preferred if the styrene-maleimide basic structural unit of the formula I is linked to the polyamic acid chains via imide bonds at x. The molecular weight is then very particularly preferably between 10,000 and 100,000 g / mol.
  • graft polyamide b.2. which has been obtained by hydrolytic polymerization from amino acids and / or lactams as basic building blocks, where preferably have at least 50% by weight of the polymer molecules more than one chain branch.
  • branched components with the following composition are added to the melt of the basic monomers:
  • Polymer of a monomer having a monofunctional action in a conventional polycondensation can be added.
  • the graft polyamide b) preferably differs from PA6, PA11 and / or
  • PA12 derives and has more than 3 arms.
  • the polyamide mixture A) in the case of the semi-crystalline linear polyamides a) comprises those which are selected, for example, from PA6, PA66, PA12, PA6T, PA6T12, PA12T, the terephthalic acid (T) here also being partly by isophthalic acid (I) or a-dipinic acid can be replaced or mixtures thereof.
  • the polyamide mixture A) also contains an amorphous polyamide c).
  • This is preferably selected from PA MACM12, PA PACM12 or mixtures of copolyamides thereof, and also PA6I, PA MXDI, PA6I / MXDI, where isophthalic acid (I) can be partly replaced by terephthalic acid (T) or adipic acid and MXDA partly by PXDA.
  • the amorphous polyamide is very particularly preferably selected from PA6I / 6T and / or PAMX-DI / MXDT / 6I / 6T.
  • the polyamide mixture A) is constructed in such a way that the components linear polyamide a) graft polyamide b) and amorphous polyamide c) and optionally carbon black d) together make up 100% by weight.
  • the polyamide mixture A) contains 0.5-95% by weight of the semi-crystalline linear polyamide a) and 5-99% by weight of the branched graft polyamide b) and 0.5-40% by weight of the amorphous polyamide c).
  • the graft polyamide is constructed as explained above. It is preferred if the polyamide mixture A) 0.5- Contains 80% by weight of the semi-crystalline linear polyamide a) and 15-98.5% by weight of the branched graft polyamide b) and 1-35% by weight of the amorphous polyamide c).
  • the weight ratios are very particularly preferably in the range from 1 to 64.5% by weight for the semi-crystalline linear polyamide a and 18-79.5% by weight for the branched graft polyamide b) and 20-35% by weight. for the amorphous polyamide c). In this case, 0.5-2% by weight of carbon black is then contained.
  • the molding composition contains 40 to 235 parts, preferably 40 to 150 parts, based on 100 parts of matrix component of reinforcing materials B).
  • the reinforcing materials B are selected from glass fibers, glass rovings, glass spheres, glass powder, polymer fibers, carbon fibers, metal fibers or minerals such as talc, kaolin, wollastonite, which preferably have small particle sizes, high tendency to disperse and high aspect ratios. Mixtures of these or suitable master batches can of course also be used.
  • the molding composition contains customarily known additives C).
  • additives C are e.g. stabilizers,
  • Lubricants dyes, metal filters, metallic pigments, stamped metal filters, flame retardants, impact modifiers, antistatic agents, conductivity additives, anti-fogging agents, optical brighteners, fragrances, etc.
  • the molding composition of the invention shows u. a. an improved melt flow.
  • the high reinforcement content of the molding composition according to the invention makes it possible to produce highly rigid end products.
  • conventional polymerization plants can be used for the production of polyamides and kneaders and / or single-screw extruders, which contain suitable conveying and kneading elements 25, can be used for the production of the mixtures.
  • suitable conveying and kneading elements 25 can be used for the production of the mixtures.
  • Matrix components and all additives / additives are metered into the feed zone of the extruder and the reinforcing materials are fed in and mixed via side feeders, as close as possible to the discharge nozzle.
  • melt temperatures are between 230 ° C and 300 ° C.
  • Individual additives can optionally also be used in the form of suitable masterbatch granules or as compactates.
  • molded parts, semi-finished products, extrudates or hollow body is carried out on commercially available systems, the suitable processing temperatures being between 250 ° C and 300 ° C.
  • individual components in the form of masterbatch granules or compactates can be added directly in the preprocessing machine.
  • Suitable regulators can be added in the preparation of the graft polyamides and the linear polyamides in order to maintain the viscosity in the desired range.
  • Monoamines or monocarboxylic acids are preferably used.
  • Regulators such as 4-amino-2, 2, 6, 6-tetraalkylopiperidine or 2, 6-dialkylphenols with methylamine or carboxyl group or types of regulators which are one or more of these are particularly preferred
  • Suitable amounts are 0.5 to 5 mol% based on the amount of lactam or diamine used.
  • catalytically active compounds based on phosphorus compounds such as hypophosphorous acid, phosphorous acid or phosphoric acid
  • suitable antioxidants such as sterically hindered hydroxyphenols or HALS stabilizers in amounts of 0. 05-0.5 Ge. -%.
  • suitable defoamers on silicone or silicone derivatives preferably in the form of stable aqueous emulsions with added silica in concentrations of 10 to 500 ppm, can be added to the polymerization batch.
  • Another variant consists in the addition of layered silicates such as, for example, montmorillonite, bentonite or mica, preferably with high aspect ratios, which are added directly during the extrusion of the molding composition and which can be present in the end product in an exfoliated form.
  • the polymerization or polycondensation batch can optionally contain suitable release agents and lubricants, such as, for example, fatty acid esters, waxes or fatty acid amides.
  • the measurements of the thermal data were carried out on dry granules (120 ° C / 24h) with a Perkin Elmer DSC device with heating rates of 20 ° C / min and cooling rates of 5 ° C / min.
  • the melting temperature was measured according to ISO 3146-C.
  • the crystallization temperature, enthalpy of crystallization and rate of crystallization were determined in the first cooling cycle.
  • Tg glass transition temperature
  • the sample was heated to about Tg + 20 ° C, quenched and in one second heating cycle (20 ° C / min) measured.
  • the impact and notched impact values were determined according to Charpy at 23 ° C according to ISO 179eü and ISO 179eA.
  • the heat resistance (HDT A and HDT C) were measured according to ISO 75.
  • the flow lengths were determined in a spiral form 1.5 x 10 mm at 290 ° C measuring temperature, 100 ° C mold temperature and 1000 bar.
  • the gloss measurements were determined using a Lange color measuring device (color pen) on color plates (FP) with a thickness of 3 mm.
  • Grilon A28 (from EMS-CHEMIE AG / CH) a linear, partially crystalline PA6 with a rel. viscosity
  • PA6 carbon black masterbatch (from EMS-CHEMIE AG / CH) with 25% carbon black content, for example: Black Pearl 880 (from Camot) and different additives common for polyamides. origin.
  • branched graft polyamide a branched polyamide 6 (PA6v), which is relevant for the invention, is used according to EP 0 409 115 and is produced as follows.
  • SMA 1000 oligomeric styrene-maleic anhydride copolymer, Mn ⁇ 1000 g / mol with ⁇ 7-8 maleic anhydride units
  • Atofina filled with 40909.5 g of caprolactam, 2353.5 g of tridecylamine and 18 l of water, heated to 265 ° C. until a pressure of 22 bar developed and held at this pressure for 5 hours. The mass was then cooled to 260 ° C. and let down to normal pressure for 6 h. The branched PA6 was discharged, granulated, extracted with water to remove residual caprolactam and oligomers, and dried.
  • the branched PA6 (PA6v) has the following properties in comparison to Grilon A23 (Table 1)

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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)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une nouvelle matière moulable polyamide servant à fabriquer des corps moulés en polyamide rigides et très brillants, laquelle matière moulable est composée d'un mélange de polyamides contenant un polyamide linéaire semi-cristallin, un polyamide greffé ramifié spécifique et un polyamide amorphe ainsi que des matières de renforcement et des additifs classiques.
EP03778296A 2002-11-04 2003-10-31 Matiere moulable polyamide, pieces moulees pouvant etre fabriquees a partir de cette matiere et utilisation de ladite matiere Withdrawn EP1563009A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10251294 2002-11-04
DE10251294A DE10251294B4 (de) 2002-11-04 2002-11-04 Polyamidformmasse und deren Verwendung
PCT/EP2003/012131 WO2004041937A1 (fr) 2002-11-04 2003-10-31 Matiere moulable polyamide, pieces moulees pouvant etre fabriquees a partir de cette matiere et utilisation de ladite matiere

Publications (1)

Publication Number Publication Date
EP1563009A1 true EP1563009A1 (fr) 2005-08-17

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ID=32115187

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03778296A Withdrawn EP1563009A1 (fr) 2002-11-04 2003-10-31 Matiere moulable polyamide, pieces moulees pouvant etre fabriquees a partir de cette matiere et utilisation de ladite matiere

Country Status (8)

Country Link
US (1) US20060247363A1 (fr)
EP (1) EP1563009A1 (fr)
JP (1) JP4452626B2 (fr)
KR (1) KR100938332B1 (fr)
CN (1) CN1329448C (fr)
AU (1) AU2003285310A1 (fr)
DE (1) DE10251294B4 (fr)
WO (1) WO2004041937A1 (fr)

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KR20050072131A (ko) 2005-07-08
JP4452626B2 (ja) 2010-04-21
DE10251294B4 (de) 2007-05-16
CN1329448C (zh) 2007-08-01
US20060247363A1 (en) 2006-11-02
AU2003285310A1 (en) 2004-06-07
DE10251294A1 (de) 2004-05-19
CN1708556A (zh) 2005-12-14
JP2006504833A (ja) 2006-02-09
KR100938332B1 (ko) 2010-01-22

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