EP1606335A1 - Copolymeres sequences organopolysiloxane / polyuree / polyurethane - Google Patents

Copolymeres sequences organopolysiloxane / polyuree / polyurethane

Info

Publication number
EP1606335A1
EP1606335A1 EP04719405A EP04719405A EP1606335A1 EP 1606335 A1 EP1606335 A1 EP 1606335A1 EP 04719405 A EP04719405 A EP 04719405A EP 04719405 A EP04719405 A EP 04719405A EP 1606335 A1 EP1606335 A1 EP 1606335A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
general formula
organopolysiloxane
polyurea
block copolymers
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Withdrawn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
EP04719405A
Other languages
German (de)
English (en)
Inventor
Oliver SCHÄFER
Franz Csellich
Sabine Delica
Andrea Kneissl
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.)
Consortium fuer Elektrochemische Industrie GmbH
Original Assignee
Consortium fuer Elektrochemische Industrie GmbH
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 Consortium fuer Elektrochemische Industrie GmbH filed Critical Consortium fuer Elektrochemische Industrie GmbH
Publication of EP1606335A1 publication Critical patent/EP1606335A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

  • the invention relates to a first object.
  • polyurethanes and silicone elastomers are complementary in a wide range.
  • Polyurethanes are characterized by their excellent mechanical strength, elasticity and very good adhesion, abrasion resistance and simple processing by extrusion from the melt.
  • Silicone elastomers on the other hand, have excellent temperature, UV and weathering stability. They maintain their elastic properties at lower temperatures and therefore do not tend to become brittle. In addition, they have special water-repellent and non-stick surface properties.
  • the combination of urethane and silicone polymers should make materials with good mechanical properties accessible, which at the same time are characterized by greatly simplified processing options compared to silicones, but still have the positive properties of silicones.
  • the combination of the advantages of both systems can lead to compounds with low glass transition temperatures, low surface energies, improved thermal and photochemical stabilities, low water absorption and physiologically inert materials. Sufficient tolerances could only be achieved by producing simple polymer blends in a few special cases. Only with the production of. Described in I. Yilgör, Polymer, 1984 (25), 1800 and in EP-A-250248
  • Polydiorganosiloxane-urea block copolymers have achieved this goal.
  • the polymer building blocks are ultimately implemented using a comparatively simple polyaddition, such as is used for the production of polyurethanes.
  • aminopropyl-terminated polysiloxanes were used as starting materials for the siloxane-urea copolymers as siloxane building blocks. These formed the soft segments in the copolymers, analogous to the polyethers in pure polyurethane systems.
  • Common diisocyanates were used as hard segments, these also being added by adding diamines, e.g. 1, 6-diaminohexane or dihydroxy compounds such as e.g. Butanediol can be modified to achieve higher strengths.
  • the reaction of the amino compounds with isocyanates takes place spontaneously and generally does not require a catalyst.
  • the silicone and isocyanate polymer building blocks can be mixed in a wide range without problems.
  • the mechanical properties are determined by the ratio of the different polymer blocks silicone soft segments and urea hard segments and essentially by the diisocyanate used.
  • the strong interactions of the hydrogen bonds between the urea units result in thermoplastic materials.
  • the production can be carried out batchwise in solution, but also continuously, e.g. described in European patent EP 0 822 951.
  • the equilibration reaction described in EP 0 250 248 is a very lengthy reaction which also requires the use of a very expensive starting material such as bisa inopropyltetramethyldisiloxane and special catalysts which have to be synthesized separately. This is not economically feasible. Furthermore, relatively large amounts of preferably between 500 and 1000 ppm of catalyst are used in the equilibration reaction. The catalyst is thermally deactivated at the end of the equilibration reaction, which leads to degradation products and thus impurities in the end product, which have an impact on the thermal stability of the materials produced in this way. During the thermal
  • the silicone oils produced in this way tend to take on a clearly visible discoloration in the form of a yellow tinge.
  • These degradation products are also responsible for a strong inherent smell of the materials synthesized from them. This smell is clearly noticeable and also leads to irritation for the user or processor of these materials.
  • the materials produced according to EP 0 822 951 generally have softening ranges above 100 ° C, which when used as e.g. Hot melt adhesive or matrix material for moisture-crosslinking siloxane masses would require application temperatures of well over 120 ° C, which in some cases with common hot melt metering systems. cannot be reached, or is too warm for plastic parts to be bonded, since these then begin to melt themselves.
  • organopolysiloxane / polyurea / polyurethane block copolymer which show a significantly reduced yellow tinge and do not evaporate any irritating substances. Furthermore, they should still soften below 100 ° C and thus a processing temperature below 1D0 ° r. anfwpiqpn.
  • the task was surprisingly achieved by using bisaminomethyl-terminated siloxanes as starting materials for the preparation of the copolymers, which are accessible in very good purity without the addition of catalysts.
  • R is a monovalent hydrocarbon radical or hydrocarbon oxy radical, optionally substituted by fluorine or chlorine, or having 1 to 20 carbon atoms
  • R 2 is a monovalent hydrocarbon radical, optionally substituted by fluorine or chlorine, having 1 to 20
  • R 4 is a monovalent hydrocarbon radical with 1 to 20, optionally substituted by fluorine or chlorine
  • Z is an oxygen atom or an amino group -NR'-
  • R ' is hydrogen or an alkyl radical having 1 to 10 carbon atoms
  • Y is a divalent hydrocarbon radical with 1 to 20, optionally substituted by fluorine or chlorine
  • D an alkylene radical which is optionally substituted by fluorine, chlorine, C 1 -C 6 -alkyl or C 1 -C 6 alkyl ester and has from 1 to 700
  • B is a functional or non-functional organic or organosilicon radical
  • n is a number from 1 to 4000
  • a is a number of at least 1
  • b is a number from 0 to 40
  • c is a number from 0 to 30
  • d is a number greater than 0.
  • R is preferably a monovalent, hydrocarbon radical or a hydrocarbon oxy radical having 1 to 6 carbon atoms, in particular unsubstituted.
  • Particularly preferred radicals R are methyl, ethyl, vinyl, phenyl, methoxy and ethoxy radicals.
  • R 2 and R 4 preferably denote a monovalent
  • Hydrocarbon radical with 1 to 6 carbon atoms in particular unsubstituted or hydrogen.
  • Particularly preferred radicals R 2 and R 4 are hydrogen.
  • Z is preferably an oxygen atom or an NH group.
  • D is preferably an alkylene radical having at least 2, in particular at least 4, carbon atoms and at most 12 carbon atoms. D is furthermore preferably a polyoxyalkylene radical, in particular polyoxyethylene radical or
  • the radical D is preferably not substituted.
  • n preferably denotes a number of at least 3, in particular at least 25 and preferably at most 800, in particular at most 400, particularly preferably at most 250.
  • A is preferably a number of at most 100.
  • b preferably means a number of at most 50 in.qhp.Rnnrlprp c preferably means a number of at most 10, in particular at most 5.
  • the polydiorganosiloxane-urea copolymer of the general formula (1) shows good mechanical properties with good processing properties.
  • the invention further relates to a process for the preparation of organopolysiloxane / polyurea / polyurethane block copolymers of the general formula (1)
  • R, R2, R3, R4, Z, R ', Y, D, B, n, a, b, c and d have the meaning given above and
  • R 3 is a monovalent hydrocarbon radical with 1 to 20 carbon atoms or hydrogen, optionally substituted by fluorine or chlorine.
  • R 3 is preferably a monovalent, hydrocarbon radical having 1 to 6 carbon atoms, in particular unsubstituted. Particularly preferred radicals R 3 are methyl, ethyl or isopropyl groups.
  • the preparation of the bisaminomethylpolydiorganosiloxane of the general formula (4) is inexpensive, proceeds under mild reaction conditions and leads to products which are colorless and odorless.
  • the resulting by-product is an alcohol and can remain in the product, but is preferably removed, for example, by treating the product under reduced pressure on a thin layer.
  • the content of cyclic silicone compounds in the bisaminomethylpolydiorganosiloxane of the general formula (4) is particularly low, since these have already been removed at the stage of the silanol-terminated starting materials of the general formula (3).
  • the Bisaminomethylpolydiorganosiloxane of the general formula (4) furthermore contains neither equilibration catalysts or their residues, since the reaction of silanol groups with the aminosilane of the general formula (2) takes place in a very short time without catalysis.
  • These functionalized silicone oils and their secondary products are therefore odorless and colorless.
  • the polymerization products contain a particularly low proportion of cyclic siloxane compounds due to the reaction with polyisocyanates. A content below 2% by weight is preferred and a content of ⁇ 0.5% by weight is particularly preferred.
  • the silanes of the general formula (2) and the educts containing silanol groups are used in equimolar ratios, since the
  • the content of active hydrogen in the starting material terminated with silanol is preferably determined, for example by titration or spectroscopy, so that an at least equimolar amount of silane can be added.
  • a small amount of remaining silanol groups of up to 5 mol% in the synthesized aminosilicones can still be tolerated for further use.
  • materials with Si-OH contents of less than 1 mol% are preferably used.
  • Bisaminomethyl-terminated siloxanes of the general formula (4) are obtained in high purity, which are outstandingly suitable for the production of high-molecular siloxane-urea block copolymers.
  • a small excess of the silane of the general formula (2) is preferably used, which is then carried out in a simple additional process step, for example by adding small amounts of water or by distillation can be removed.
  • This reaction can be carried out either at room temperature or with heating.
  • chain extenders such as dihydroxy compounds or water in addition to the urea groups, a further improvement in the mechanical properties can be achieved. In this way, materials can be obtained that are mechanically comparable to conventional silicone rubbers, but have increased transparency and in which no additional active filler has to be incorporated.
  • the chain extenders preferably have the general formula (6)
  • diisocyanates of the general formula (5) to be used are aliphatic compounds such as isophorone diisocyanate, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyanate and methylene dicyclohexy-4, 4 - diisocyanate or aromatic compounds such as methylene diphenyl 4,4 ⁇ - diisocyanate, 2, 4-toluene diisocyanate, 2, 5-toluene diisocyanate, 2, 6-toluene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, m-xylene diisocyanate, tetramethyl-m-xylene diisocyanate or mixtures of these isocyanates.
  • aliphatic compounds such as isophorone diisocyanate, hexamethylene-1, 6-diisocyanate, tetramethylene-1, 4-diisocyan
  • alkylenes of the general formula (6) are preferably polyalkylenes or polyoxyalkylenes. These are preferably largely free of contamination from mono-, tri- or higher-functional polyoxyalkylenes.
  • Polyester polyols, polycaprolactone diols but also ⁇ , ⁇ -OH-terminated polyalkylenes based on polyvinyl acetate, polyvinyl acetate ethylene copolymers, polyvinyl chloride copolymer, polyisobutyl diols can be used.
  • Polyoxyalkyls are preferably used, particularly preferred
  • Polypropylene glycols Such compounds are commercially available as base materials, inter alia, for flexible polyurethane foams and for coating applications with molecular weights Mn of up to over 10,000. Examples include the BAYCOLL® polyether polyols and polyester polyols from Bayer AG, Germany or the Acclaim® polyether polyols from Lyondell Inc., USA. Monomeric ⁇ , ⁇ -alkylene diols, such as ethylene glycol, propanediol, butanediol or hexanediol, can also be used. Furthermore, dihydroxy compounds in the context of the invention are likewise to be understood as bishydroxyalkyl silicones, such as those e.g. by the company Goldschmidt under the name Tegomer H-Si 2111, 2311 and 2711.
  • copolymers of the general formula (1) described above can be prepared both in solution and in
  • Solid substance continuously or discontinuously. It is essential that the selected polymer mixture is mixed optimally and homogeneously under the reaction conditions and that phase incompatibility is prevented, if necessary, by solubilizers.
  • the production depends on the solvent used. If the proportion of hard segments such as urethane or urea units is large, then a solvent with a high solubility parameter such as dimethylacetamide may have to be selected. THF has proven to be sufficiently suitable for most syntheses. All components are preferably dissolved in an inert solvent. Synthesis without solvent is particularly preferred.
  • the homogenization of the mixture is of crucial importance during the reaction.
  • the polymerization can also be controlled by the choice of the reaction sequence in a step synthesis.
  • heated reactors such as e.g. Extruder used. It should be noted that the oxygen content in the reaction mixture to be extruded or its components is as low as possible in order to avoid possible yellowing of the polymer.
  • Reproducibility generally takes place with the exclusion of moisture and under protective gas, usually nitrogen or argon.
  • the reaction is preferably carried out, as is customary in the production of polyurethanes, by adding a catalyst.
  • Suitable catalysts for the preparation are dialkyltin compounds, such as dibutyltin dilaurate, dibutyltin diacetate, or tertiary amines such as N, N-dimethylcyclohexanamine, 2-dimethylaminoethanol, 4-dimethylaminopyridine.
  • Preferred applications of the polydiorganosiloxane-urea copolymers of the general formula (1) are uses as a component in adhesives and sealants, as a base material for thermoplastic elastomers such as, for example, cable coverings, hoses, seals, keyboard mats, for membranes, such as selectively gas-permeable membranes, as additives in Polymer blends, or for coating applications, for example in non-stick coatings, tissue-compatible coatings, flame-retardant coatings and as biocompatible materials.
  • Other possible applications are sealants, additives for polymer processing. anti-foulin ⁇ Coatings, cosmetics, personal care products, paint additives, auxiliary agents in detergents and textile processing, for modifying resins or for modifying bitumen.
  • thermoplastic materials in sealants, adhesives, as a material for fibers, as a plastic additive, e.g. as an impact improver or flame retardant, as a material for defoamer formulations, as a high-performance polymer (thermoplastic, thermoplastic elastomer, elastomer), as packaging material for electronic components , in insulation or shielding materials, in cable sheaths, in antifouling materials, as an additive for cleaning, cleaning or care products, as an additive for personal care products, as a coating material for wood, paper and cardboard, as a mold release agent, as a biocompatible material in medical applications such as contact lenses, as a coating material for textile fibers or textile fabrics, as a coating material for natural materials such as leather and furs, as a material for membranes and as a material for photoactive systems, for example for lithographic processes, optical data backup or optical data transmission.
  • thermoplastic thermoplastic elastomer, elastomer
  • packaging material for electronic components in insulation or shielding materials, in cable
  • Example 1 1500 g of bishydroxy-terminated polydimethylsiloxane with a molecular weight of 3150 g / mol were placed in a 2000 ml flask with a dropping funnel and reflux condenser. Then 116 q aminomethvldimethvlmethoxvsilan were at room temperature added dropwise and then left to stand for 2 hours. The methanol by-product was then removed in vacuo. This gave a bisaminomethyl-terminated polydimethylsiloxane with a molecular weight of 3280 g / mol, which according to 9 Si-NMR was free of Si-OH groups.
  • Example 3 40 g of bisaminomethyl-terminated PDMS (Example 1, molecular weight 3280 g / mol) in a solvent mixture of 80 ml of dry THF and 20 ml of dimethylacetamide were placed in a 250 ml flask with a dropping funnel and reflux condenser. A solution of 2.33 g of methylene di-p-phenyldiisocyanate in 20 ml of dry THF was then added dropwise at room temperature and the mixture was then boiled under reflux for 1 hour. After the solution had cooled, the polymer was precipitated by dropping it into hexane. A was obtained which showed a softening range at 144 ° C. in the TMA.
  • Example 3 a bisaminomethyl-terminated PDMS with a molecular weight of 3280 g / mol (analogously to Example 1) or 11000 g / mol (analogously to Example 2) was used with the diisocyanates isophorone diisocyanate (IPDI), hexamethylene-1,6-diisocyanate
  • HMDI tetramethylene-1,4-diisocyanate
  • TDI tetramethylene-1,4-diisocyanate
  • TXDI tetramethyl-m-xylene diisocyanate
  • H12MDI methylene-bis- (4-isocvanatocvclohexane
  • Nitrogen atmosphere metered the diisocyanate in the first heating zone and the aminomethyl-terminated silicone oil with a molecular weight of 3280 g / mol from Example 1 in the second heating zone.
  • the temperature profile of the heating zones was programmed as follows: Zone 1 45 ° C, Zone 2 100 ° C, Zone 3 150 ° C, Zone 4 140 ° C, Zone 5 140 ° C, Zone 6 130 ° C. The speed was 50 rpm.
  • the diisocyanate methylene bis (4-isocyanatocyclohexane)
  • Example 17 32 g of bisaminomethyl-terminated PDMS with a molecular weight of 3280 g / mol and 0.9 g of butanediol in a solvent mixture of 80 ml of dry THF and 20 ml of dimethylacetamide were placed in a 250 ml flask with a dropping funnel and reflux condenser. After adding 3 drops of dibutyltin dilaurate, a solution of 4.5 g of isophorone diisocyanate (IPDI) in 20 ml of dry THF was added dropwise at room temperature and then boiled under reflux for 2 hours. After the solution had cooled, the polymer was precipitated by dropping it into hexane. A copolymer with a molecular weight of 63000 g / mol was obtained.
  • IPDI isophorone diisocyanate
  • methylene-bis (4-isocyanatocyclohexane (H12MDI) was heated in a nitrogen atmosphere in the first heating zone and an aminopropyl-terminated silicone oil (produced by equilibration according to EP 0 250 248, molecular weight 3250 g / mol)
  • the temperature profile of the heating zones was programmed as follows: Zone 1 30 ° C, Zone 2 100 ° C, Zone 3 150 ° C, Zone 4 180 ° C, Zone 5 170 ° C, Zone 6 140 ° C.
  • the speed was 50 rpm, the diisocyanate was metered in zone 1 at 304 mg / min and the amine oil (3250 g / mol) was metered in zone 2 at 3.5 g / min
  • a polydimethylsiloxane-polyurea block copolymer with a softening temperature of 133 ° C. could be removed from the extruder.
  • the materials based on the aminomethyl-terminated PDMS have lower softening ranges, a lower 100% modulus, lower Shore A hardness, lower intrinsic color and a lower intrinsic odor.

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Cosmetics (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Silicon Polymers (AREA)

Abstract

L'invention concerne des copolymères séquencés organopolysiloxane / polyurée / polyuréthane de formule générale B-{[NR<4>-CR<2>2-SiR2-(O-SiR2)n-CR<2>2-NR<4>-CO-NH-Y-NH-CO]a-[Z-D-Z-CO-NH-Y-NH-CO]b-[NR<4>-CR<2>2-SiR2-(O-SiR2)n-CR<2>2-NR<4>-CO-NH-Y-NH-CO-NH-Y-NH-CO]c}d-B (1), obtenus par réaction de polydiméthylsiloxanes à terminaison aminométhyle avec des diisocyanates et, éventuellement, des allongeurs de chaîne. L'invention concerne également un procédé pour leur production, ainsi que leur utilisation.
EP04719405A 2003-03-27 2004-03-11 Copolymeres sequences organopolysiloxane / polyuree / polyurethane Withdrawn EP1606335A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10313936 2003-03-27
DE2003113936 DE10313936A1 (de) 2003-03-27 2003-03-27 Organopolysiloxan/Polyharnstoff/Polyurethan-Blockcopolymere
PCT/EP2004/002532 WO2004085516A1 (fr) 2003-03-27 2004-03-11 Copolymeres sequences organopolysiloxane / polyuree / polyurethane

Publications (1)

Publication Number Publication Date
EP1606335A1 true EP1606335A1 (fr) 2005-12-21

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Application Number Title Priority Date Filing Date
EP04719405A Withdrawn EP1606335A1 (fr) 2003-03-27 2004-03-11 Copolymeres sequences organopolysiloxane / polyuree / polyurethane

Country Status (6)

Country Link
US (1) US20060036055A1 (fr)
EP (1) EP1606335A1 (fr)
JP (1) JP2006521420A (fr)
CN (1) CN1764685A (fr)
DE (1) DE10313936A1 (fr)
WO (1) WO2004085516A1 (fr)

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CN1764685A (zh) 2006-04-26

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