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
  • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
• • 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
  • C08G18/48—Polyethers
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
  • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
• • 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G2120/00—Compositions for reaction injection moulding processes

Definitions

• the present invention relates to soft crosslinkable polyurethane compositions which have improved long-term elasticity and moldings produced therefrom. These consist of diols, polyols and at least one plasticizer which has an NCO-reactive group and is crosslinked with an at least trifunctional isocyanate.
• crosslinked or thermoplastic polyurethane compositions are known. These are crosslinked compositions based on polyols together with di- or polyisocyanates. Such polyurethanes are usually relatively hard and have only a low elasticity. It is known to incorporate plasticizers in such polyurethane compositions. The plasticizers have the task of making the hard base polymer elastic and deformable.
• thermoplastic polyurethane elastomers which describes thermoplastic polyurethane elastomers.
• the thermoplastic polyurethane is prepared from an organic diisocyanate, reacted with mixtures of polypropylene oxide with polyesters of aliphatic dicarboxylic acids with C 2 to C 6 diols and a chain-extending diol having a molecular weight of up to 400.
• inorganic fillers are contained in the composition as well as Phenolalkylsulfonklaer or Benzyl butyl.
• the corresponding uncrosslinked compositions can be used as a molding compound.
• thermoplastic polyurethane elastomers which are prepared on the basis of a polyisocyanate, a Polypropylenoxiddi- ols and diethylene glycol, wherein the molar fraction of Diethy- lenglykols 2: 1 to 20: 1 based on the polypropylene oxide.
• Such PU elastomers according to the prior art can be set very soft. They are used as a sealant only limited if they are highly viscous due to their low crosslinking and must be encapsulated. When the soft elastic composition is adjusted by plasticizers, it is a known problem that such plasticizers can migrate from the PU mass. These effects occur especially at elevated temperature and regularly lead to embrittlement of the sealant. This is mechanically only slightly resilient.
• composition for the preparation of crosslinked polyurethane elastomers consisting of a polyol component A) containing 30 to 80 wt .-% polyether and / or polyester diols, 10 to 40 wt .-% at least 3 OH-containing polyols, up to 50% by weight of at least one monofunctional compound having an isocyanate-reactive group, a crosslinker component B) containing an at least trifunctional isocyanate, characterized in that the two components have an NCO / OH ratio of 0.90 to 1, 2 and the monofunctional compound has a molecular weight below 2500.
• the invention further relates to shaped articles which can be produced from such soft PU elastomers, and to processes for their preparation.
• Suitable difunctional compounds for the composition of this invention which can be reacted with the isocyanates include linear terminal difunctional compounds having two NCO reactive groups, such as NH, OH, SH groups.
• these are polyoxyalkylene ether diols, thioether glycols, polyoxyalkylene amines or polyester diols.
• These are compounds having a molecular weight above 400 to 20,000.
• molecular weight in this invention is meant the number average molecular weight (M N ) which can be obtained by GPC measurement.
• Suitable polyether diols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule containing two active hydrogen atoms.
• alkylene oxides are preferably ethylene oxide, 1, 2-propylene oxide, 1, 2 or 2,3-butylene oxide.
• ethylene oxide, propylene oxide and mixtures thereof are suitable. They may be mixed polymers or block polymers.
• Suitable polyether diols are also the hydroxyl-containing polymerization of tetrahydrofuran.
• Suitable polyester diols can be prepared, for example, from dicarboxylic acids having 2 to 12 carbon atoms and dihydric alcohols.
• suitable dicarboxylic acids are aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid and sebacic acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid.
• the dicarboxylic acids can be used individually or as a mixture. - -
• dicarboxylic acid derivatives such as carboxylic acid diesters having 1 to 4 carbon atoms in the alcohol radical, carboxylic anhydrides or carboxylic acid chlorides, instead of the dicarboxylic acids.
• dihydric alcohols are glycols having 2 to 10 C atoms, such as ethylene glycol, diethylene glycol, butanediol-1, 4, pentanediol-1, 5, hexanediol-1, 6, decanediol-1, 10, 2,2-dimethylpropanediol-1 , 3, propanediol-1, 3 and dipropylene glycol.
• the dihydric alcohols can be used individually or mixed with one another.
• esters of carbonic acid with the diols mentioned in particular those having 4 to 6 carbon atoms, such as butanediol-1, 4 and / or hexanediol-1, 6, condensation products of ⁇ -hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid and preferably polymerization of Lactones, for example optionally substituted ⁇ -caprolactones.
• polyacetals are understood as meaning compounds obtainable from glycols, for example diethylene glycol or hexanediol or their mixture with formaldehyde. Polyacetals which can be used in the context of the invention can likewise be obtained by the polymerization of cyclic acetals.
• polyester diols are known to the person skilled in the art.
• a preferred embodiment of the composition contains at least 75% of polyether diols as the diol component.
• Another embodiment of the invention uses terminally reacted with ethylene oxide polyester or in particular polyether diols. ⁇ 0 "
• the amount of the diol component should be between 30 and 80% by weight, based on the amount of all NCO-reactive constituents of component A, in particular between 40 and 70% by weight.
• linear polyether diols having a molecular weight of 600 to 10,000 are suitable. They can be used both individually and in the form of mixtures.
• Suitable polyols which are to have at least three OH groups are, in principle, corresponding higher-functional polyols which are generally known for polyester production. It may be low molecular weight polyols having a molecular weight of less than 500 or those having a molecular weight greater than 500. Low molecular weight polyols are, for example trimethylolethane, trimethylololpropane, glycerol, 1, 2, 4-butanetriol, 1, 2,6-hexanetriol, pentaerythritol or sugar-based polyols such as sorbitol.
• liquid polyesters which are obtained by condensation of di- or tricarboxylic acids, such as, for example, Adipic acid, sebacic acid, glutaric acid, azelaic acid, hexahydrophthalic acid or phthalic acid can be prepared with low molecular weight diols or proportions of triols.
• diols or triols can be used. Possibly.
• these polyesters can be reacted at the terminal OH groups with glycols.
• polyhydroxy-polyethers having a molecular weight of 400 to 15,000, preferably 600 to 10,000, having 3 to 10 OH groups per molecule.
• Such polyhydroxypolyethers are obtained in a conventional manner by alkoxylation of suitable starter molecules, for.
• suitable starter molecules for.
• Suitable alkoxylating agents are in particular propylene oxide and ethylene oxide, which can lead to random or block copolymers.
• the polyols are used in amounts of from 10 to 40% by weight, based on the amount of all NCO-reactive constituents of component A, in particular of 12 -O-
• the diols and polyols of the composition according to the invention have terminal OH groups.
• Suitable at least trifunctional polyisocyanates of component B for the preparation of the composition according to the invention are the organic polyisocyanates known per se. Suitable examples include aliphatic, cycloaliphatic, arylaliphatic and aromatic polyfunctional isocyanates.
• aliphatic diisocyanates such as ethylene, 1, 4-tetramethylene, 1, 6-hexamethylene and 1, 12-dodecane diisocyanate
• cycloaliphatic diisocyanates such as cyclohexane-1, 3- and -1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane, 2,4- and 2,6-hexahydrotoluylene diisocyanate, 4,4'- and 2,4'-diisocyanato-dicyclohexylmethane
• aromatic diisocyanates such as 1, 3- and 1, 4-phenyl diisocyanate, 2,4- and 2,6-tolylene diisocyanate, 2,2'- and 2, 4 'and 4,4'-diphenylmethane diisocyanate and naphthalene -1, 5-diisocyanate
• Aromatic diisocyanates such as ethylene
• Suitable as at least trifunctional isocyanates are polyisocyanates obtained by trimerization or oligomerization of diisocyanates or by reaction of the above-mentioned diisocyanates with low molecular weight polyfunctional hydroxyl- or amino-containing compounds, such as trimethylolpropane or glycerol.
• polyisocyanates or poly-isocyanate mixtures having an allophanate structure based on HDI, IPDI 1 2,4- or 4,4-MDI, TMXDI and / or 2,4 '- or 4,4' -Diisocyanatodi-cyclohexyl-methane, wherein as isocyanates HDI, MDI, TDI or IPDI are particularly preferred.
• suitable polyisocyanates are also commercially available or can be prepared by methods known to those skilled in the art.
• aliphatic isocyanates in particular polyisocyanates having an average functionality of from 3 to 5. Addition of proportions of higher-functional isocyanates gives rise to more crosslinked PU elastomers.
• the PU elastomer which can be prepared according to the invention must contain at least one monofunctional compound which has only one isocyanate-reactive group in the molecule. This ingredient generally acts as an internal plasticizer. These compounds are usually liquid at 25 ° C.
• H-acid groups can be used, such as OH groups, NH groups, SH groups, COOH groups. These may be secondary or primary OH groups, primary or secondary amino groups, carboxylic acid or carboxylic acid amide groups. Particular preference is given to primary or secondary OH groups or secondary amino groups as the NCO-reactive group.
• the monofunctional compounds which are suitable according to the invention can be synthesized on a different polymeric basis. However, it is necessary that these compounds be compatible with the PU polymer.
• suitable monofunctional plasticizers are monofunctional polyethers based on ethylene oxide, propylene oxide, butylene oxide; Polythioether compounds having a terminal SH group; Polyalkylene oxides based on C 2 to C 4 diols which have a terminal primary or secondary amino group; hydroxyalkyl kylphenyltagenen having a primary or secondary OH group in the alkyl group; Polyalkylene oxide modified phenol derivatives; hydroxy-functionalized alkylbenzyl esters, hydroxy-functional alkylsulfonic acid esters having a primary or secondary OH group; N-alkyl-substituted benzoic acid amides or benzenesulfonamides having a primary or secondary OH group in the alkyl radical; Alkylarylsulfonic esters or sulfonamides
• the molecular weight of the monofunctional compound should be below 2500, preferably below 1000.
• they are alkyl-substituted aromatic sulfonic acid alkyl esters or N-alkyl-substituted aromatic sulfonic acid amides which contain a secondary or primary OH group in the alkyl substituent.
• the alkyl radical should have up to 10 C atoms, in particular up to 6 C atoms. It can be linear or branched. Particular preference is given to compounds which carry a secondary OH group on the alkyl radical.
• the reactive compound should be used in an amount of 1 to 50 wt .-% based on the amount of all NCO-reactive components of component A, in particular between 5 and 35 wt .-%.
• the components A and B are reacted in amounts such that the ratio of NCO groups to the sum of the NCO-reactive groups, in particular the OH groups, 0.9: 1 to 1, 2: 1, preferably 0.95: 1 to 1, 1: 1.
• polyurethane catalysts may be present in the reaction mixture. Suitable are basic polyurethane catalysts, in - ⁇ -
• tertiary amines such as dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N 1 , N 1 -tetramethyldiamino-diethyl ether, bis (dimethylaminopropyl) urea, N-methyl- or N-ethylmorpholine, dimethylpiperazine, Py - ridine, 1, 2-dimethylimidazole, 1-azobicyclo- (3,3,0) -octane, dimethylaminoethanol, 2- (N, N-dimethylaminoethoxy) ethanol, N, N ', N "-tris- (dialkylaminoalkyl) -
• metal salts such as iron (II) chloride, zinc chloride, lead octoate and preferably tin salts, such as tin dioctoate, dibutyltin dilaurate, tin oxides
• catalyst based on tertiary amines and / or from 0.01 to 0.5% by weight, preferably from 0.05 to 0, are used.
• additives may be included in the reaction mixture to vary certain properties, such as color, hardness, hydrophobicity, processing properties. These may be, for example, dyes, fillers or pigments, such as titanium dioxide, talc, barium sulfate, calcium carbonate, carbon black, silicic acids, phyllosilicates, filler fibers and the like.
• the compositions of the invention may contain additives such. As thixotropic agents, adhesion promoters, release agents or stabilizers. Stabilizers include, for example, antioxidants or sunscreens.
• the additives should be chosen so that they do not migrate or evaporate from the crosslinked PU elastomer. Volatile compounds, such as solvents, should not be included.
• the additives or additives may be present in the composition according to the invention up to 10% by weight, preferably up to 5% by weight, in particular up to 2% by weight.
• plasticizers examples include medicinal white oils, naphthenic see mineral oils, paraffinic hydrocarbon oils, terminally reacted polypropylene glycols and polybutylene glycols, liquid polyesters and glycerol esters or softeners based on aromatic dicarboxylic acid esters.
• These plasticizers should be compatible with the polymer. They should have a high boiling point and should not migrate from the PU elastomer. In general, the amount of such non-reactive plasticizers is below 15% by weight, based on the total composition, in particular below 5% by weight, or the compositions according to the invention are free from such plasticizers. Solvents should preferably not be present in the composition according to the invention.
• component A comprises those components which can react with NCO groups, in particular the diol component, the triol component, the monofunctional NCO-reactive component.
• these ingredients can be mixed by known methods. It may be a mixture which is liquid at room temperature or it becomes liquid at elevated temperatures up to 100 ° C. If appropriate, individual or all additives can also be added to this mixture, for example catalyst, pigments, stabilizers or adhesion promoters.
• the mixing of the individual components can be carried out on known aggregates. For example, it is possible to liquid components by intensive mixing in high-speed stirring units, eg. As dissolvers to homogenize. If solid components are to be added, these can also be dispersed. Possibly. such components can also be ground. If this mixture is highly viscous or solid at room temperature, the viscosity can be reduced by heating.
• the starting materials used should in particular contain no water.
• the crosslinker constituents ie the polyisocyanates
• the crosslinker constituents should preferably be present.
• These can also be mixed with Additven, as far as it is ensured that these additives do not react with the isocyanate groups.
• Additven may be solid or preferably liquid mixtures.
• a homogeneous mixture is produced after a mixing ratio predetermined by the NCO / OH ratio. This can be done for example by the above-mentioned mixing units. But it is sufficient if the mixing is carried out directly after the metering units by static mixer or dynamic mixing equipment. This mixture is then introduced into known injection molding machines in a suitable form and preferably cured at elevated temperature. Another procedure for preparing the PU elastomers according to the invention can be done so that the two individual liquid components are mixed together during injection into the mold when the viscosity is sufficiently low at the processing temperature.
• the OH and NCO components are reactive with each other even at room temperature.
• catalysts are usually added and an elevated temperature can be used to accelerate crosslinking.
• the polyurethane elastomer according to the invention is characterized by a high flexibility. It is permanently elastic and this elasticity remains even after prolonged storage.
• the covalently bonded plasticizer avoids that plasticizer components can migrate out of the polymer during prolonged exposure and at elevated temperatures. Likewise, the use of health-endangering plasticizers, in particular phthalate esters can be dispensed with.
• the Shore hardness of the composition according to the invention should be between 90 and 5 Shore 00 or 90 to 40 Shore 000 (measured according to DIN ASTM D 2240). Preferably, the hardness should be between 10 and 50 Shore 00.
• the elongation at break of the PU elastomers according to the invention is high. It is usually above 100%, preferably above 200%, in particular above 400% (measured according to DIN 53504). Even after 4 weeks of processing at elevated temperature up to 90 C C only a slight change is observed of Sho re hardness.
• the glass transition temperature (Tg) (determined with DSC) of the crosslinked polymers is generally below -20 0 C, preferably below -40 ° C. Due to the reduced migration of plasticizer components, the Tg is constant even after prolonged storage.
• the invention furthermore relates to moldings of the polyurethane elastomers according to the invention.
• the PU elastomers according to the invention are soft elastic crosslinked polymers. Molded articles can be produced from these polymers. It may be individual moldings or they are incorporated, for example, as a molded body directly to other moldings made of plastic or metal. The production of the moldings can be carried out by known methods, for example by injection molding.
• Moldings of the PU elastomers or moldings according to the invention in conjunction with metallic moldings or plastic moldings can be used, for example, as a seal.
• such elastomers are produced as a seal in a ring or sleeve shape, or such shaped bodies can be incorporated directly into other sealing components.
• inserts into the injection mold and to connect them during curing directly with a PU elastomer of the invention to the molding In a production method according to the invention, insert parts made of metal or plastic are optionally inserted into an injection mold. This is closed and then injected into the cavity an unreacted mixture of the individual components. By heating, possibly under pressure, the molding can be crosslinked and this is then removed from the mold.
• the PU elastomers according to the invention form a shaped body. These shaped bodies can have a tack-free surface. But it is also possible - IO ⁇
• a surface tackiness can facilitate positioning of the molded articles and possibly influences the sealing properties.
• the shaped body can be deformed and elastically adapted to the contours of the parts to be sealed.
• Due to the permanently elastic properties, a seal can be repeatedly opened and closed even after storage while retaining its sealing properties.
• Another advantage of the composition of the invention is a high thermal stability, which does not allow migration of the plasticizer even after prolonged or cyclic temperature stress and the elastic, soft properties are retained.
• the elastic PU polymers according to the invention can also be used, for example, as substitute material for silicone.
• the permanently elastic properties are particularly important under elevated temperature load for many applications.
• silicone materials that are subject to thermal stress be replaced from corresponding moldings of the PU polymer of the invention. Examples of such fields of application are the automotive industry or engine construction. Possibly.
• elastic seals can be made from such PU elastomers. Reducing migration or evaporation of plasticizer ensures a long-lasting performance spectrum.
• the mixture is sprayed immediately after manufacture in a mold and cured at about 8O 0 C.
• the result is an elastic, slightly sticky shaped body.
• the elongation at break is determined several times. It is above 800% (measured according to DIN 53504).
• the hardness is measured as Shore 00 hardness. It is about 50 (measured according to ASTM D 2240).
• the elongation at break and Shore hardness are determined again.
• the elongation at break is over 900%, the Shore 00 hardness at a value of 50 - 55.
• the mixture is sprayed immediately after manufacture in a mold and cured at about 8O 0 C.
• the result is an elastic, slightly sticky shaped body.
• the hardness Shore 00 hardness 85.
• the Shore 00 Hardness is 85.
• the mixture is injected into a mold immediately after production and crosslinked at about 100 ° C.
• the result is an elastic, slightly sticky shaped body.
• the elongation at break is determined several times. It is above 800%.
• the Shore 00 hardness is 35.
• 17.6 parts (by weight) of a trifunctional polyether polyol (molecular weight about 4300) having primary hydroxyl end groups are mixed with 41.2 parts of a polyether diol (molecular weight about 4000) based on polypropylene glycol. There are added 0.5 parts of a commercial stabilizer (Irganox 1135, Ciba) and 0.05 parts of DBTL. The mixture is additionally mixed homogeneously with 17.6 parts of an N-hydroxyalkyl-substituted benzenesulfonic acid amide. - -
• the mixture is injected into a mold immediately after production and crosslinked at about 80 ° C.
• the result is an elastic, slightly sticky shaped body.
• the elongation at break is above 800%.
• the Shore 00 hardness is one
• the mixture is injected into a mold immediately after production and crosslinked at about 80 ° C.
• the result is an elastic, slightly sticky shaped body.
• the elongation at break is about 500%.
• the Shore 00 Hardness is around 65.

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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)
• Polyurethanes Or Polyureas (AREA)
• Injection Moulding Of Plastics Or The Like (AREA)

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• 2006
  • 2006-03-20 DE DE102006013103A patent/DE102006013103A1/de not_active Ceased
• 2007
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  • 2007-02-08 CA CA002646681A patent/CA2646681A1/en not_active Abandoned
  • 2007-02-08 WO PCT/EP2007/001058 patent/WO2007107210A1/de not_active Ceased
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