Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
  • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D1/00—Treatment of filament-forming or like material
  • D01D1/06—Feeding liquid to the spinning head
  • D01D1/065—Addition and mixing of substances to the spinning solution or to the melt; Homogenising
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/16—Synthetic fibres, other than mineral fibres
  • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M2101/38—Polyurethanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/30—Flame or heat resistance, fire retardancy properties
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
  • D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
• • D—TEXTILES; PAPER
  • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
  • D10B2401/00—Physical properties
  • D10B2401/04—Heat-responsive characteristics

Definitions

• the invention relates to elastic polyurethane fibers, in particular polyurethane urea fibers, the have no discoloration due to required process steps for the production of textiles and in aqueous, chlorine-containing environments, such as swimming pools, for swimwear can be used.
• the invention relates to elastic polyurethane urea fibers, the coated hydrotalcites included.
• Elastic polyurethane fibers can be analogous to Polyurethane urea fibers are built. The main difference is that for the polymerization instead of Amine Diols.
• Yarns from the aforementioned fibers are made with hard fibers such as polyamide or polyester or other fibers such as cotton or viscose Manufacture of knitted fabrics used in their own right for textiles, including for Corsetry, stockings and sportswear, e.g. Swimsuits or swimwear, are suitable.
• thermal treatment in textile production is therefore particularly required for the production of textiles with light shade, as well in the manufacture of textiles having a high content of polyurethane urea fibers, e.g. greater as 10% by weight. At the same time a good resistance of the fiber material to one through Be assured of chlorine-induced degradation.
• polyesters As swimwear produced low molecular weight mono-, di- or polyhydroxy-functional polymer. aliphatic However, polyesters show a high biological activity. That's why they have this Polymer-made polyurethane ureas have the disadvantage of being easily removed by microbes and fungi be reduced. Furthermore, it has been shown that the chlorine water resistance of Polyurethanhamstoffen based on polyesters is not satisfactory.
• JP 59-133 248 is to improve the chlorine water resistance the Incorporation of hydrotalcite into filaments of segmented polyurethane ureas.
• hydrotalcite in polar solvents such as dimethylacetamide or dimethylformamide and even in spinning solutions strongly agglomerated for polyurethane urea fibers.
• EP-A-843 029 is a polyurethaneurea composition and specifically described from polyurethane urea elastic fibers, with polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane coated Hydrotalcites and / or other basic metal-aluminum-hydroxy compounds.
• disadvantage This composition is that in the polyurethaneurea fibers described in a continuous spinning process over a longer period of time disturbances in the spinning process possible are and after a few days spinning time, the thread when winding on the bobbin demolish can start.
• Another disadvantage of this composition is that even from this Polyurethaneurea composition produced filaments in the further processing to a Textile, due to a heat-setting or a molding process, ie a thermal Treatment, can lead to an unwanted color change.
• EP 1 200 518-A1 is a polyurethaneurea composition and specifically resulting Polyhamstoffmaschinen described as an additive hydrotalcite and a Contain dialkylsulfosuccinate, which increases the strength of the fiber.
• EP 1 200 518-A1 shows even with this polyurethaneurea composition and filaments made from it, that it during further processing into a textile, due to a heat-setting or a molding process, So a thermal treatment, come to an undesirable color change can.
• the invention is based on the object, a polyurethaneurea composition in particular to provide for polyurethane urea fibers (also called elastane fibers) opposite the prior art, no unwanted discoloration due to thermal stress of Polyurethane urea fibers, such as those during heat-setting or molding in the process chain for the production of knitted fabrics or fabrics or textiles may occur, and a has good chlorine water resistance.
• the object is achieved in that the polyurethane urea fibers an effective Amount of finely divided, with dialkyl sulfosuccinate coated hydrotalcites is added.
• the amount of dialkylsulfosuccinate-coated hydrotalcite incorporated into the polyurethaneurea is finely divided fibers is 0.30 wt .-% to 10 wt .-%, preferably 0.5 wt .-% to 8 wt .-%, particularly preferably 1.5 wt .-% to 7 wt .-% and most preferably 2 wt .-% to 6 wt .-%, based on the weight of the polyurethane urea fiber.
• the amount of hydrotalcite is distributed within the elastane fibers and / or on the fiber surface.
• hydrotalcites are in particular preferably those as are shown, for example, in the formulas (2) and (3): mg 6 al 2 (OH) 16 (A 2 ) ⁇ WH 2 O mg 4 al 2 (OH) 12 (A 2 ) ⁇ WH 2 O
• a 2 has the meaning given above for formula (1) and 1 ⁇ w ⁇ 15.
• hydrotalcites are those having the formulas (4) and (5): mg 6 al 2 (OH) 16 CO 3 .5H 2 O mg 4 al 2 (OH) 12 CO 3 .4H 2 O
• dialkyl sulfosuccinates described are used to coat the hydrotalcites from 1 to 15 wt.% Based on the weight of the coated hydrotalcite used.
• Hydrotalcites are used, which are coated with 1.5 to 12 wt .-% dialkyl sulfosuccinate. In particular, preference is given to using hydrotalcites containing from 2 to 8% by weight of dialkylsulfosuccinate are coated.
• the preparation of the dialkylsulfosuccinates can according to known methods, such as in Literature C.R. Carly, Ind. Eng. Chem., Vol. 31, page 45, 1939 described.
• dialkyl sulfosuccinates are sodium diisobutyl sulfosuccinate, sodium bis (n-octyl) sulfosuccinate, Sodium bis (2-ethylhexyl) sulfosuccinate, sodium dihexylsulfosuccinate, Sodium diamyl sulfosuccinate and sodium dicyclohexyl sulfosuccinate.
• Very particularly preferred dialkylsulfosuccinate is sodium bis (2-ethylhexyl) sulfosuccinate.
• dialkylsulfosuccinates used for coating hydrotalcites can be described as Single substances or as mixtures of several Dialkylsulfosuccinate be used.
• the coating of the hydrotalcites can be achieved by spraying and / or mixing in the dialkylsulfosuccinate preferably in front of and / or together or separately in any order during a final grinding of the hydrotalcite. It does not matter if that Dialkylsulfosuccinat in the preparation of the hydrotalcite resulting moist filter cake, Pastes or slurries is mixed before drying or if it is the dry good immediately before the final grinding in a suitable manner, for example by spraying, added or, in the case of steam jet drying, the steam immediately at the Feed is added to the jet mill.
• the dialkylsulfosuccinate may be optionally before the addition is converted into an emulsion.
• hydrotalcites as such is carried out, for example, by basically known methods. Such methods are e.g. described in the published patent EP 129 805-A1.
• the preparation of the hydrotalcites coated with dialkylsulfosuccinate preferably takes place from their starting compounds, for example from MgCO 3 , Al 2 O 3 and water in the presence of dialkylsulfosuccinate and a solvent such as, for example, B. water or a C 1 -C 8 alcohol with subsequent drying by z. B. spray drying and optionally subsequent grinding by, for example, a bead mill.
• coated hydrotalcites having a mean diameter (number average) of at most 5 ⁇ m, particularly preferably those having at most 3 ⁇ m, very particularly preferably those having at most 2 ⁇ m and especially very preferably those having at most 1 ⁇ m mean Diameter.
• the dialkyl sulfosuccinate-coated hydrotalcites may be the polyurethane urea composition added at any point in the production of polyurethane urea fibers become.
• the dialkylsulfosuccinate-coated hydrotalcites may be in the form a solution or slurry to a solution or dispersion of other fiber additives and then mixed upstream with the polymer solution with respect to the fiber spinning nozzles or be injected into it.
• those coated with dialkyl sulfosuccinate Hydrotalcites also separated to the polymer dope solution as dry powders or as a slurry be added in a suitable medium.
• coated hydrotalcites may also be used as mixtures with uncoated ones or with known coating agents (e.g., metal fatty acids or polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane) Hydrotalcites for the production of polyurethane urea fibers according to the above described procedure be used when the above-described disadvantages of known coated hydrotalcites are tolerable in the mixture.
• coating agents e.g., metal fatty acids or polyorganosiloxane or a mixture of polyorganosiloxane and polyorganohydrogensiloxane
• hydrotalcites coated with dialkylsulfosuccinates takes place in Polyurethaneurea compositions according to the procedure described below.
• a 20% dispersion of dialkyl sulfosuccinate-coated hydrotalcites becomes by mixing in a suitable solvent, e.g. Dimethylacetamide, prepared.
• the Dispersion may optionally by means of a bead mill, z. B. Fryma mill, type MSZ 12, Fryma-96bau GmbH, ground.
• the dispersion is treated with a polyurethaneurea spinning solution adjusted so that in the resulting dispersion, a 12 to 16% iger Content (wt .-%) of dialkylsulfosuccinate-coated hydrotalcites results.
• This dispersion ensures that the dialkyl sulfosuccinate-coated hydrotalcites do not sediment and also finely distributed after storage.
• the mean diameter (number average) of hydrotalcites coated with dialkyl sulfosuccinates in this dispersion is preferred at most 3 microns, more preferably at most 2 microns and most preferably at most 1 micron.
• the polyurethane urea fibers of the present invention may be a variety of different others Additives for various purposes, for example matting agents, fillers, antioxidants, Dyes, stains, stabilizers against heat, light, UV radiation and Fumes.
• antioxidants examples include stabilizers from the group of sterically hindered phenols, HALS stabilizers (h indered a mine l ight s tabilizer), triazines, benzophenones and benzotriazoles.
• pigments and matting agents are titanium dioxide, zinc oxide and barium sulfate.
• dyes examples include acid dyes, disperse and pigment dyes and optical brighteners.
• the stabilizers mentioned can also be used in mixtures and contain an organic or inorganic coating agent. The said additives should preferably be metered in such amounts that they do not show any effects opposite to the dialkyl sulfosuccinate-coated hydrotalcites.
• Hydrotalcites may agglomerate as described in the beginning under certain circumstances in polar solvents such as. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, in the dry or Wet spinning process commonly used to make polyurethaneurea fibers become. For this reason, spinning solutions with incorporated hydrotalcites can be used during the spinning process difficulties due to blockages of the spinnerets occur, resulting in a greatly increasing nozzle pressure results and / or tearing off the freshly formed fibers comes before or during winding on a bobbin.
• polar solvents such as. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide
• dialkylsulfosuccinate coated hydrotalcites When incorporated with dialkylsulfosuccinate coated hydrotalcites in polyurethane urea spinning solutions according to the invention no agglomeration occurs in the spinning solution and the mean grain size of dialkylsulfosuccinate coated hydrotalcite remains essentially unchanged. This ensures the service life of the spinnerets and, associated with this, the operational safety and economic efficiency in the dry or wet-spinning process of the polyurethane urea fibers according to the invention.
• the invention also provides a process for the production of polyurethane urea fibers, in which a long-chain synthetic polymer with at least 85% segmented polyurethane in an organic solvent, e.g. Dimethylacetamide, dimethylformamide or dimethyl sulfoxide, in a proportion of 20 to 50% by weight with respect to the polyurethaneurea composition, preferably at a level of from 25 to 40% by weight with respect to the polyurethaneurea composition dissolved, and this solution then through spinnerets after the dry or wet spinning process is spun into filaments, characterized in that with a dialkylsulfosuccinate coated hydrotalcite in an amount of 0.30 wt .-% to 10 wt .-%, preferably from 0.5% to 8% by weight, more preferably from 1.5% to 7% by weight Wt .-%, and most preferably an amount of 2 wt .-% to 6 wt .-%, based on the Weight of the polyurethane
• the dispersion of substantially more than 10 wt .-% of the dialkylsulfosuccinate coated Hydrotalcites within the filament and optionally also on the filament surface can lead to adverse physical properties of the fibers and is therefore less recommended.
• the improved polyurethane urea fibers according to the invention consist of segmented polyurethanes, for example, those based on polyethers, polyesters, polyether esters, polycarbonates and the like.
• Such fibers can be prepared by basically known methods are prepared, for example, according to those methods which are described in the documents WO 94/23100-A1 or WO 98/25986-A1.
• the polyurethane urea fibers from thermoplastic polyurethanes their preparation for example in the published patent application EP 1 379 591-A1.
• the segmented polyurethanes are in principle in particular a linear homo- or Copolymer with one hydroxyl group at the end of the molecule and a molecular weight of 600 up to 4000, e.g. from the group of polyester diols, polyether diols, polyester amidodiols, polycarbonate diols, Polyacryldiols, Polythioesterdiole, Polythioetherdiole, Polyhydrocarbonklarediole or a Mixture or copolymers of compounds of this group, prepared. Furthermore, this is based segmented polyurethane in particular on organic diisocyanates and chain extenders with several active hydrogen atoms, such as. As di- and polyols, di- and polyamines, hydroxylamines, Hydrazines, polyhydrazides, polysemicarbazides, water or a mixture of these Components.
• polyurethane urea fibers are polyether-based polyurethane urea much more sensitive than polyurethane urea fibers from one on polyester based polyurethaneurea. For this reason, polyurethane urea fibers are particularly preferably comprising polyether-based polyurethane ureas.
• dialkyl sulfosuccinate-coated hydrotalcites are non-dialcohol additives Contain heavy metal and harmless from a toxicological point of view and are therefore preferred. This can ensure that in the further processing of polyurethane urea fibers such as. the coloring does not produce effluents, which is the functioning of a biological reduce or destroy the working sewage treatment plant.
• Another object of the invention are textile goods, in particular knitted, knitted or woven goods, prepared using the polyurethane urea fibers according to the invention, preferably in Mixture with synthetic hard fibers such as polyamide, polyester or polyacrylic fibers and / or with Natural fibers such as wool, silk or cotton.
• synthetic hard fibers such as polyamide, polyester or polyacrylic fibers
• Natural fibers such as wool, silk or cotton.
• the color change or yellowing is suitable for making fibers Polyurethaneurea compositions and the resulting polyurethaneurea fibers shown containing hydrotalcite coated with various agents.
• the polyurethaneurea compositions are made on the basis of polyether diols and contain those with different Agents coated hydrotalcites as an internal additive.
• polyurethane urea spinning solutions were prepared from a polyether diol, consisting of polytetrahydrofuran (PTHF) with an average molecular weight of 2000 g / mol produced.
• the diol was treated with methylene bis (4-phenyl diisocyanate) (MDI) with a capped molar ratio of 1 to 1.65, diluted in dimethylacetamide and then with a Mixture of ethylenediamine (EDA) and diethylamine (DEA) chain-extended in dimethylacetamide.
• MDI methylene bis (4-phenyl diisocyanate)
• EDA ethylenediamine
• DEA diethylamine chain-extended in dimethylacetamide.
• the molecular weight of the polyether is based on the number average.
• the content of Polymer in the produced polyurethaneurea spinning solution is 30% by weight.
• Hydrotalcites coated with various coating agents were 20% in dimethylacetamide dispersed as solvent by means of an Ultra-Turrax and then in the above-described Polyurethane urea spinning solution incorporated in the manner that the content of coated Hydrotalcite based on the polymer in the polyurethane urea spinning solution 10 wt .-% is.
• the examination of yellowing was made by passing the films through a tenter with a Speed of 5 m / min at a temperature of 195 ° C were performed. This pass by a tenter corresponds to the processing step of the hot air fixing during manufacture of textiles. The throughput time of the films through the tenter was 50 seconds.
• the polyurethaneurea spinning solution described above was added to the following stock of the following stock solutions:
• the first stock mixture consisted of 55.3% by weight of dimethylacetamide (DMAC), 11.1% by weight of Cyanox® 1790 ((1,3,5-tris (4-tert-butyl-3-hydroxy-2, 5-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione, from Cytec), 7.6% by weight of Aerosol OT® 100 (sodium bis- (2-ethylhexyl) sulfosuccinate, Cytec), 26.0 wt .-% 30% spinning solution and 0.001 wt .-% of the dye Makrolex® violet (Bayer AG) .This stock was added to the spinning solution so that in the finished fiber, the content of Cyanox® 1790 was 1% by weight, based on the solids of the fiber polymer.
• DMAC dimethylacetamide
• This spinning solution was admixed with a second stock mixture consisting of 30.9% by weight titanium dioxide Type RKB 3 (Kerr-McGee Pigments GmbH & Co. KG), 44.5 wt .-% DMAC and 24.6 % By weight 30% spinning solution, such that in the finished fiber a titanium dioxide content of 0.20 Wt .-% based on the polyurethane-urea polymers resulted.
• This polyurethaneurea spinning solution is now mixed with a third stock solution.
• This consists of 5.5% by weight of Silwet® L 7607 (polyalkoxy-modified polydimethylsiloxane; Viscosity: 50 mPas (at 25 ° C.), molecular weight 1000 g / mol, from OSI Specialties), 5.5% by weight Magnesium stearate, 45.0 wt .-% DMAC and 44.0 wt .-% of a 30% spinning solution and is added so that a magnesium stearate content of 0.27 wt .-%, based on the solids of Polyurethane-urea polymers resulted.
• Silwet® L 7607 polyalkoxy-modified polydimethylsiloxane; Viscosity: 50 mPas (at 25 ° C.), molecular weight 1000 g / mol, from OSI Specialties
• Magnesium stearate 45.0
• This spinning solution was admixed with a fourth stock mixture consisting of 13.8% by weight of the Coated hydrotalcites indicated in Table 2, 55.2% by weight of dimethylacetamide and 31.0 % By weight 30% spinning solution, in such a way that in the finished elastane fiber 3.0 wt .-% of in Table 2 reported coated hydrotalcites based on the polyurethane-urea polymers resulted.
• the finished spinning solutions became filaments through spinnerets in a typical spinning apparatus spun dry with a titer of 15 dtex, each with three individual filaments to coalescing filament yarns having a total titer of 44 dtex.
• the Fiber preparation consisting of polydimethylsiloxane having a viscosity of 5 cSt / 25 ° C was about a spin finish, with about 4.0 wt .-% based on the weight of the fiber were applied. The fiber was then wound at a speed of 900 m / min.
• the examination of yellowing was made by the filaments by means of a knitting machine to a Knitted hose and this then by a tenter at a speed of 5 m / min at a temperature of 195 ° C was performed.
• the lead time of the knitted tubes through the clamping frame was 50 seconds.
• the good service life of the spinnerets and the associated reliability in the dry spinning process was shown in a 14-day spinning trial. During this time, 5.0% by weight of the dialkyl sulfosuccinate-coated hydrotalcite with respect to the finished elastane fiber. There was no disturbance of the spinning process by e.g. an agglomeration of the with dialkyl sulfosuccinate coated hydrotalcites with the potential consequences of a build-up of pressure upstream of the filter in the spinneret or thread breaks in the spinning process. The durability the polyurethaneurea fibers thus produced against a chlorine water induced Degradation remained at a high level.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Mechanical Engineering (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Coloring (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
• Woven Fabrics (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2004
  • 2004-06-17 DE DE102004029274A patent/DE102004029274A1/de not_active Withdrawn
• 2005
  • 2005-06-11 EP EP05012586A patent/EP1607499A1/de not_active Withdrawn
  • 2005-06-13 US US11/151,380 patent/US20050288417A1/en not_active Abandoned
  • 2005-06-14 SG SG200503747A patent/SG118374A1/en unknown
  • 2005-06-15 CA CA002510039A patent/CA2510039A1/en not_active Abandoned
  • 2005-06-16 MX MXPA05006539A patent/MXPA05006539A/es unknown
  • 2005-06-16 JP JP2005176964A patent/JP2006002336A/ja not_active Withdrawn
  • 2005-06-17 CN CNA2005100922503A patent/CN1782148A/zh active Pending
  • 2005-06-17 KR KR1020050052205A patent/KR20060046472A/ko not_active Application Discontinuation

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