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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/61—Polyamines polyimines
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
  • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
  • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
• • 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
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
  • D06M13/325—Amines
  • D06M13/332—Di- or polyamines
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/34—Ignifugeants
• • 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
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/03—Non-macromolecular organic compounds
  • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
  • D21H17/10—Phosphorus-containing compounds
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
  • D21H17/56—Polyamines; Polyimines; Polyester-imides
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
  • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material

Definitions

• the invention relates to a process for the flame-retardant finishing of fiber products.
• RM Rowell describes the chemical modification of lignocelluloses in "Proceedings, International Workshop on Frontiers of Surface Modification and Characterization of Lignocellulosic Fibers” (Sweden, May 30-31, 1996) (ISBN 91-7197-593-4).
• DE-A 30 03 648 and DE-A 42 44 194 describe the use of nitrogen-containing condensation products in papermaking.
• EP-A 542 071 describes wood preservatives which contain copper salts and which may additionally contain polyethyleneimine and / or phosphonic acid.
• the object of the present invention was to develop an improved method, to provide fiber products flame-retardant, in particular also fiber products with a high proportion of cellulose fibers produced by a wet process, Good flame retardant effects can be imparted.
• wet processes are namely the problems often greater than in dry processes, so that in known wet processes the danger is that the flame retardant component in the course of the preparation of the Fiber product is washed out. In this case, deterioration usually occurs the flame-retardant properties of the final article.
• fiber products are products which contain 20 to 100% by weight of cellulose fibers. This range of cellulose fiber content refers to the anhydrous fiber product.
• the fiber products may be finished products, such as paper, press plates (eg medium-density fibreboards or high-density fibreboards), which can be used in the furniture, packaging, construction and automotive industries.
• Such fiber or press plates often contain in addition to fibers still a fixing binder, wherein the fibers are the component which determines the strength of the press plates.
• the inventive method presented here is preferably used to achieve the flame-retardant properties of such fiberboard or press plates. For many uses of such press plates flame retardant properties are required.
• Cellulosic fibers may be blended with additives such as binder resins or hydrophobizing agents to make such fiberboards, optionally adding water to obtain an aqueous fiber suspension.
• the resulting mixture is shaped, dried and pressed into plates under the action of heat and pressure.
• a preferred embodiment is to carry it out during the manufacturing process of the finished fiber products, ie at a precursor of the finished fiber product.
• This precursor is preferably an aqueous suspension which contains cellulose fibers and optionally further additives, for example those of the type mentioned above.
• such fiber suspensions may be, for example, precursors in papermaking.
• aqueous fiber suspensions of cellulose fibers to fiberboard such as press plates or insulation boards
• the process of the invention is advantageously applicable, wherein the aqueous fiber suspension, for example a pulp (English Pulp) is treated with the components A and B.
• the fiber suspension is poured onto a filter screen, wherein a thin layer is formed, starting from which the finished fiber product is prepared by drying and pressing under heat and pressure.
• the said fiber suspension which contains cellulose fibers, water and optionally the abovementioned further components, is normally 0.3 to 15% by weight of cellulose fibers, preferably 0.5 to 1.5% by weight.
• This proportion of cellulose fibers must be such that the finished fiber product after removal of the water contains 20 to 100% by weight of cellulose fibers, based on the fiber product without water and without the components A and B. It is advantageous not to carry out the process according to the invention on the finished fiber product (fibreboard, paper) but on a precursor thereof.
• This precursor is a cellulosic fiber-containing product which is formed during the manufacture of the finished fiber product and processed into the finished fiber product.
• aqueous cellulose fiber suspensions are well suited as precursors for carrying out the process according to the invention.
• the inventive method not on the finished fiber product perform (although this is also possible in certain cases), but on a precursor of the type mentioned, is therefore advantageous because this normally a more effective flame retardancy is achieved. It is believed that this is because in this case better bonding of component A and / or B to the cellulosic fibers is achieved, favored by the subsequent action of heat and pressure.
• An advantageous embodiment of the method according to the invention is characterized in that the cellulose fibers of the fiber product are partly or completely present in the form of lignocellulose-containing fibers.
• Lignocellulose is a vegetable composite of cellulose, polyoses and lignin.
• a fiber product or, preferably, a precursor thereof is treated successively or simultaneously with a component A and a component B.
• a and B can be applied simultaneously, for example in the form of a mixture containing components A and B.
• this method is less preferred and in many cases not suitable. Rather, it is more advantageous to apply the components A and B successively, wherein it is further preferred to apply the component A (polyethyleneimine) earlier on the fiber product than component B (phosphonic acid). It has been found that in many cases with this approach, a more effective flame retardant effect can be achieved than with the other mentioned process variants. It has already been mentioned that it is preferable not to apply components A and B to the finished fiber product but to a precursor thereof.
• This precursor is preferably an aqueous suspension containing the cellulose fibers.
• component A and / or the component B are not applied in a pure form to the fiber product or its precursor, but in the form of a mixture. It is particularly advantageous if both component A and component B are applied in each case in the form of a mixture which contains component A or component B and additionally water.
• component A can be used in the form of a mixture containing 50 to 500 parts by weight of water per 100 parts by weight of component A, and component B in the form of a mixture containing 20 to 300 parts by weight of water per 100 parts by weight Component B contains.
• One or both of these mixtures may contain other components, for example polymaleic acid or partially hydrolyzed polymaleic anhydride.
• the addition of partially or fully hydrolyzed polymaleic anhydride is, if such an additive is used, preferably in the range of 1 to 5% by weight, based on total mixture containing component A or component B and water.
• polymaleic acid or partially hydrolyzed polymaleic anhydride is used, it is preferably added to a mixture containing component A and water. This addition causes, in a number of cases, an increase in the permanence of the flame retardant effect. This could be because the additional use of partially or completely hydrolyzed polymaleic anhydride leads to a better fixation of component A and / or component B on the fiber product.
• the fiber product or its precursor Contains 10 to 25% lignin, in addition to a partial ester of orthophosphoric acid on the Apply fiber product or its precursor.
• the application of this partial ester can simultaneously with the application of component A or component B or, which is preferred is to be done separately in a separate operation.
• the amount of orthophosphoric acid partial ester, which is applied is preferably in the range from 2 to 10% by weight, based on anhydrous fiber product or anhydrous precursor.
• a phosphoric acid partial ester include mono- or diesters of orthophosphoric acid having 6 to 12 carbon atoms suitable in the alcohol component of the ester, or mixtures of such mono- and diesters.
• An example of this is diisooctyl phosphate or diphenyl phosphate or bis (t-butyl-phenyl) phosphate.
• the addition of such esters is often the flame retardant effect increase.
• This is an advantage for cost and environmental reasons and also prevents the finished fiber products from being colored by metal ions are.
• component B in up to 50% of the bound to phosphorus Hydroxy groups are the hydrogen atoms by alkali metal or ammonium ions replaced, but this is not preferred.
• component A, component B or of a mixture which contains water other than component A or component B, to the fiber product or its precursor can be carried out by any desired methods. It is best to use an aqueous suspension containing cellulose fibers as a precursor and to apply to this precursor a mixture containing water and component A and then a mixture containing water and component B. Regardless of whether the components A and B are each applied as a mixture with water or in a pure form on the fiber product or the precursor, a preferred embodiment of the method according to the invention is that the weight ratio of the applied to the fiber product or its precursor amount Component A to the amount of applied component B is in the range of 1: 1.3 to 1: 4.0.
• the amount of component A and component B, which on the fiber product or its Pre-applied, is preferably such that on the finished fiber product 3 to 10% by weight of component A and 7 to 20% by weight of component B are present on anhydrous fiber product.
• Component A is a polyethyleneimine. As is customary with polymers, this is normally not a product which consists of all the same molecules, but is a mixture of products of different chain lengths.
• polyethyleneimines the fact known from the literature is added that under normal conditions there is a mixture of branched polymers whose individual molecules also differ in the number of branching units. This is expressed by the ratio of the number of secondary to primary amino groups as detailed below and to tertiary amino groups.
• Polyethyleneimines are products known from the literature. They can be prepared inter alia by reacting 1,2-ethylenediamine with 1,2-dichloroethane.
• polyethyleneimines which can be prepared by polymerization of unsubstituted aziridine (ethyleneimine). This polymerization can be carried out by known methods, if appropriate with addition of acidic catalysts, for example hydrochloric acid, and optionally in the presence of water.
• acidic catalysts for example hydrochloric acid
• Polyethyleneimines suitable for the process according to the invention are available on the market, for example from BASF, Germany (LUPASOL® grades and POLYMIN® grades) or from Nippon Shokubai Co. Ltd., Japan. US Pat. No. 6,451,961 B2 and US Pat. No. 5,977,293 describe polyethyleneimines and processes for their preparation.
• polyethyleneimines described there can be used for carrying out the process according to the invention, provided they meet the conditions mentioned above and in claim 1. Further, DA Tomalia et al in "Encyclopedia of Polymer Science and Engineering, Vol. 1, Wiley NY 1985, pages 680-739, describes suitable polyethyleneimines and methods for their preparation. Polyethyleneimines, their preparation and properties are also described in D. Horn, “Polyethyleneimine Physicochemical Properties and Applications”, “Polymeric Amines and Ammonium Salts", Goethals EJ, Pergamon Press: Oxford, New York 1980, pages 333-355 .
• the polyethyleneimines suitable as component A for the process according to the invention are branched. That is, the polymer having end groups of formula H 2 N-CH 2 -CH 2 - and within the polymer chain, units of the formula -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH- additionally has units of the formula within the chain contains.
• the polymer thus contains primary, secondary and tertiary amino groups.
• the numerical ratios between the individual amino groups must assume values in a certain range.
• the ratio of the number of secondary amino groups to the number of primary amino groups must be in the range of 1.00: 1 to 2.50: 1, and the ratio of the number of secondary amino groups to the number of tertiary amino groups in the range of 1.20: 1 to 2.00: 1.
• the values for the numerical ratios of the various amino groups present in a particular polyethyleneimine or mixture of polyethylenimines can be determined by 13 C-NMR spectroscopy. This is discussed in T. St. Pierre and M. Geckle, 13 C-NMR Analysis of Branched Polyethyleneimines, J. Macromol SCI.-CHEM., Vol. A 22 (5-7), pages 877-887 ( 1985) ".
• Component A which, as is usual in polymers, is normally a mixture of polymers and consists of polyethyleneimine molecules of different molecular weight and different degrees of branching, has a weight average molecular weight in the range of 5,000 to 1,500,000, preferably in the range of 10,000 to 1,000,000.
• the individual value for this average molecular weight can be determined by methods known from the polymer literature, for example by gel permeation chromatography and detection by means of light scattering.
• the column used is one or more "PSS Suprema” types (available from “Polymer Standards Service GmbH”, Mainz, DE), which are adjusted to the intended molecular weight range; Eluant 1.5% formic acid in water; Multi-angle light scattering detector MALLS (also available from, among others, "Polymer Standards Service”); an internal standard may be used in addition.
• PSS Suprema available from “Polymer Standards Service GmbH”, Mainz, DE
• MALLS Multi-angle light scattering detector
• an internal standard may be used in addition.
• the values for the weight-average molecular weight referred to above and in claim 1 relate to this determination method.
• the average molecular weight of polyethyleneimines can be controlled by varying the parameters in their preparation.
• a preferred embodiment of the method according to the invention is that component A a Polyethyleneimine formed by polymerization of ethyleneimine and having the following structure (formula (V)) wherein the polymerization is optionally catalysed acid, wherein the individual units which contain tertiary amino groups and the individual units which contain secondary amino groups can be distributed as desired over the polymer chain, in which b is greater than a and wherein a and b have such values that the conditions given in claim 1 for the molecular weight and for the numerical ratios of Amino groups are satisfied with each other or wherein component A is a mixture of such polyethyleneimines.
• component A is normally a mixture of polyethylenimines.
• component A being a mixture of compounds of the formula (V).
• the values of a and b in the compounds of the formula (V) must, of course, be chosen so that the values for the ratios of the individual amino groups to one another and for the average molecular weight determined in the mixture are in the ranges stated above and in claim 1 , The control of these values can, as mentioned, be done via the parameters in the production of the polyethyleneimines.
• Component B is a phosphonic acid of the formula (I), of the formula (II) or of the formula (III)
• Component B may also be a mixture of compounds selected from compounds of formula (I), formula (II) and formula (III).
• R represents a linear or branched alkyl radical. This alkyl group contains 1 to 7 carbon atoms in the case that the below-mentioned R 1 is a hydroxy group. If R 1 is hydrogen, the radical R contains 3 to 7 carbon atoms.
• the radical R 1 in formula (I) is H or OH.
• the radical R 2 is the radical
• y can take the values 0, 1 or 2. Preferably, y has the value 0, which analogously to the case described above results in an increase in the phosphorus content on the fiber product.
• All radicals R 4 present in compounds of the formula (III) independently of one another represent hydrogen or or for a radical of the formula (IV)
• t is 0 or a number from 1 to 10.
• 50 to 100% of all radicals R 4 present are
• Phosphonic acids of formulas (I), (II) and (III) are commercially available products, e.g. Masquol P 210-1 Protex-Extrosa or Briquest 301-50 A from Rhodia or the Cublen products D50 (Zschimmer & Schwarz, DE), or Diquest 2060 S (Solutia, Belgium). Phosphonic acids of the formulas (I), (II) and (III) can be generally known from the literature Establish methods.
• a particularly advantageous embodiment of the process according to the invention is characterized in that component B is a mixture of phosphonic acids of the formula (I) and of the formula (II), both of which are present in completely unneutralized form.
• the mixing ratio of phosphonic acid of the formula (I) and phosphonic acid of the formula (II) may take any values.
• the weight ratio of the two types of phosphonic acid can assume values of 0: 100 to 100: 0.
• suspension 1 10 g of fiber raw material were slurried in 300 g of water at room temperature with stirring.
• the fiber raw material consisted of about 90% by weight of cellulose fibers and 10% by weight of lignin). Subsequently, this slurry was diluted with water with stirring to a total weight of 1050 g.
• suspension 2 10 g of a fiber raw material were slurried with 600 g of water with stirring. (This fiber raw material consisted of 70-75% by weight of cellulose fibers and 25-30% by weight of lignin).
• the products obtained from suspensions 1 and 2 were further treated as follows: First, the products were sucked through a suction filter and pressed while already a significant portion of the water was removed. Subsequently, some of the samples were pressed at room temperature and a pressure of 35 kp / cm 2 for 3 minutes and then dried at 120 ° C for 20 minutes and then conditioned at room temperature for 10 minutes. Some other samples were not pressed at room temperature but at elevated temperature. These samples were then no longer dried. The weight was then determined on all the samples thus obtained.
• DIOP di-iso-octyl phosphate
• the following table gives the quantities of suspension 1 or suspension 2 used, the amounts of components A and B used and optionally DIOP used, as well as the conditions of the pressing and drying process and the weight of the finished fibreboard.
• the firing time referred to in the right-hand column of the table as "BZ” represents a measure of the flame-retarding effect of the combination of component A and component B used in the process according to the invention.
• the “BZ” indicates the time in seconds during which the pattern still burns after being exposed to a flame for 15 seconds and then that flame is removed. A higher value for "BZ” thus means worse flame retardant properties of the sample.
• Patterns 3 to 7 show significantly better flame-retardant properties than Patterns 1 and 2 (non-inventive comparative experiments).
• a comparison of the patterns 6 shows and 7 that in the case of higher lignin contents (suspension 2) in the fiber suspension an additive from DIOP can bring a further improvement.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Paper (AREA)
• Fireproofing Substances (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

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• 2003
  • 2003-12-05 EP EP03027959A patent/EP1538261A1/fr not_active Withdrawn
• 2004
  • 2004-11-25 AU AU2004295417A patent/AU2004295417A1/en not_active Abandoned
  • 2004-11-25 CA CA002541504A patent/CA2541504A1/fr not_active Abandoned
  • 2004-11-25 WO PCT/EP2004/013357 patent/WO2005054576A1/fr not_active Ceased
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