WO2008061920A1 - Composition destinée au traitement de fils, son procédé de fabrication et son utilisation - Google Patents

Composition destinée au traitement de fils, son procédé de fabrication et son utilisation Download PDF

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Publication number
WO2008061920A1
WO2008061920A1 PCT/EP2007/062301 EP2007062301W WO2008061920A1 WO 2008061920 A1 WO2008061920 A1 WO 2008061920A1 EP 2007062301 W EP2007062301 W EP 2007062301W WO 2008061920 A1 WO2008061920 A1 WO 2008061920A1
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WO
WIPO (PCT)
Prior art keywords
composition
threads
composition according
silicone oil
weight
Prior art date
Application number
PCT/EP2007/062301
Other languages
German (de)
English (en)
Inventor
Stefan Wirag
Claudia Alpers
Original Assignee
Dystar Textilfarben Gmbh & Co Deutschland Kg
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 Dystar Textilfarben Gmbh & Co Deutschland Kg filed Critical Dystar Textilfarben Gmbh & Co Deutschland Kg
Publication of WO2008061920A1 publication Critical patent/WO2008061920A1/fr

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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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or 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
    • D06M13/02—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with hydrocarbons
    • 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
    • D06M13/10—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 oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or 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
    • D06M13/10—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 oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or 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
    • 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
    • D06M15/53—Polyethers
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M7/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • 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
    • D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions

Definitions

  • composition for the treatment of threads as well as methods for their production and their use
  • the invention relates to a composition for treating threads, a method of making the composition and the use of the composition.
  • the industrial sewing with threads is carried out at high speed, with regularly performed about 4000 to 6000 stitches per minute.
  • Thread can lead. For this reason, the threads are pretreated with an agent
  • Spray applied to the threads A prerequisite for this is that the agents are liquid at room temperature.
  • a composition for the treatment of yarns which is liquid at room temperature and (A) 50 to 95 wt .-% of a silicone oil with a viscosity of 5 to 5000 centistokes at 25 0 C, ( B) 5 to 40 wt .-% of a wax emulsion, wherein the wax may be selected from paraffin waxes, semi-crystalline waxes, polyethylene waxes, ester waxes and natural waxes having a melting point of more than 40 ° C, and (C) 0.5 bis 5 wt .-% of a silicone as a surfactant.
  • the wax emulsion is an emulsion in water, ie the composition is water-containing.
  • this composition Since this composition is liquid at room temperature, it can be applied to threads by means of a godet roll.
  • the composition has the disadvantage that at longer runtime often thickening of the composition by evaporation of the water occurs, whereby the subsequent application to the threads is difficult or impossible.
  • the threads must be dried later. If no drying of the threads, there is a risk of mold growth on the coils.
  • Hydrous compositions also promote corrosion of machine parts.
  • Another disadvantage of this hydrous Emulsions for the treatment of yarns is the segregation of the phases that often occurs after some time, which leads to staining on the sewn textiles.
  • composition of DE 199 01 4508 By this composition of DE 199 01 458, the damage and destruction of the treated threads, for which the friction is a measure, significantly reduced in industrial sewing and achieved a good heat shield. Furthermore, the composition is liquid at room temperature and can therefore be applied to threads by means of a godet without the need for heating the composition. In addition, the composition of DE 199 01 458 has no added water, i. it is essentially anhydrous, so that the disadvantages described above, such as the thickening of the composition, mold growth and corrosion of machine parts, are avoided.
  • the silica or hydrophobized silica added has the disadvantage that it is very expensive and the silica particles tend to aggregate, which may cause lumps in the composition.
  • the beneficial effect of the added silica repealed, for example, the product stability achieved, and on the other hand, the aggregates formed (lumps) the finishing step and the subsequent sewing influence negatively.
  • the lumps may clog the conduits of the device used.
  • An object of the present invention is therefore to provide an improved composition which overcomes these disadvantages of the prior art and is suitable for the treatment of filaments. This object is achieved by a composition for treating threads that
  • composition of the invention is at room temperature, i. liquid at about 20 ° C and can therefore be applied to threads without prior heating using, for example, godets or pumps at room temperature.
  • compositions according to the invention after being applied to threads, led to a significantly reduced friction of the threads compared to untreated threads and even the friction properties of the compositions of DE 199 01 458 could be improved, as well as the antistatic properties of the treated threads could be improved. Furthermore, the composition of the invention shows no lump formation.
  • the silicone oil present in the composition according to the invention contributes substantially to the sewability of threads treated therewith, in particular of yarns, and ensures good heat shielding of the treated threads.
  • the silicone oil is usually a substantially clear, colorless, neutral and odorless liquid having a molecular weight of about 1,000 to 150,000 and a density of about 0.94 to 0.97 g / cm 3 .
  • the silicone oil may be, for example, a linear, branched, cyclic or crosslinked polydimethylsiloxane in which a part or all of the methyl groups are replaced by other organic groups, such as alkyl groups, e.g. B. with 2 to 15 carbon atoms, and / or aryl groups, such as phenyl groups may be replaced.
  • the chain ends are usually formed by trimethylsilyl groups and / or hydroxyl groups.
  • the silicone oil present in the composition according to the invention may comprise one or more silicone oils different from one another. Examples of the silicone oil are polydimethylsiloxanes, hydroxyl-terminated polydimethylsiloxanes or mixtures thereof. - A -
  • the viscosity of the silicone oil used for the composition of the invention is suitably chosen so that on the one hand a good processability and a good applicability to the threads is achieved, it should be neither too thin nor too thick.
  • the amount of silicone oil present in the composition according to the invention is preferably 75% by weight to 95% by weight, more preferably 80% by weight to 93% by weight and even more preferably 85% by weight to 92% by weight.
  • the composition according to the invention may comprise one or more silicone oils different from one another, for example two or three silicone oils.
  • Component b) of the composition according to the invention is at least one wax which is present in an amount of from 2% by weight to 15% by weight, preferably from 3% by weight to 12% by weight, in particular from 4% by weight to 10% Wt .-%, is present in the composition. Most preferred is an amount of 4-8% by weight, based on the total composition. With this wax, especially in these amounts, a very good reduction in friction of treated with the composition of the invention threads is achieved. If the amount of wax is greater than 15% by weight, the composition of the invention may be solid at room temperature; If the amount of wax is less than 2% by weight, the friction is often not sufficiently reduced.
  • the composition according to the invention may comprise one or more waxes, for example two or three waxes.
  • suitable waxes are petroleum waxes such as paraffin waxes, microcrystalline waxes and semi-crystalline waxes, synthetic waxes such as polyethylene waxes, Fischer-Tropsch waxes and chemically modified hydrocarbon waxes, natural waxes such as beeswax and carnauba wax, and mixtures of two or more of these waxes with paraffin waxes being preferred.
  • the wax present in the composition according to the invention has a melting point of 40 ° C or higher, in particular 50 ° C or higher.
  • Particularly preferred are paraffin waxes having a melting point of 55-65 ° C. This ensures that a particularly good manufacturability and processability of the composition according to the invention is ensured.
  • the upper limit for the melting point of the wax should not exceed about 120 ° C.
  • Component c) of the composition according to the invention is at least one alkyl polyglycol ether which contributes substantially to the good antistatic properties of the threads treated with the composition.
  • the viscosity of the composition according to the invention can be controlled via the alkyl polyglycol ether (s) and stabilization of the composition is achieved. For example, by adding alkyl polyglycol ethers, it is possible to increase the proportion of wax, which is not possible to the same extent without alkylpolyglycol ether, without the composition becoming solid or segregating.
  • alkyl polyglycol ether or a mixture of two or more alkyl polyglycol ethers may be used.
  • alcohol ethoxylates (RO (CH 2 CH 2 O) m H)
  • alcohol propoxylates for example RO (CH 2 CH (CH 3 ) O) m H
  • alcohol ethoxylates / propoxylates or alcohol propoxylates / ethoxylates in each case randomly or in blocks arranged, present.
  • the alkyl radical R with 4-36 carbon atoms preferably has 8-28 and more preferably 10-22 carbon atoms.
  • the number of ethylene glycol molecules m and of the propylene glycol molecules n copolymerized in random or blockwise amounts to 0 to 150, preferably to 3 to 120, independently of one another.
  • composition according to the invention comprises in addition to the components a), b) and c) at least one fatty acid.
  • the composition according to the invention additionally comprises at least one fatty acid salt, at least one fatty acid ester and / or at least one fatty acid amide or mixtures of these.
  • fatty acids saturated or unsaturated aliphatic carboxylic acids with a branched or preferably unbranched carbon skeleton.
  • the fatty acids used in the composition of the invention may be C 10 to C 24 fatty acids. These fatty acids may have one or more, for example two or three double bonds per fatty acid molecule.
  • Examples of the fatty acids present in the composition according to the invention are palmitic acid, stearic acid, palm oil fatty acid and coconut oil fatty acid, of which stearic acid and coconut oil fatty acid are preferred.
  • the composition of the invention may be present several different fatty acids.
  • the alkali or alkaline earth salts such as the Li, Na and K salts or the Mg and Ca salts, of fatty acids, especially those mentioned above Fatty acids, are used.
  • the composition of the invention may be present several different salts of fatty acids.
  • esters of a fatty acid examples include the esters, in particular those of the fatty acids described above, with CVCVAIkoholen, z. As methanol, ethanol and butanol. In the composition of the invention may be present several different esters of fatty acids.
  • amide of a fatty acid is understood to mean compounds of any type obtainable by reacting NH 3 or an amine with a fatty acid, in particular a fatty acid described in more detail above, wherein “amines” are understood as meaning ammonia-derived compounds of any type.
  • amines are understood as meaning ammonia-derived compounds of any type.
  • composition according to the invention several mutually different amides of a fatty acid may be present.
  • Examples of the amines are represented by the general formula HN (R 1 ) R 2 (1) wherein R 1 and R 2 may be the same or different and are H or a C 1 to C 5 alkyl group such as methyl, ethyl and propyl, stand.
  • R 1 and R 2 may be the same or different and are H or a C 1 to C 5 alkyl group such as methyl, ethyl and propyl, stand.
  • the amines may also be polyamines, "polyamines” being understood to mean saturated, open-chain or cyclic compounds having a plurality of primary, secondary and tertiary amino groups.
  • the amount of the one or more fatty acids, the one or more fatty acid salts, the one or more fatty acid esters and / or the one or more fatty acid amides or the mixture thereof in the composition according to the invention is preferably 0.1% by weight to 10% by weight. %, in particular 0.5 to 5 wt .-%, particularly preferably 1 to 3 wt .-%, based on the composition according to the invention.
  • the salts of the fatty acids, the esters of the fatty acids and the amides of the fatty acids is achieved that the friction and thus the friction of the threads to which the composition according to the invention is applied, is reduced during sewing.
  • the three components of silicone oil (s), wax (s) and alkyl polyglycol ethers may each independently consist of one or more components, for example 2, 3, 4 or 5 components.
  • the composition according to the invention may be a silicone oil, one or two Waxes and one, two, three or four alkyl polyglycol ethers and other optional components such as a fatty acid, or two fatty acids.
  • compositions of the invention may be one or two silicone oils, one or two paraffin waxes, one or two fatty acids and one, two, three or four alkyl polyglycol ethers, e.g.
  • fatty alcohol ethoxylates exist, which compositions may of course contain the usual impurities of the components usually used in the form of technical products. It is further preferred that the composition according to the invention contains no silica and no hydrophobized silica.
  • the composition of the invention is preferably added no additional water, so that in the composition only the residual water content contained in the components used, that is.
  • the composition is essentially anhydrous, which is understood as meaning an amount of less than 1% by weight of water, preferably less than 0.5% by weight of water, more preferably less than 0.2% by weight of water.
  • the composition of the invention may also be anhydrous, which is understood as meaning a water content of less than 0.1% by weight and preferably less than 0.05% by weight of water, based on the total composition.
  • composition according to the invention has essentially no organic solvents, ie. it is substantially free of organic solvents, which avoids both odor nuisance and health hazards possibly caused by the organic solvents.
  • substantially free of organic solvents the same explanations apply as in the expression "essentially anhydrous”.
  • the composition of the present invention is useful for treating (finishing) threads to improve their slip properties and to protect the threads from heat, thereby achieving overall diminishing friction.
  • threads are understood to be all thread-like materials, the composition according to the invention being particularly suitable for finishing textile fiber threads.
  • a preferred use of the composition according to the invention is the finishing of yarns and twists, in particular of sewing and embroidery threads as well as sewing and embroidery threads.
  • the threads and thus the yarns may include natural fibers and / or synthetic fibers, for example Cotton, wool, polyester, polyamide or viscose.
  • the composition according to the invention can be applied to the threads by means of a galette or a pump system known per se.
  • the applied amount of the composition according to the invention is generally 1 to 8 wt .-%, preferably 1 to 6 wt .-%, based on the thread.
  • the at least one silicone oil, the at least one wax and the at least one alkylpolyglycol ethers and optionally further components are mixed with heating.
  • constituents used in the process according to the invention are in particular the components described above in the composition according to the invention.
  • compositions according to the invention can be prepared in a simple, rapid and cost-effective manner.
  • silicone oil polydimethylsiloxane, viscosity about 1000 Centistoke
  • silicone oil polydimethylsiloxane, viscosity about 1000 Centistoke
  • 6 kg of paraffin wax are added and 1 kg of stearic acid in the form of flakes at 95 - 98 ° C sprinkled.
  • the mixture is allowed to melt completely and then sucks at 90 - 95 ° C 5.6 kg of alkyl polyglycol ether in the mixture.
  • 57.4 kg of silicone oil polydimethylsiloxane, viscosity about 1000 centistokes
  • After completion of the silicone oil addition is stirred for 15 min at 90 - 95 0 C and the mixture is allowed to cool with stirring to below 40 ° C.
  • the cooled mixture is withdrawn through a filter bag (400 microns).
  • compositions obtained according to Examples 1 and 2 were each applied in an amount of about 5 wt .-% of polyester yarn by the yarn by a product loaded sponge and allowed to dry. Subsequently, the frictions and antistatic properties were measured with a commercially available Honigmann ⁇ -meter (including Isoprobe Electrostatik Voltmeter, Model 244 A and FAG 478 Thread Extractor). As a comparison, untreated polyester yarn (raw yarn) and polyester yarn treated with 5% by weight of the compositions according to DE 199 01 458 were selected. The results are listed in the table below.
  • Table Comparison of prior art compositions of the invention including the measured values of friction and antistatic properties of the treated filaments; Ingredients in wt .-%.
  • the friction of filaments after treatment with the compositions of the present invention is markedly lower than that of raw yarn and slightly reduced over filaments treated with prior art compositions.
  • the antistatic properties could be significantly improved.

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

Abstract

L'invention concerne une composition destinée au traitement de fils, comprenant (a) 70 à 97 % en poids d'au moins une huile de silicone, (b) 2 à 15 % en poids d'au moins une cire et (c) 1 à 15 % en poids d'au moins un éther d'alkyle polyglycol. En outre, l'invention concerne un procédé de fabrication de la composition et l'utilisation de la composition pour le traitement des fils.
PCT/EP2007/062301 2006-11-22 2007-11-14 Composition destinée au traitement de fils, son procédé de fabrication et son utilisation WO2008061920A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06024233.6 2006-11-22
EP06024233A EP1925721A1 (fr) 2006-11-22 2006-11-22 Composition pour le traitement de fils, méthode de fabrication et utilisation de cette composition

Publications (1)

Publication Number Publication Date
WO2008061920A1 true WO2008061920A1 (fr) 2008-05-29

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Application Number Title Priority Date Filing Date
PCT/EP2007/062301 WO2008061920A1 (fr) 2006-11-22 2007-11-14 Composition destinée au traitement de fils, son procédé de fabrication et son utilisation

Country Status (2)

Country Link
EP (1) EP1925721A1 (fr)
WO (1) WO2008061920A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19901458A1 (de) * 1999-01-15 2000-07-20 Boehme Chem Fab Kg Zusammensetzung zur Behandlung von Fäden sowie Verfahren zu deren Herstellung und deren Verwendung
WO2004063456A1 (fr) * 2003-01-14 2004-07-29 Cht R. Beitlich Gmbh Avivage de fils a coudre independant de la valeur du ph dans le cadre du procede par epuisement

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19901458A1 (de) * 1999-01-15 2000-07-20 Boehme Chem Fab Kg Zusammensetzung zur Behandlung von Fäden sowie Verfahren zu deren Herstellung und deren Verwendung
WO2004063456A1 (fr) * 2003-01-14 2004-07-29 Cht R. Beitlich Gmbh Avivage de fils a coudre independant de la valeur du ph dans le cadre du procede par epuisement

Also Published As

Publication number Publication date
EP1925721A1 (fr) 2008-05-28

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