EP1705285A1 - Process for the stabilisation of cellulosic fibres, especially of a textile web comprising cellulosic fibres - Google Patents

Process for the stabilisation of cellulosic fibres, especially of a textile web comprising cellulosic fibres Download PDF

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Publication number
EP1705285A1
EP1705285A1 EP05102374A EP05102374A EP1705285A1 EP 1705285 A1 EP1705285 A1 EP 1705285A1 EP 05102374 A EP05102374 A EP 05102374A EP 05102374 A EP05102374 A EP 05102374A EP 1705285 A1 EP1705285 A1 EP 1705285A1
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EP
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Prior art keywords
cellulose fibers
water
treatment solution
binding component
treatment
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EP05102374A
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German (de)
French (fr)
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EP1705285B1 (en
Inventor
Thomas c/o Inst. für Textilchemie and Bechtold
Constanta c/o Inst. für Textilchemie & Ibanescu
Christian c/o Inst. für Textilchemie and Schimper
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Benninger AG Maschinenfabrik
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Benninger AG Maschinenfabrik
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Priority to EP05102374A priority Critical patent/EP1705285B1/en
Application filed by Benninger AG Maschinenfabrik filed Critical Benninger AG Maschinenfabrik
Priority to AT05102374T priority patent/ATE490367T1/en
Priority to DE502005010612T priority patent/DE502005010612D1/en
Priority to BRPI0609467-8A priority patent/BRPI0609467A2/en
Priority to CNA2006800089038A priority patent/CN101146949A/en
Priority to PCT/EP2006/060924 priority patent/WO2006100249A1/en
Priority to RU2007139334/04A priority patent/RU2007139334A/en
Publication of EP1705285A1 publication Critical patent/EP1705285A1/en
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/44Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic Table; Zincates; Cadmates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/07Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/07Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11Treating 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 halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/38Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/58Treating 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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/59Treating 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 nitrogen or compounds thereof, e.g. with nitrides with ammonia; with complexes of organic amines with inorganic substances
    • D06M11/60Ammonia as a gas or in solution
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/58Treating 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 nitrogen or compounds thereof, e.g. with nitrides
    • D06M11/67Treating 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 nitrogen or compounds thereof, e.g. with nitrides with cyanogen or compounds thereof, e.g. with cyanhydric acid, cyanic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid or their salts, or with cyanamides; with carbamic acid or its salts
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating 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
    • D06M13/144Alcohols; Metal alcoholates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating 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
    • D06M13/144Alcohols; Metal alcoholates
    • D06M13/148Polyalcohols, e.g. glycerol or glucose
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating 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
    • D06M13/325Amines
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating 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
    • D06M13/402Amides imides, sulfamic acids
    • D06M13/432Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03Polysaccharides or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/20Treatment influencing the crease behaviour, the wrinkle resistance, the crease recovery or the ironing ease
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/45Shrinking resistance, anti-felting properties

Definitions

  • the invention relates to a process for the stabilization of cellulose fibers, in particular of substantially exclusively cellulose fibers comprising materials according to the preamble of the independent method claim.
  • the invention further relates to the use of a water-binding component as an additive in a treatment solution for stabilizing cellulose fibers or, in particular, substantially exclusively cellulose fibers comprising materials.
  • ammonia is present as an anhydrous liquid swelling agent which, although very concentrated, is a much weaker alkali than aqueous alkali solutions. Accordingly, there is a changed swelling of the cellulose structure and it forms a limited stable form of cellulose, which is summarized under the term cellulose III.
  • the effect of a liquid ammonia treatment is particularly present on removal of the ammonia by evaporation and is in behavior with a weakly alkaline "Fixation" comparable. If the textile is processed alkaline in the following treatment steps, the effect of a preceding ammonia treatment is largely lost.
  • the treatment of textiles in liquid ammonia is therefore of low permanence, but of great importance when the treatment step is placed immediately before a refining.
  • the high-grade finishing process can be carried out as dry crosslinking or as wet crosslinking. This fixation creates textile products with excellent wrinkling properties and a soft feel. This peculiarity explains why the technically complex, process-technically demanding and thus very expensive process, a treatment of cotton textiles in liquid ammonia, is carried out.
  • the ammonia process therefore also has certain advantages in practice, the disadvantage of this process is the high design complexity of the treatment devices, which is necessary due to the ammonia to be liquefied. Their tightness in connection with strictly controlled pressure and / or temperature conditions, and the associated , high cost of such a facility.
  • This object is achieved by a method for stabilizing cellulose fibers with the features of the independent method claim and the use of a water-binding component as an additive in a treatment solution for the stabilization of cellulose fibers.
  • the cellulosic fibers or materials comprising cellulose fibers are substantially, preferably completely, free of regenerated cellulose based yarns and fibers.
  • Regenerated cellulose-based yarns and fibers are understood here to mean in particular: viscose (CV), lyocell fibers (CLY), modal (CMD), cellulose fibers (CU) produced by the copper ammonia spinning process, viscose chemisides, rayon, viscose spun silk, viscose rayon, copper chemisides, copper chemical spun fiber, modifier - or modal fibers, (HWM) polynosic (cf. M. Peter, Handbook for Textile Engineers and Textile Practitioners, Foundations of Textile Finishing, 10th Edition 1970, Dr. Ing. Spohr publishing house, Stuttgart ).
  • a water-binding component (a) used is an alcohol, in particular a polyhydric, preferably aliphatic, alcohol, more preferably selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1.3 Propanediol, 1,2-propanediol, 1,2,3-propanetriol, 1-butanol, 2-butanol, tert-butyl alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and mixtures thereof.
  • Such a component (a) under standard treatment conditions in the liquid phase, as described in the introductory part, in turn additionally and particularly advantageously on solvent properties, in addition to the existing water.
  • water-binding components (a) in another preferred embodiment of the invention as a water-binding component (a) a solid is added to the treatment solution, which is selected from the group consisting of carbohydrates, such as, for example, glucose, sucrose, Fructose, galactose, mannose, as well as other monosaccharides, disaccharides, oligosaccharides, their corresponding carboxylic acid derivatives such as gluconic acids, glucuronic acids; Urea, inorganic salts (especially with cations such as sodium, potassium, ammonium, magnesium, calcium, and anions such as chloride, nitrate, sulfate, phosphate, polyphosphate, silicate, and mixtures thereof); Particularly preferred inorganic salts are NaCl, KCl, MgCl 2 , Na 2 SO 4 , K 2 SO 4 , MgSO 4 , Na 3 PO 4 , K 3 PO 4 , NaNO 3 ,
  • the water-binding component (a) used is either 1,2,3-propanetriol or NaCl, or mixtures thereof; these water-binding components (a) have been found to be particularly advantageous in practice because of their ease of handling as well as more common and less expensive Availability and good to excellent resulting fiber properties proved.
  • the proportion of the water-binding component (a) in the treatment solution is at least 10% by weight.
  • the amount of water-binding component (a) preferably to be used can be easily determined by the person skilled in the art on the basis of routine experiments and / or calculation, in particular depending on the solubility or miscibility with water and the compatibility with the swelling agent (b).
  • the proportion of water-binding component (a) can be up to 90 wt .-%.
  • the proportion of component (a) in the treatment solution accounts for the largest single portion of the total treatment solution.
  • the proportion and / or the nature of the water-binding component (a) in the treatment solution is selected such that an available, free water content - as the not bound by the water-binding component (a) water content - the treatment solution of at most 35 mol / l, preferably at most 25 mol / l, particularly preferably at most 15 mol / l results.
  • the proportion and / or the nature of the water-binding component (a) in the treatment solution is particularly advantageously selected such that essentially values of fiber rigidity (detectable by the handle), fiber swelling (detectable by cross section, X-ray diffraction), dye absorption (detectable by dyeing tests) , Crosslinkability in the refining (detectable by dry and wet wrinkle recovery angle (especially with good dimensional stability), abrasion values and strength), as obtained in the conventional treatment in liquid ammonia.
  • the adjustment of said pH values can be additionally supported by suitable selection and proportion of the water-binding component (a).
  • the swelling agent (b) employed is at least one chemical selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, amines (in particular ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenediamine, triethylenediamine, hexamethylenediamine, hexamethylenetetramine, Diethylamine, triethylamine, isopropylamine, t-butylamine, glycine, serine), thiocyanates (especially sodium, potassium, ammonium and / or calcium thiocyanate), potassium and / or sodium iodide, metal complexes (especially iron tartaric acid, solutions the Cu or Cuoxam complexes), ammonia solution, and mixtures thereof.
  • amines in particular ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenediamine, triethylenediamine, hexamethylenediamine, hexamethylenetetramine,
  • the inventive method for stabilization at a temperature between -10 ° C and 180 ° C, preferably at a temperature between 15 ° C and 105 ° C is performed.
  • the residence time is advantageously between 1 h and 4 h, with continuous implementation, the residence time in the treatment bath is advantageously between 1 and 30 min. In any case, it is important to adjust the composition of the treatment solution according to the invention of the possible treatment time.
  • a high-level refinement of the cellulose fibers or of the material which in particular essentially exclusively comprises cellulose fibers is carried out.
  • Processes of high-grade finishing are here and below understood to mean processes which improve the serviceability of the finished product in one or more directions in a permanent manner, in particular by changing the appearance of the goods by mechanical action (eg, rapping, moire, guarding, pleating, producing gloss effects , etc.), by chemical action (eg creation of breakthrough effects, Dévorant, air tips, stiffening equipment, swelling processes, stiff-finishings, lapping, softening, matting, metallization) or by combined mechanical / chemical treatment (eg Cloqués, Seersucker, Köselkrepp, Craquelé, Klebcloqués), but also methods for increasing the utility value for Effecting better fullness, resistance, swelling resistance, shrinkage-free, crease-free, etc.
  • the handle of the fabric may be stiffer, while with reduced caustic concentration, the fabric's feel gets softer.
  • the water retention capacity increases with higher lye concentration, which increases the differences to results of conventional liquid ammonia treatment.
  • the high-grade finishing can be carried out after treatment with the treatment solution according to the invention either with or without intermediate drying.
  • a particularly advantageous feature of the method according to the invention is that the treatment can be carried out without bonded goods guide. Due to the total reduced in the context of the invention, fiber swelling also occur much lower shrinkage forces, so that the jump of the product is lower than Mercerisierphal in the liquid phase according to the prior art.
  • the invention further relates to the use of a water-binding component as additive in a treatment solution for stabilizing cellulose fibers, or of materials substantially exclusively comprising cellulose fibers, to increase the resulting proportion of cellulose fibers swollen in amorphous regions and / or to reduce the resulting proportion of cellulose fibers crystalline areas of swollen cellulose fibers.
  • STK shock drying condensation.
  • 40 g / l Arkofix® NDF DMDHEU-based product, Clariant AG, Basel, Switzerland
  • 10 g / l MgCl 2 were used as catalyst at a liquor pick-up of about 50-70%. After drying for 1 min at 130 ° C., condensation took place at 170 ° C. (duration 45 sec).

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

Method for stabilizing cellulose fibers (A) and/or materials, particularly textile fabrics, made from them, by treatment with a solution containing a water-binding component (I); a swelling agent (II) and water.

Description

Die Erfindung betrifft ein Verfahren zur Stabilisierung von Cellulosefasern, insbesondere von im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien gemäss dem Oberbegriff des unabhängigen Verfahrensanspruchs. Die Erfindung betrifft weiter die Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern oder von insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien.The invention relates to a process for the stabilization of cellulose fibers, in particular of substantially exclusively cellulose fibers comprising materials according to the preamble of the independent method claim. The invention further relates to the use of a water-binding component as an additive in a treatment solution for stabilizing cellulose fibers or, in particular, substantially exclusively cellulose fibers comprising materials.

Die Behandlung von Cellulosefasern und Materialien, welche aus Cellulosefasern bestehen oder diese umfassen, wie beispielsweise Baumwollmaterialien, in alkalischem Milieu ist im Stand der Technik bekannt. Diese alkalische Behandlung wird häufig unter dem Begriff der Mercerisierung zusammengefasst, gelegentlich wird auch zwischen Mercerisierung (höhere Laugenkonzentration und Spannung der Ware) und Laugierung (niedrigere Laugenkonzentration, keine Warenspannung) unterschieden. Oftmals wird auch zwischen Mercerisierung einerseits und Ammoniakbehandlung andererseits differenziert (vergl. Bernard P. Corbman, Textiles: Fiber to Fabric, 6th Edition 1983, McGraw-Hill Book Company ).The treatment of cellulosic fibers and materials consisting of or including cellulosic fibers, such as cotton materials, in alkaline medium is known in the art. This alkaline treatment is often summarized under the term mercerization, occasionally a distinction is also made between mercerisation (higher alkali concentration and product tension) and leaching (lower alkali concentration, no product tension). Often, a distinction is also made between mercerization on the one hand and ammonia treatment on the other hand (cf. Bernard P. Corbman, Textiles: Fiber to Fabric, 6th Edition, 1983, McGraw-Hill Book Company ).

Bei tiefen Temperaturen oder hohem Druck liegt Ammoniak als wasserfreies flüssiges Quellmittel vor, welches zwar sehr konzentriert ist, jedoch eine wesentlich schwächere Lauge darstellt als wässrige Alkalilösungen. Dementsprechend erfolgt eine veränderte Quellung der Cellulosestruktur und es bildet sich eine begrenzt stabile Form der Cellulose, die unter dem Begriff Cellulose III zusammengefaßt wird. Der Effekt einer Flüssigammoniakbehandlung ist insbesondere bei Entfernung des Ammoniaks durch Abdampfen vorhanden und ist im Verhalten mit einer schwach alkalischen "Fixierung" vergleichbar. Wird das Textil in den folgenden Behandlungsschritten alkalisch bearbeitet, so geht der Effekt einer vorhergehenden Ammoniakbehandlung zum größten Teil verloren. Die Behandlung von Textilien in flüssigem Ammoniak ist daher von geringer Permanenz, jedoch von großer Bedeutung wenn der Behandlungsschritt unmittelbar vor einer Hochveredlung angeordnet wird. Der Hochveredlungsprozess kann dabei als Trockenvernetzung oder als Feuchtvernetzung durchgeführt werden. Durch diese Fixierung entstehen textile Produkte mit besten Knittereigenschaften und weichem Griff. Diese Besonderheit erklärt, warum der sicherheitstechnisch aufwendige, prozesstechnisch anspruchsvolle und damit sehr teure Prozess, einer Behandlung von Baumwolltextilien in flüssigem Ammoniak, durchgeführt wird.At low temperatures or high pressure, ammonia is present as an anhydrous liquid swelling agent which, although very concentrated, is a much weaker alkali than aqueous alkali solutions. Accordingly, there is a changed swelling of the cellulose structure and it forms a limited stable form of cellulose, which is summarized under the term cellulose III. The effect of a liquid ammonia treatment is particularly present on removal of the ammonia by evaporation and is in behavior with a weakly alkaline "Fixation" comparable. If the textile is processed alkaline in the following treatment steps, the effect of a preceding ammonia treatment is largely lost. The treatment of textiles in liquid ammonia is therefore of low permanence, but of great importance when the treatment step is placed immediately before a refining. The high-grade finishing process can be carried out as dry crosslinking or as wet crosslinking. This fixation creates textile products with excellent wrinkling properties and a soft feel. This peculiarity explains why the technically complex, process-technically demanding and thus very expensive process, a treatment of cotton textiles in liquid ammonia, is carried out.

Entsprechend der Bedeutung der Ammoniakbehandlung vorgängig zu einer Hochveredlung wurden verschiedenste Alternativen mit geringem Erfolg erprobt. Hierzu gehören Verwendung wässriger Ammoniaklösungen, Einsatz anderer Amine und Quellmittel (Cuoxamlösungen, Thiocyanate). Generell haben diese Prozesse jedoch keine vorteilhaften Behandlungsresultate erreicht.According to the importance of ammonia treatment previously to a high-grade finishing various alternatives were tested with little success. These include use of aqueous ammonia solutions, use of other amines and swelling agents (cuoxam solutions, thiocyanates). Generally, however, these processes have not achieved beneficial treatment results.

Obschon das Ammoniakverfahren also in der Praxis durchaus auch gewisse Vorteile aufweist, ist nachteilig bei diesem Verfahren der aufgrund des zu verflüssigenden Ammoniaks notwendige, hohe konstruktive Aufwand der Behandlungsvorrichtungen bzgl. deren Dichtigkeit in Verbindung mit strikt kontrollierten Druck-und/oder Temperaturbedingungen, und damit verbundene, hohe Kosten einer solchen Anlage.Although the ammonia process therefore also has certain advantages in practice, the disadvantage of this process is the high design complexity of the treatment devices, which is necessary due to the ammonia to be liquefied. Their tightness in connection with strictly controlled pressure and / or temperature conditions, and the associated , high cost of such a facility.

Es ist daher eine Aufgabe der Erfindung, die Nachteile des Stands der Technik, insbesondere des Ammoniakverfahrens, zu überwinden, also ein alternatives Verfahren zur Stabilisierung von Cellulosefasern und/oder eines Cellulosefasern enthaltenden Materials, insbesondere einer textilen Warenbahnen enthaltend Cellulosefasern bereitzustellen, welches einfach, kostengünstig und vorzugsweise auf konventionellen Behandlungsvorrichtungen durchführbar ist, wobei sich Fasereigenschaften nach dem Stabilisierungsverfahren - bzw. ggf. nach einer anschliessenden Hochveredelung - ergeben, welche mit denen vergleichbar oder besser sind, als sie durch eine konventionelle Ammoniakbehandlung - bzw. ggf. nach einer anschliessenden Hochveredelung - im Stand der Technik erzielt werden.It is therefore an object of the invention to overcome the disadvantages of the prior art, in particular of the ammonia process, that is to say an alternative process for stabilizing cellulose fibers and / or cellulose fibers Provide material, in particular a textile webs containing cellulose fibers, which is simple, inexpensive and preferably feasible on conventional treatment devices, with fiber properties after the stabilization process - or possibly after a subsequent refining - result, which are comparable or better than they by a conventional ammonia treatment - or possibly after a subsequent refining - be achieved in the prior art.

Diese Aufgabe wird gelöst durch ein Verfahren zur Stabilisierung von Cellulosefasern mit den Merkmalen des unabhängigen Verfahrensanspruchs sowie der Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern.This object is achieved by a method for stabilizing cellulose fibers with the features of the independent method claim and the use of a water-binding component as an additive in a treatment solution for the stabilization of cellulose fibers.

Das erfindungsgemässe Verfahren zur Stabilisierung von Cellulosefasern, insbesondere von im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien, ist dadurch gekennzeichnet, dass die Cellulosefasern mit einer Behandlungslösung in Kontakt gebracht werden, wobei die Behandlungslösung umfasst:

  • (a) eine wasserbindende Komponente,
  • (b) ein Quellmittel, sowie
  • (c) Wasser.
Die zu behandelnden Cellulosefasern liegen besonders bevorzugt als textile Warenbahn vor; aber auch die Behandlung von nichtbahnförmigen Cellulosefasern, wie bspw. Fäden, Garnen etc. ist im Rahmen der Erfindung möglich. Durch das Vorsehen einer wasserbindenden Komponente (a) kann der Wassergehalt der Behandlungslösung variiert und insbesondere niedrig eingestellt werden, so dass Resultate erhalten werden, welche mit denen der wasserfreien Ammoniakbehandlung vergleichbar bzw. überlegen sind. Jedoch muss der Wassergehalt (c) zumindest derart hoch gewählt sein, dass sich eine homogene Lösung insbesondere des Quellmittels (b) ergibt. Trotz dieses Restwassergehalts ergeben sich jedoch überraschend Eigenschaften der behandelten Fasern, welche den Eigenschaften von Fasern, welche einer aus dem Stand der Technik bekannten Ammoniakbehandlung unterzogen wurden, vergleichbar sind bzw. diese sogar übertreffen. Die wasserbindende Komponente bindet einen Teil des Wassers der Behandlungslösung vorzugsweise in einer sog. Hydratschicht bzw. über Wasserstoffbrücken, so dass dieser Wasseranteil nicht dem freien Wasseranteil zuzurechnen ist. Der freie Wasseranteil, also der nicht von der wasserbindenden Komponente (a) gebundene Anteil des Wassers (c), kann somit über die Auswahl und/oder die Menge der wasserbindenden Komponente (a) eingestellt und insbesondere minimiert werden.The process according to the invention for stabilizing cellulose fibers, in particular materials comprising essentially exclusively cellulose fibers, is characterized in that the cellulose fibers are brought into contact with a treatment solution, the treatment solution comprising:
  • (a) a water-binding component,
  • (b) a swelling agent, as well
  • (c) water.
The cellulose fibers to be treated are particularly preferably present as a textile material web; but also the treatment of non-web cellulose fibers, such as, for example, threads, yarns, etc. is possible within the scope of the invention. By providing a water-binding component (a), the water content of the treatment solution can be varied and in particular set low, so that results are obtained which are comparable or superior to those of the anhydrous ammonia treatment. However, the water content (c) must be at least as high be that results in a homogeneous solution, in particular the swelling agent (b). However, in spite of this residual water content, properties of the treated fibers surprisingly result which are comparable or even exceed the properties of fibers which have been subjected to an ammonia treatment known from the prior art. The water-binding component preferably binds part of the water of the treatment solution in a so-called hydrate layer or via hydrogen bridges, so that this water content is not attributable to the free water content. The free water content, that is to say the proportion of the water (c) which is not bound by the water-binding component (a), can thus be set and, in particular, minimized via the selection and / or the amount of the water-binding component (a).

In einer besonders bevorzugten Ausführungsform sind die Cellulosefasern bzw. die Cellulosefasern umfassenden Materialien im wesentlichen, vorzugsweise vollständig frei von auf regenerierter Cellulose basierenden Garnen und Fasern. Unter auf regenerierter Cellulose basierenden Garnen und Fasern werden hierbei insbesondere verstanden: Viskose (CV), Lyocellfasern (CLY), Modal (CMD), nach dem Kupferammoniakspinnverfahren hergestellte Cellulosefasern (CU), Viskosechemieseide, Reyon, Viskosespinnseide, Zellwolle, Kupferchemieseide, Kupferchemiespinnfaser, Modifier- oder Modalfasern, (HWM) Polynosic (vergl. M. Peter, Handbuch für Textilingenieure und Textilpraktiker, Grundlagen der Textilveredlung, 10. Auflage 1970, Dr. Spohr-Verlag, Stuttgart ).In a particularly preferred embodiment, the cellulosic fibers or materials comprising cellulose fibers are substantially, preferably completely, free of regenerated cellulose based yarns and fibers. Regenerated cellulose-based yarns and fibers are understood here to mean in particular: viscose (CV), lyocell fibers (CLY), modal (CMD), cellulose fibers (CU) produced by the copper ammonia spinning process, viscose chemisides, rayon, viscose spun silk, viscose rayon, copper chemisides, copper chemical spun fiber, modifier - or modal fibers, (HWM) polynosic (cf. M. Peter, Handbook for Textile Engineers and Textile Practitioners, Foundations of Textile Finishing, 10th Edition 1970, Dr. Ing. Spohr publishing house, Stuttgart ).

Gemäss einer weiteren Ausführungsform der Erfindung wird als eine wasserbindende Komponente (a) ein Alkohol, insbesondere ein mehrwertiger, vorzugsweise aliphatischer Alkohol, verwendet, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus Methanol, Ethanol, 1-Propanol, 2-Propanol, 1,3-Propandiol, 1,2-Propandiol, 1,2,3-Propantriol, 1-Butanol, 2-Butanol, tert.-Butylalkohol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 2,3-Butandiol und Mischungen hiervon. Eine derartige Komponente (a) weist unter gängigen Behandlungsbedingungen in flüssiger Phase, wie im einleitenden Teil beschrieben, ihrerseits zusätzlich und besonders vorteilhaft Lösungsmitteleigenschaften auf, zusätzlich zum vorhandenen Wasser.According to a further embodiment of the invention, a water-binding component (a) used is an alcohol, in particular a polyhydric, preferably aliphatic, alcohol, more preferably selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1.3 Propanediol, 1,2-propanediol, 1,2,3-propanetriol, 1-butanol, 2-butanol, tert-butyl alcohol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and mixtures thereof. Such a component (a), under standard treatment conditions in the liquid phase, as described in the introductory part, in turn additionally and particularly advantageously on solvent properties, in addition to the existing water.

Alternativ oder zusätzlich zu einer der vorstehend genannten, wasserbindenden Komponenten (a) wird in einer weiteren bevorzugten Ausführungsform der Erfindung als eine wasserbindende Komponente (a) ein Feststoff der Behandlungslösung beigegeben, welcher ausgewählt ist aus der Gruppe bestehend aus Kohlenhydraten wie z.B. Glucose, Saccharose, Fructose, Galaktose, Mannose, sowie andere Monosaccharide, Disaccharide, Oligosacharide, deren entsprechende Carbonsäurederivate wie Gluconsäuren, Glucuronsauren; Harnstoff, anorganischen Salzen (insbesondere mit Kationen wie z.B Natrium, Kalium, Ammonium, Magnesium, Calzium; und Anionen wie z.B. Chlorid, Nitrat, Sulfat, Phosphat, Polyphosphat, Silikat; und Mischungen hiervon); besonders bevorzugte anorganische Salze sind NaCl, KCl, MgCl2, Na2SO4, K2SO4, MgSO4, Na3PO4, K3PO4, NaNO3, KNO3, Mg(NO3)2.
Diese Stoffe sind derart auszuwählen und/oder werden in ihrer Menge derart beigegeben, dass sie sich in der vorstehend genannten, flüssigen wasserbindenden Komponente (a) und/oder dem Wasser (c) löst, so dass sich eine homogene Behandlungslösung ergibt.
Alternatively or additionally to one of the abovementioned, water-binding components (a), in another preferred embodiment of the invention as a water-binding component (a) a solid is added to the treatment solution, which is selected from the group consisting of carbohydrates, such as, for example, glucose, sucrose, Fructose, galactose, mannose, as well as other monosaccharides, disaccharides, oligosaccharides, their corresponding carboxylic acid derivatives such as gluconic acids, glucuronic acids; Urea, inorganic salts (especially with cations such as sodium, potassium, ammonium, magnesium, calcium, and anions such as chloride, nitrate, sulfate, phosphate, polyphosphate, silicate, and mixtures thereof); Particularly preferred inorganic salts are NaCl, KCl, MgCl 2 , Na 2 SO 4 , K 2 SO 4 , MgSO 4 , Na 3 PO 4 , K 3 PO 4 , NaNO 3 , KNO 3 , Mg (NO 3 ) 2 .
These substances are to be selected and / or added in their amount in such a way that they dissolve in the aforementioned liquid water-binding component (a) and / or the water (c), so that a homogeneous treatment solution results.

In einer besonders bevorzugten Ausführungsform wird als wasserbindende Komponente (a) entweder 1,2,3-Propantriol oder NaCl, oder Mischungen hiervon verwendet; diese wasserbindenden Komponenten (a) haben sich in der Praxis als besonders vorteilhaft aufgrund einfacher Handhabbarkeit sowie gängiger und kostengünstiger Verfügbarkeit sowie guten bis hervorragenden resultierenden Fasereigenschaften erwiesen.In a particularly preferred embodiment, the water-binding component (a) used is either 1,2,3-propanetriol or NaCl, or mixtures thereof; these water-binding components (a) have been found to be particularly advantageous in practice because of their ease of handling as well as more common and less expensive Availability and good to excellent resulting fiber properties proved.

Gemäss einer weiteren Ausführungsform der Erfindung beträgt der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung mindestens 10 Gew.-%. Die vorzugsweise einzusetzende Menge an wasserbindender Komponente (a) kann vom Fachmann aufgrund von Routineversuchen und/oder Berechnung, insbesondere in Abhängigkeit von der Löslichkeit bzw. Mischbarkeit mit Wasser und der Verträglichkeit mit dem Quellmittel (b), leicht ermittelt werden. Gegebenenfalls kann der Anteil an wasserbindender Komponente (a) bis zu 90 Gew.-% betragen. Besonders bevorzugt macht der Anteil der Komponente (a) an der Behandlungslösung den grössten Einzelanteil der gesamten Behandlungslösung aus.According to a further embodiment of the invention, the proportion of the water-binding component (a) in the treatment solution is at least 10% by weight. The amount of water-binding component (a) preferably to be used can be easily determined by the person skilled in the art on the basis of routine experiments and / or calculation, in particular depending on the solubility or miscibility with water and the compatibility with the swelling agent (b). Optionally, the proportion of water-binding component (a) can be up to 90 wt .-%. With particular preference, the proportion of component (a) in the treatment solution accounts for the largest single portion of the total treatment solution.

Gemäss einer besonders vorteilhaften Ausführungsform der Erfindung ist der Anteil und/oder die Art der wasserbindenden Komponente (a) an der Behandlungslösung derart ausgewählt, dass ein verfügbarer, freier Wasseranteil - als der nicht von der wasserbindenden Komponente (a) gebundene Wasseranteil - der Behandlungslösung von höchstens 35 mol/l, vorzugsweise von höchstens 25 mol/l, besonders bevorzugt von höchstens 15 mol/l resultiert.According to a particularly advantageous embodiment of the invention, the proportion and / or the nature of the water-binding component (a) in the treatment solution is selected such that an available, free water content - as the not bound by the water-binding component (a) water content - the treatment solution of at most 35 mol / l, preferably at most 25 mol / l, particularly preferably at most 15 mol / l results.

Besonders vorteilhaft ist der Anteil und/oder die Art der wasserbindenden Komponente (a) an der Behandlungslösung derart ausgewählt, dass im wesentlichen Werte der Fasersteifigkeit (feststellbar durch den Griff), Faserquellung (feststellbar durch Querschnitt, Röntgenbeugung), Farbstoffaufnahme (feststellbar durch Färbeversuche), Vernetzbarkeit in der Hochveredlung (feststellbar durch Trocken- und Nassknittererholungswinkel (insbesondere bei guter Dimensionsstabilität), Scheuerwerte und Festigkeit) erhalten werden, wie sie bei der konventionellen Behandlung in Flüssigammoniak erhalten werden.The proportion and / or the nature of the water-binding component (a) in the treatment solution is particularly advantageously selected such that essentially values of fiber rigidity (detectable by the handle), fiber swelling (detectable by cross section, X-ray diffraction), dye absorption (detectable by dyeing tests) , Crosslinkability in the refining (detectable by dry and wet wrinkle recovery angle (especially with good dimensional stability), abrasion values and strength), as obtained in the conventional treatment in liquid ammonia.

Als Quellmittel (b) wird besonders bevorzugt eine Chemikalie oder eine Mischung von Chemikalien verwendet, welche insbesondere bei einer Konzentration von bereits 1 mol/l in der Behandlungslösung und bei einem Wasseranteil von etwa 85 Gew.-% in einem pH Wert von >= 9, vorzugsweise von >= 11, besonders bevorzugt von >= 13 resultiert. Selbstverständlich kann im Rahmen der Erfindung die Einstellung der genannten pH Werte zusätzlich auch durch geeignete Auswahl und Anteil der wasserbindenden Komponente (a) unterstützt werden.As swelling agent (b) it is particularly preferred to use a chemical or a mixture of chemicals which, in particular at a concentration of already 1 mol / l in the treatment solution and at a water content of about 85 wt%, have a pH of> = 9 , preferably of> = 11, particularly preferably of> = 13 results. Of course, in the context of the invention, the adjustment of said pH values can be additionally supported by suitable selection and proportion of the water-binding component (a).

In weiteren, besonders vorteilhaften Ausführungsformen der Erfindung wird als Quellmittel (b) mindestens eine Chemikalie eingesetzt, welche ausgewählt ist aus der Gruppe bestehend aus Alkalimetallhydroxiden, Erdalkalimetallhydroxiden, Aminen (insbesondere Ethanolamin, Diethanolamin, Triethanolamin, Ethylendiamin, Diethylendiamin, Triethylendiamin, Hexamethylendiamin, Hexamethylentetramin, Diethylamin, Triethylamin, Isopropylamin, t-Butylamin, Glycin, Serin), Thiocyanaten (insbesondere Natrium-, Kalium-, Ammonium-, und/oder Calciumthiocyanat), Kalium-und/oder Natriumiodid, Metallkomplexen (insbesondere Eisen-Weinsäure-Natronlauge, Lösungen der Cuen- bzw. Cuoxamkomplexe), Ammoniak-Lösung, und Mischungen hiervon.In further, particularly advantageous embodiments of the invention, the swelling agent (b) employed is at least one chemical selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, amines (in particular ethanolamine, diethanolamine, triethanolamine, ethylenediamine, diethylenediamine, triethylenediamine, hexamethylenediamine, hexamethylenetetramine, Diethylamine, triethylamine, isopropylamine, t-butylamine, glycine, serine), thiocyanates (especially sodium, potassium, ammonium and / or calcium thiocyanate), potassium and / or sodium iodide, metal complexes (especially iron tartaric acid, solutions the Cu or Cuoxam complexes), ammonia solution, and mixtures thereof.

Verfahren gemäss einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Komponenten (a), (b) und (c) und ihre Anteile an der Behandlungslösung derart ausgewählt sind, dass eine Quellung der Cellulosefasern vorwiegend in amorphen Bereichen bewirkt wird. Es wird derzeit angenommen, dass durch das vorgeschlagene Verfahren eine Quellung der Cellulosefasern vorwiegend in amorphen Bereichen erfolgt (Bildung von Cellulose III/IV), wohingegen bei der Mercerisierung in flüssiger Phase vorwiegend in kristallinen Bereichen erfolgt (Bildung von Cellulose II); hierdurch können gemäss der Erfindung besonders vorteilhafte Fasereigenschaften erzielt werden, welche mit jenen des Ammoniakverfahrens vergleichbar oder diesen sogar überlegen sind.Method according to one of claims 1 to 10, characterized in that the components (a), (b) and (c) and their proportions of the treatment solution are selected such that a swelling of the cellulose fibers is effected predominantly in amorphous regions. It is currently believed that the proposed method swells the cellulose fibers mainly in amorphous areas (formation of cellulose III / IV), whereas in the mercerization in the liquid phase occurs predominantly in crystalline areas (formation of cellulose II); As a result, particularly advantageous fiber properties can be achieved according to the invention, which are comparable or even superior to those of the ammonia process.

Typischerweise wird das erfindungsgemässe Verfahren zur Stabilisierung bei einer Temperatur zwischen -10°C und 180°C, bevorzugt bei einer Temperatur zwischen 15°C und 105°C durchgeführt. Bei Durchführung als batch-Prozess beträgt die Verweilzeit vorteilhaft zwischen 1 h und 4 h, bei kontinuierlicher Durchführung beträgt die Verweilzeit im Behandlungsbad vorteilhaft zwischen 1 und 30 min. Wichtig ist hierbei jedenfalls, die Zusammensetzung der Behandlungslösung entsprechend der Erfindung der möglichen Behandlungszeit anzupassen.Typically, the inventive method for stabilization at a temperature between -10 ° C and 180 ° C, preferably at a temperature between 15 ° C and 105 ° C is performed. When carried out as a batch process, the residence time is advantageously between 1 h and 4 h, with continuous implementation, the residence time in the treatment bath is advantageously between 1 and 30 min. In any case, it is important to adjust the composition of the treatment solution according to the invention of the possible treatment time.

Selbstverständlich können die im Rahmen der im Stand der Technik üblicherweise zu optimierenden Parameter wie Behandlungsdauer, Behandlungstemperatur und Warenspannung während der Behandlung auch im Rahmen des erfindungsgemässen Verfahrens, insbesondere auf den jeweiligen Anwendungsfall abgestimmt, eingestellt werden. Die Einstellung dieser Parameter kann vom Fachmann, ggf. auf der Basis von Routineversuchen, leicht vorgenommen werden.Of course, within the scope of the parameters usually to be optimized in the state of the art, such as treatment duration, treatment temperature and product tension during the treatment, it is also possible to adjust the method according to the invention, in particular to the particular application. The adjustment of these parameters can easily be carried out by a person skilled in the art, possibly on the basis of routine tests.

In besonders vorteilhaften Ausführungsformen des erfindungsgemässen Verfahrens wird nach der Quellbehandlung eine Hochveredelung der Cellulosefasern oder des insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materials durchgeführt. Unter Verfahren der Hochveredlung werden hier und im folgenden Verfahren verstanden, welche die Gebrauchstüchtigkeit des Fertigerzeugnisses nach einer oder mehreren Richtungen hin in einer dauerhaften Art verbessern, insbesondere durch Änderung des Warenbildes durch mechanische Einwirkung (z.B. Ratinieren, Moirieren, Gaufrieren, Plissieren, Erzeugen von Glanzeffekten, etc.), durch chemische Einwirkung (z.B. Erzeugen von Durchbrucheffekten, Dévorant, Luftspitzen, Steifausrüstungen, Quellungsverfahren, Steif-Appreturen, Versehen mit Einbügelstoffen, Weichmachen, Mattieren, Metallisierung) oder durch kombinierte mechanische/chemische Behandlung (z.B. Cloqués, Seersucker, Kräuselkrepp, Craquelé, Klebcloqués), aber auch Verfahren zur Erhöhung des Gebrauchswerts zur Bewirkung von besserer Fülle, Widerstandsfähigkeit, Quellfestigkeit, Schrumpffreiheit, Knitterfreiheit, etc. (siehe hierzu auch M. Peter, Handbuch für Textilingenieure und Textilpraktiker, Grundlagen der Textilveredlung, 10. Auflage 1970, Dr. Spohr-Verlag, Stuttgart ). Es hat sich in der Praxis gezeigt, dass das erfindungsgemässe Verfahren zur Stabilisierung überraschenderweise oftmals insbesondere nach einem anschliessenden Hochveredlungsverfahren herausragend zum Tragen kommt.In particularly advantageous embodiments of the process according to the invention, after the swelling treatment, a high-level refinement of the cellulose fibers or of the material which in particular essentially exclusively comprises cellulose fibers is carried out. Processes of high-grade finishing are here and below understood to mean processes which improve the serviceability of the finished product in one or more directions in a permanent manner, in particular by changing the appearance of the goods by mechanical action (eg, rapping, moire, guarding, pleating, producing gloss effects , etc.), by chemical action (eg creation of breakthrough effects, Dévorant, air tips, stiffening equipment, swelling processes, stiff-finishings, lapping, softening, matting, metallization) or by combined mechanical / chemical treatment (eg Cloqués, Seersucker, Kräuselkrepp, Craquelé, Klebcloqués), but also methods for increasing the utility value for Effecting better fullness, resistance, swelling resistance, shrinkage-free, crease-free, etc. (see also M. Peter, Handbook for Textile Engineers and Textile Practitioners, Foundations of Textile Finishing, 10th Edition 1970, Dr. Ing. Spohr publishing house, Stuttgart ). It has been shown in practice that the stabilization process according to the invention surprisingly often has an outstanding effect, in particular after a subsequent high-grade finishing process.

Es ist daher im Rahmen der Erfindung besonders vorteilhaft, in Abhängigkeit von einer nach der Hochveredelung zu erzielenden Eigenschaft die Komponenten (a), (b) und (c) der Behandlungslösung auszuwählen und/oder in ihren Anteilen an der Behandlungslösung aufeinander abzustimmen. Eine derartige Anpassung der individuellen Behandlungslösung in Abhängigkeit einer nach der Hochveredlung gewünschten Eigenschaft ist vom Fachmann in Routineversuchen leicht vorzunehmen. Insbesondere hohe Laugenkonzentration beeinflusst die Modifikation der Cellulosefaser in Richtung der konventionellen Mercerisation; geringere Laugenkonzentrationen und höherer Anteil an der wasserbindenden Komponente (a) verschieben das erzielbare Produktprofil näher zu Resultaten der konventionellen Flüssigammoniakbehandlung. Unterschiede in den Eigenschaften werden insbesondere durch die Auswahl der Komponenten (a) und (b) bzw. deren Mischungsverhältnisse in der Behandlungslösung gesteuert. Z.B. kann durch Erhöhung der Laugenkonzentration der Griff des Textils steifer erhalten werden, während bei verminderter Laugenkonzentration der Griff des Textils weicher wird. Ebenso erhöht sich das Wasserrückhaltevermögen mit höherer Laugenkonzentration, was die Unterschiede zu Ergebnissen der konventionellen Flüssigammoniakbehandlung vergrössert.It is therefore particularly advantageous within the scope of the invention to select the components (a), (b) and (c) of the treatment solution and / or to coordinate them in their proportions to the treatment solution, depending on a property to be achieved after the high-grade refinement. Such an adaptation of the individual treatment solution as a function of a desired after the refining property is easily carried out by the expert in routine experiments. In particular, high alkali concentration influences the modification of the cellulose fiber in the direction of conventional mercerization; lower lye concentrations and higher proportion of the water-binding component (a) shift the achievable product profile closer to the results of the conventional liquid ammonia treatment. Differences in properties are controlled in particular by the selection of components (a) and (b) or their mixing ratios in the treatment solution. For example, by increasing the caustic concentration, the handle of the fabric may be stiffer, while with reduced caustic concentration, the fabric's feel gets softer. Similarly, the water retention capacity increases with higher lye concentration, which increases the differences to results of conventional liquid ammonia treatment.

Die Hochveredlung kann hierbei nach der Behandlung mit der erfindungsgemässen Behandlungslösung entweder mit oder ohne Zwischentrocknung durchgeführt werden.The high-grade finishing can be carried out after treatment with the treatment solution according to the invention either with or without intermediate drying.

Eine besonders vorteilhafte Eigenschaft des erfindungsgemässen Verfahrens ist, dass die Behandlung ohne gebundene Warenführung erfolgen kann. Durch die insgesamt im Rahmen der Erfindung verringerte Faserquellung treten auch wesentlich geringere Schrumpfkräfte auf, so dass auch der Einsprung der Ware geringer ist als bei Mercerisierverfahren in flüssiger Phase gemäss Stand der Technik.A particularly advantageous feature of the method according to the invention is that the treatment can be carried out without bonded goods guide. Due to the total reduced in the context of the invention, fiber swelling also occur much lower shrinkage forces, so that the jump of the product is lower than Mercerisierverfahren in the liquid phase according to the prior art.

Die Erfindung betrifft weiter die Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern, oder von insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien, zur Erhöhung des resultierenden Anteils der in amorphen Bereichen gequollenen Cellulosefasern und/oder zur Verringerung des resultierenden Anteils der in kristallinen Bereichen gequollenen Cellulosefasern.The invention further relates to the use of a water-binding component as additive in a treatment solution for stabilizing cellulose fibers, or of materials substantially exclusively comprising cellulose fibers, to increase the resulting proportion of cellulose fibers swollen in amorphous regions and / or to reduce the resulting proportion of cellulose fibers crystalline areas of swollen cellulose fibers.

Die Erfindung wird nachfolgend anhand eines konkreten Ausführungsbeispiels näher erläutert, ohne dass der Gegenstand der Erfindung jedoch hierauf zu beschränken wäre.The invention will be explained in more detail with reference to a concrete embodiment, without, however, the subject matter of the invention would be limited thereto.

Ein Textil aus 100% Baumwolle wurde bei Raumtemperatur mit den in Tabelle 1 genannten Behandlungslösungen auf einem Foulard mit 1 m/min Warengeschwindigkeit mit einer Flottenaufnahme von 50 - 66% imprägniert und 4 h bei RT in der Lösung verweilt. Anschliessend wurde mit kaltem Weichwasser ausgewaschen, mit 1 ml/l Essigsäure neutralisiert, bei 40°C getrocknet und nach dem üblichen STK-Verfahren (STK = Schock Trocknung Kondensation) hochveredelt. Für die Hochveredlung wurden bei einer Flottenaufnahme von rund 50-70% 40 g/l Arkofix® NDF (DMDHEU-basiertes Produkt, Clariant AG, Basel, Schweiz) und 10 g/l MgCl2 als Katalysator eingesetzt. Nach 1 min Trocknung bei 130°C erfolgte Kondensation bei 170°C (Dauer 45 sec).A textile made of 100% cotton was treated at room temperature with the treatment solutions listed in Table 1 on a padder at a speed of 1 m / min with a liquor pick-up of 50%. 66% impregnated and 4 h at RT in the solution. Subsequently, it was washed with cold soft water, neutralized with 1 ml / l acetic acid, dried at 40 ° C and highly refined by the usual STK process (STK = shock drying condensation). For refining, 40 g / l Arkofix® NDF (DMDHEU-based product, Clariant AG, Basel, Switzerland) and 10 g / l MgCl 2 were used as catalyst at a liquor pick-up of about 50-70%. After drying for 1 min at 130 ° C., condensation took place at 170 ° C. (duration 45 sec).

Eine Bewertung des erreichten Effekts erfolgt durch Bestimmung des Wasserrückhaltevermögens (WRV) und des Trockenknitterwinkels (TKW K+S) nach DIN 53890 mit 5 Minuten Erholungszeit, der Steifigkeit (%) und der Schrumpfung (%) des ausgerüsteten Produkts. Zum Vergleich sind Resultate jeweils nach einer Behandlung mit 125 bzw. 200 g/l NaOH bzw. KOH in Wasser und nach einer Flüssigammoniakbehandlung, und anschließender, identischer Hochveredlung aufgeführt. Es zeigt sich, dass die resultierenden Eigenschaften des Textils unter Verwendung des erfindungsgemässen Verfahrens nach der Hochveredlung mit den Eigenschaften eines Textils nach einer Ammoniakbehandlung mit nachfolgender, identischer Hochveredlung vergleichbar, bzw. überlegen ist. Hohe TKW bestätigen gutes Knitterverhalten der erfindungsgemäss behandelten Proben, insbesondere im Vergleich zu den konventionell NH3 behandelten Proben. Die konventionelle Mercerisation fällt bei den Ergebnissen deutlich ab. Vergleichbare Werte bei Wasserrückhaltevermögen, Steifigkeit und Schrumpfung bestätigen die Möglichkeit durch systematische Anpassung der Zusammensetzung der Behandlungslösung Eigenschaften der textilen Materialien gezielt verändern zu können. Tabelle 1: Vergleichsmessungen Behandlung NaOH Glycerin NaCl TKW WRV Steifigk. Schrumpf. g/l g/l g/l ° % % % 125 200 - 241,7 27,3 89,5 97,3 125 230 - 221,7 35,7 102,6 94,5 125 460 - 236,8 32,4 84,2 95,5 125 - 100 196,6 32,5 92,1 93,6 NH3 (klassisch) - - - 243,6 27,9 105,3 92,9 Merc./Laug. 125 - - 187,3 30,91 76,3 94,5 Merc./Laug. 200 - - 188,8 35,02 97,4 86,6 Behandlung KOH Glycerin NaCl TKW WRV Steifigk. Schrumpf. g/l g/l g/l ° % % % 175 200 - 231,8 26,1 89,5 97,3 NH3 (klassisch) - - - 243,6 27,9 105,3 92,9 Merc./Laug. 175 - - 190,2 30,9 84,2 92,7 Merc./Laug. 280 - - 203,5 36,5 115,8 85,0 An evaluation of the achieved effect is carried out by determining the water retention capacity (WRV) and the dry crease angle (TKW K + S) according to DIN 53890 with 5 minutes recovery time, the stiffness (%) and the shrinkage (%) of the finished product. For comparison, results are given in each case after treatment with 125 g or 200 g / l NaOH or KOH in water and after liquid ammonia treatment, followed by identical high-grade finishing. It can be seen that the resulting properties of the textile using the process according to the invention after finishing are comparable or superior to the properties of a textile after ammonia treatment followed by identical high-grade finishing. High TKWs confirm good crease behavior of the samples treated according to the invention, in particular in comparison with the conventional NH 3- treated samples. Conventional mercerization falls significantly in the results. Comparable values for water retention, rigidity and shrinkage confirm the possibility of systematically adjusting the composition of the treatment solution to be able to change the properties of the textile materials in a targeted manner. Table 1: Comparison measurements treatment NaOH glycerin NaCl TKW WRV Steifigk. Shrinking. g / l g / l g / l ° % % % 125 200 - 241.7 27.3 89.5 97.3 125 230 - 221.7 35.7 102.6 94.5 125 460 - 236.8 32.4 84.2 95.5 125 - 100 196.6 32.5 92.1 93.6 NH 3 (classic) - - - 243.6 27.9 105.3 92.9 Merc./Laug. 125 - - 187.3 30.91 76.3 94.5 Merc./Laug. 200 - - 188.8 35.02 97.4 86.6 treatment KOH glycerin NaCl TKW WRV Steifigk. Shrinking. g / l g / l g / l ° % % % 175 200 - 231.8 26.1 89.5 97.3 NH 3 (classic) - - - 243.6 27.9 105.3 92.9 Merc./Laug. 175 - - 190.2 30.9 84.2 92.7 Merc./Laug. 280 - - 203.5 36.5 115.8 85.0

Claims (16)

Verfahren zur Stabilisierung von Cellulosefasern und/oder eines Cellulosfasern enthaltenden Materials, insbesondere einer textilen Warenbahn enthaltend Cellulosefasern, dadurch gekennzeichnet, dass die Cellulosefasern mit einer Behandlungslösung in Kontakt gebracht werden, wobei die Behandlungslösung umfasst: (a) eine wasserbindende Komponente, (b) ein Quellmittel, sowie (c) Wasser. A process for stabilizing cellulose fibers and / or a cellulose fiber-containing material, in particular a textile web containing cellulose fibers, characterized in that the cellulose fibers are brought into contact with a treatment solution, the treatment solution comprising: (a) a water-binding component, (b) a swelling agent, as well (c) water. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass das Cellulosefasern enthaltende Material, insbesondere die textile Warenbahn im wesentlichen ausschliesslich Cellulosefasern umfasst.A method according to claim 1, characterized in that the cellulosic fibers-containing material, in particular the textile web essentially comprises exclusively cellulose fibers. Verfahren gemäss Anspruch 1, dadurch gekennzeichnet, dass das Cellulosefasern enthaltende Material, insbesondere die textile Warenbahn enthaltend Cellulosefasern, im wesentlichen, vorzugsweise vollständig, frei ist von auf regenerierter Cellulose basierenden Garnen und Fasern.A method according to claim 1, characterized in that the cellulose fiber-containing material, in particular the textile web containing cellulose fibers, substantially, preferably completely, is free of regenerated cellulose-based yarns and fibers. Verfahren gemäss einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass als eine wasserbindende Komponente (a) ein Alkohol, insbesondere ein mehrwertiger, vorzugsweise aliphatischer Alkohol, verwendet wird, besonders bevorzugt ausgewählt aus der Gruppe bestehend aus Methanol, Ethanol, 1-Propanol, 2-Propanol, 1,3-Propandiol, 1,2-Propandiol, 1,2,3-Propantriol, 1-Butanol, 2-Butanol, tert.-Butylalkohol, 1,2-Butandiol, 1,3-Butandiol, 1,4-Butandiol, 2,3-Butandiol und Mischungen hiervon.Method according to one of claims 1 to 3, characterized in that as a water-binding component (a) an alcohol, in particular a polyhydric, preferably aliphatic alcohol is used, more preferably selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1,3-propanediol, 1,2-propanediol, 1,2,3-propanetriol, 1-butanol, 2-butanol, tert-butyl alcohol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, 2,3-butanediol and mixtures thereof. Verfahren gemäss einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass als eine wasserbindende Komponente (a) ein Feststoff der Behandlungslösung beigegeben wird, welcher ausgewählt ist aus der Gruppe bestehend aus Kohlenhydraten, Harnstoff, anorganischen Salzen und Mischungen hiervon.A process according to any one of claims 1 to 4, characterized in that as a water-binding component (a) a solid is added to the treatment solution, which is selected from the group consisting of carbohydrates, urea, inorganic salts and mixtures thereof. Verfahren gemäss einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass als wasserbindende Komponente (a) 1,2,3-Propantriol, NaCl und Mischungen hiervon verwendet werden.A process according to any one of claims 1 to 5, characterized in that the water-binding component (a) used is 1,2,3-propanetriol, NaCl and mixtures thereof. Verfahren gemäss einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung mindestens 10 Gew.-% beträgt, vorzugsweise zwischen 10 Gew.-% und 90 Gew.-%.Method according to one of claims 4 to 6, characterized in that the proportion of the water-binding component (a) in the treatment solution is at least 10 wt .-%, preferably between 10 wt .-% and 90 wt .-%. Verfahren gemäss einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass der Anteil der wasserbindenden Komponente (a) an der Behandlungslösung derart ausgewählt ist, dass ein verfügbarer, freier Wasseranteil der Behandlungslösung von höchstens 35 mol/l, vorzugsweise von höchstens 25 mol/l, besonders bevorzugt von höchstens 15 mol/l resultiert.A method according to any one of claims 4 to 7, characterized in that the proportion of the water-binding component (a) is selected on the treatment solution such that an available, free water content of the treatment solution of at most 35 mol / l, preferably of at most 25 mol / l , particularly preferably at most 15 mol / l results. Verfahren gemäss einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass als Quellmittel (b) eine Chemikalie oder eine Mischung von Chemikalien verwendet wird, welche insbesondere bei einer Konzentration von mindestens 1 mol/l in der Behandlungslösung in einem pH Wert von >= 9, vorzugsweise von >= 11, besonders bevorzugt von >= 13 resultiert.A method according to any one of claims 1 to 8, characterized in that the swelling agent (b) is a chemical or a mixture of chemicals is used, which in particular at a concentration of at least 1 mol / l in the treatment solution in a pH of> = 9 , preferably of> = 11, particularly preferably of> = 13 results. Verfahren gemäss Anspruch 9, dadurch gekennzeichnet, dass als Quellmittel (b) mindestens eine Chemikalie eingesetzt wird, welche ausgewählt ist aus der Gruppe bestehend aus Alkalimetallhydroxiden, Erdalkalimetallhydroxiden, Aminen, Thiocyanaten, Iodiden, Metallkomplexen, Ammoniak-Lösung, und Mischungen hiervon.A method according to claim 9, characterized in that as the swelling agent (b) at least one chemical is used which is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, amines, thiocyanates, iodides, metal complexes, ammonia solution, and mixtures thereof. Verfahren gemäss einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass die Komponenten (a), (b) und (c) und ihre Anteile and der Behandlungslösung derart ausgewählt sind, dass eine Quellung der Cellulosefasern vorwiegend in amorphen Bereichen bewirkt wird.A process according to any one of claims 1 to 10, characterized in that the components (a), (b) and (c) and their proportions in the treatment solution are selected such that swelling of the cellulose fibers is effected predominantly in amorphous regions. Verfahren gemäss einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die Stabilisierung bei einer Temperatur zwischen -10°C und 180°C, bevorzugt bei einer Temperatur zwischen 15°C und 105°C durchgeführt wird.Method according to one of claims 1 to 11, characterized in that the stabilization at a temperature between -10 ° C and 180 ° C, preferably at a temperature between 15 ° C and 105 ° C is performed. Verfahren gemäss einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass nach der Quellbehandlung eine Hochveredelung der Cellulosefasern oder des insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materials durchgeführt wird, insbesondere ein Schock-Trocknung-Kondensationsverfahren oder bevorzugt ein Verfahren der Feuchtvernetzung.Method according to one of claims 1 to 12, characterized in that after the swelling treatment, a refining of the cellulose fibers or of the material comprising in particular essentially exclusively cellulose fibers is carried out, in particular a shock-drying condensation process or preferably a process of wet crosslinking. Verfahren gemäss Anspruch 13, dadurch gekennzeichnet, dass in Abhängigkeit von einer nach der Hochveredelung zu erzielenden Eigenschaft die Komponenten (a), (b) und (c) der Behandlungslösung ausgewählt und/oder in ihren Anteilen an der Behandlungslösung aufeinander abgestimmt werden.A method according to claim 13, characterized in that depending on a property to be achieved after the refining property components (a), (b) and (c) of the treatment solution are selected and / or matched in their proportions of the treatment solution. Verfahren gemäss einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass die Stabilisierung in einem kontinuierlichen Prozess und mit ungebundener Warenführung, insbesondere mit ungebundener Warenführung erfolgt.Method according to one of claims 1 to 14, characterized in that the stabilization takes place in a continuous process and with unbound goods management, in particular with unbound goods management. Verwendung einer wasserbindenden Komponente als Zusatz in einer Behandlungslösung zur Stabilisierung von Cellulosefasern, oder von insbesondere im wesentlichen ausschliesslich Cellulosefasern umfassenden Materialien, zur Erhöhung des resultierenden Anteils der in amorphen Bereichen gequollenen Cellulosefasern und/oder zur Verringerung des resultierenden Anteils der in kristallinen Bereichen gequollenen Cellulosefasern.Use of a water-binding component as additive in a treatment solution for the stabilization of cellulose fibers, or of materials substantially exclusively comprising cellulose fibers, to increase the resulting proportion of cellulose fibers swollen in amorphous regions and / or to reduce the resulting proportion of cellulose fibers swollen in crystalline regions.
EP05102374A 2005-03-24 2005-03-24 Process for the stabilisation of cellulosic fibres, especially of a textile web comprising cellulosic fibres Not-in-force EP1705285B1 (en)

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AT05102374T ATE490367T1 (en) 2005-03-24 2005-03-24 METHOD FOR STABILIZING CELLULOSE FIBERS, IN PARTICULAR A TEXTILE WEB CONTAINING CELLULOSE FIBERS
DE502005010612T DE502005010612D1 (en) 2005-03-24 2005-03-24 Process for the stabilization of cellulose fibers, in particular a textile web containing cellulose fibers
EP05102374A EP1705285B1 (en) 2005-03-24 2005-03-24 Process for the stabilisation of cellulosic fibres, especially of a textile web comprising cellulosic fibres
CNA2006800089038A CN101146949A (en) 2005-03-24 2006-03-21 Process for the stabilisation of cellulosic fibres, especially of a textile web comprising cellulosic fibres
BRPI0609467-8A BRPI0609467A2 (en) 2005-03-24 2006-03-21 a method for stabilizing cellulose fibers, especially of a textile web comprising cellulose fibers
PCT/EP2006/060924 WO2006100249A1 (en) 2005-03-24 2006-03-21 Method for stabilizing cellulose fibers, especially of a textile web that comprises cellulose fibers
RU2007139334/04A RU2007139334A (en) 2005-03-24 2006-03-21 METHOD FOR STABILIZING CELLULOSE FIBERS, ESPECIALLY TEXTILE FABRIC CONTAINING CELLULOSE FIBERS

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Publication number Priority date Publication date Assignee Title
GB516162A (en) * 1937-07-27 1939-12-22 Walter Rotta Process for producing wash-resistant stiffening effects on textiles
GB612745A (en) * 1946-05-31 1948-11-17 Calico Printers Ass Ltd Improvements in the treatment of regenerated cellulose fabrics to reduce their tendency to shrink
GB727882A (en) * 1950-01-17 1955-04-13 Tootal Broadhurst Lee Co Ltd Improvements in and relating to textile materials
DE2405006A1 (en) * 1973-02-14 1974-08-29 Heberlein & Co Ag METHOD AND DEVICE FOR IMPROVING THE FIBER STRUCTURE OF TEXTILE MATERIAL CONTAINING CELLULOSE FIBERS
WO2003050346A1 (en) * 2001-12-11 2003-06-19 Kimberly-Clark Worldwide, Inc. High wet resiliency curly cellulose fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB516162A (en) * 1937-07-27 1939-12-22 Walter Rotta Process for producing wash-resistant stiffening effects on textiles
GB612745A (en) * 1946-05-31 1948-11-17 Calico Printers Ass Ltd Improvements in the treatment of regenerated cellulose fabrics to reduce their tendency to shrink
GB727882A (en) * 1950-01-17 1955-04-13 Tootal Broadhurst Lee Co Ltd Improvements in and relating to textile materials
DE2405006A1 (en) * 1973-02-14 1974-08-29 Heberlein & Co Ag METHOD AND DEVICE FOR IMPROVING THE FIBER STRUCTURE OF TEXTILE MATERIAL CONTAINING CELLULOSE FIBERS
WO2003050346A1 (en) * 2001-12-11 2003-06-19 Kimberly-Clark Worldwide, Inc. High wet resiliency curly cellulose fibers

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RU2007139334A (en) 2009-04-27
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