EP0976866B1 - Textile fabrics - Google Patents

Textile fabrics Download PDF

Info

Publication number
EP0976866B1
EP0976866B1 EP99114691A EP99114691A EP0976866B1 EP 0976866 B1 EP0976866 B1 EP 0976866B1 EP 99114691 A EP99114691 A EP 99114691A EP 99114691 A EP99114691 A EP 99114691A EP 0976866 B1 EP0976866 B1 EP 0976866B1
Authority
EP
European Patent Office
Prior art keywords
hydroxide
oxide
fibers
textile fabric
meth
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP99114691A
Other languages
German (de)
French (fr)
Other versions
EP0976866A1 (en
Inventor
Hermann Seyffer
Ralf Mossbach
Klaus Haas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of EP0976866A1 publication Critical patent/EP0976866A1/en
Application granted granted Critical
Publication of EP0976866B1 publication Critical patent/EP0976866B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/425—Cellulose series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • D04H1/645—Impregnation followed by a solidification process
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/44—Oxides or hydroxides of elements of Groups 2 or 12 of the Periodic System; Zincates; Cadmates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic System; Aluminates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/80—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides
    • D06M11/82—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with boron or compounds thereof, e.g. borides with boron oxides; with boric, meta- or perboric acids or their salts, e.g. with borax
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
    • D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol

Definitions

  • the present invention relates to textile fabrics which a structure of fibers comprising, which by means of a polymer Binders are interconnected (nonwovens) and a Process for their production.
  • a structure of fibers is used to produce a nonwoven (Fleece), which is then solidified or glued.
  • the fibers can have a preferred direction or non-directional his.
  • Various processes are known for producing nonwovens, e.g. (1) the mechanical formation of fleece from staple fibers or filaments; (2) aerodynamic web formation from staple fibers or filaments; (3) hydrodynamic web formation from staple fibers or filaments and (4) electrostatic web formation Fine fibers or filaments.
  • the so obtained Nonwovens become nonwovens using different processes solidified.
  • Nonwovens are used for a large number of applications used. For example, nonwovens are increasingly as cleaning and Wipes, dishcloths and napkins used. In these applications it is important that e.g. spilled liquids, such as milk, coffee, etc., quickly and completely when wiping over soaked up and completely dried on damp surfaces become. The speed and completeness with which Liquids are sucked up, determine the usage properties of a cleaning and wiping cloth and are the main criteria for the goodness of the item.
  • a cleaning cloth absorbs liquids the quicker the faster their transport takes place on the fiber surface.
  • a hydrophilic The surface is easily and quickly wetted by water. The water spreads very quickly over the entire surface of the nonwoven and the water is "sucked away" from the contact point. hydrophobic In contrast, surfaces are not wetted. You run the Liquid therefore also no further and are for one use unsuitable as cleaning cloth or wipe.
  • Crucial for the crowd of liquid that can be absorbed is, among other things also the swelling behavior of the fiber.
  • a hydrophobic binder that largely envelops the fiber affects the kinetics of the Water intake.
  • nonwovens To improve the water absorption properties of nonwovens are sometimes surface-active hydrophilizing in their manufacture Agents such as emulsifiers, surfactants or wetting agents are used. This makes for excellent initial hydrophilicity reached.
  • these nonwovens have the disadvantage that the hydrophilic agents through water or other aqueous media be washed out gradually. After repeated contact with water the product becomes increasingly hydrophobic. The flushing, cleaning or Wipe thus loses its ability to wash soak up aqueous liquids quickly. The cloth will consequently unusable for further use, and must be disposed of be, although the mechanical strength of the cloth for further Cycles of use are still sufficient. This is with regard to one responsible handling of raw materials disadvantageous.
  • the present invention was therefore based on the object To provide hydrophilic fabrics, its hydrophilicity is retained even after repeated washing.
  • the present invention therefore relates to a textile fabric, which comprises a structure of fibers, which by means of a polymer Binder are interconnected, and characterized is that the fabric is an oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn in a colloidal dispersion and one selected from sulfosuccinates and sulfosuccinamates Contains wetting agents.
  • the present invention further relates to a method of manufacture of a textile fabric, in which a structure of Impregnated fibers with a dispersion of a polymeric binder, dried, and optionally hardened, the result is characterized in that the structure also (i) with a colloidal Suspension of an oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn is impregnated or with a solution Precursor of an oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn is impregnated and the formation of the oxide and / or Hydroxide is induced in a colloidally disperse distribution and (ii) the structure with one among sulfosuccinates and sulfosuccinamates selected wetting agent is impregnated.
  • the textile fabric according to the invention preferably contains 1 - 20% by weight, based on the dry weight of the polymeric binder, in particular 3-15% by weight and particularly preferably 5-15% by weight, oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn.
  • the textile fabric according to the invention preferably contains 1 - 20% by weight, based on the dry weight of the polymeric binder, in particular 2-10% by weight, wetting agent.
  • oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn is intended to be a broad one for the purposes of the present invention Have meaning. So in addition to the simple Oxides and hydroxides of the specified elements also their hydrated Forms with changing water content and the oxoanion salts with e.g. Alkali metal or alkaline earth metal cations, e.g. the silicates and aluminates. Furthermore, the term Include oxides and hydroxides in different condensation stages, e.g. the island, ribbon and layered silicates, as well as mixed Oxides and / or hydroxides. Preferred oxides and / or hydroxides are silica, aluminum oxide, aluminum hydroxide, aluminosilicates, e.g. Bentonite, Montmorillonite.
  • Sulfosuccinic diesters have proven to be particularly useful which the alcohols used for the esterification have a chain length of 4 to 8 carbon atoms, e.g. Sodium di (ethylhexyl) sulfosuccinate.
  • the invention is not subject to any of the fibers used significant restrictions. All types of fibers are suitable currently used in the manufacture of nonwovens e.g. Polypropylene, polyester, polyamide fibers, cellulose fibers, such as viscose fibers, two-component fibers, e.g. Polyester copolyester, Polypropylene-polyethylene, polyester-polyamide, Polyester-polypropylene and polyamide-6-polyamide-6,6 fibers.
  • Other suitable fibers are polyacrylonitrile, polyimide, Polytetrafluoroethylene and poly (phenylene sulfide) fibers, mineral Fibers or glass fibers and semi-synthetic fibers such as acetate fibers. Polypropylene fibers, polyester fibers and cellulose fibers and mixed fibers of the materials mentioned are preferred.
  • All commonly used polymeric binders can be used. These include in particular the polyacrylate dispersions, for example based on C 1 -C 4 -alkyl (meth) acrylates, (meth) acrylic acid and / or (meth) acrylamide.
  • Amide-containing polymers or copolymers can be crosslinked with NN-methylol compounds, such as urea-formaldehyde or melamine-formaldehyde resins. Internal crosslinking takes place when N-methylol (meth) acrylamide is incorporated.
  • Rubber latices such as synthetic styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR), polyvinyl ester dispersions, optionally copolymerized with ethylene and / or vinyl chloride, such as copolymers of vinyl acetate and ethylene or vinyl acetate, vinyl chloride and ethylene, and also polyvinyl alcohols are also suitable suitable.
  • Polyurethane dispersions and aminoplast and phenoplast precondensates can also be mentioned.
  • binder which comprises a polymer of monomers which, under C 1 to C 4, alkyl (meth) acrylates, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, styrene, butadiene, ( Meth) acrylonitrile, C 1 to C 6 alkanoic acid vinyl esters, vinyl chloride, ethylene and vinyl alcohol are selected.
  • the application amount of binder, expressed as dry binder, based on the total weight of the bonded nonwoven, is generally 10 to 40% by weight, preferably about 20% by weight.
  • the oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn in the nonwoven fabric according to the invention in a colloidally disperse distribution is present.
  • coarser particles as they occasionally do as anti-blocking additives or other additives the intended effect is not achieved.
  • Cold disperse is intended to mean that the majority of the particles, e.g. more than 90% by weight of the oxide and / or hydroxide one size of ⁇ 1 ⁇ m, in particular ⁇ 0.1 ⁇ m.
  • the colloidal disperse Distribution can be within the scope of the present invention e.g. achieve by using a colloidal suspension of the oxide and / or hydroxide, e.g. a sol, such as a hydrosol, or one Gel starts or the formation of the oxide and / or hydroxide in colloidal form e.g. as a gel, induced in the fleece.
  • Al 3+ salts tend to coagulate the dispersion or coagulation occurs when an attempt is made to convert the Al 3+ salts into Al (OH) 3 by adding a base, for example ammonia.
  • a base for example ammonia.
  • a colloidal suspension preferably a freshly produced colloidal suspension
  • it is possible to impregnate the fleece with the solution of a precursor of the oxide and / or hydroxide and to induce the formation of the oxide and / or hydroxide in the fleece.
  • the fleece can be impregnated with a solution of Al 3+ ions, for example an Al 2 (SO 4 ) 3 solution or an Al (NO 3 ) 3 solution, and preferably dried.
  • the fleece is then impregnated with the binder dispersion.
  • the neutral to slightly alkaline pH of the dispersion leads to a conversion of the Al 3+ ions to Al (OH) 3 .
  • a pH-regulating substance for example a buffer, can be added to the binder dispersion in order to establish a neutral to slightly alkaline pH, for example in the range from 6 to 9.
  • the fleece or the nonwoven fabric could also be impregnated with a water glass solution, ie sodium orthosilicate solution, after which colloidal silica can be produced by treatment with dilute mineral acid, for example hydrochloric acid.
  • a water glass solution ie sodium orthosilicate solution
  • colloidal silica can be produced by treatment with dilute mineral acid, for example hydrochloric acid.
  • Another example is treatment with an aqueous solution of borax (Na 2 B 4 O 7 .10 H 2 O) followed by drying.
  • the impregnation of the fleece or nonwoven with the colloidal Suspension of the oxide / hydroxide or the impregnation with the Solution of the precursor and induction of oxide / hydroxide formation can be at any time during manufacture of the textile fabric. It is preferred that they before or simultaneously with the impregnation with the binder respectively.
  • the impregnation of the fleece or nonwoven fabric with the wetting agent can be at any time during manufacture of the fabric according to the invention take place. In general it is advisable to impregnate with the wetting agent to be carried out simultaneously with the impregnation of the binder. For this purpose, the wetting agent simply becomes the aqueous binder dispersion given.
  • Polyester cellulose fleeces (70PES / 30ZW; 1.7 dtex; fiber length 38 mm; 30 g / m 2 ) a length of 35 to 50 cm and a width of 25 to 28 cm were lengthways in an impregnation and suction system an endless PES sieve belt through a 25% binder liquor and over a suction device.
  • the binder dispersion used was Acronal DS 2350 X TM (polyacrylate dispersion based on butyl acrylate and acrylonitrile).
  • the belt speed was 1 to 2 m per min.
  • the wet application was set to approximately 160% via the adjustable strength of the suction, which corresponds to a dry application of approximately 40%.
  • the binder liquor contained the additives listed in the table below (% by weight, based on the dry weight of the binder).
  • the impregnated nonwovens were placed on the belt of a Mathis sieve belt dryer type TH, secured against slipping and dried at 150 ° C. for 2 minutes. The top of each fleece was marked and the quantity applied was determined by weighing.
  • the nonwovens thus obtained were immediately and after five times Wash subjected to a wetting test.
  • the colored Run test used for the quantitative determination of the hydrophilicity. This test basically works as follows ab: On the diagonally clamped nonwoven, a defined amount of colored water applied. Depending on the hydrophilicity the water runs off or penetrates more or less quickly into the nonwoven. Characteristic color spots, e.g. circular for quick penetration into the nonwoven or narrow and elongated for slow penetration and preferred Expire, get. The assessments are based on a grading scale assigned.
  • test specimen measuring 21 x 5 cm is clamped in a frame that describes an inclination of 30 degrees with respect to the horizontal.
  • the side at the top in the dryer faces down during this test.
  • 0.5 ml of test liquid is applied from a height of 10 mm and a distance from the upper fleece edge of 30 mm.
  • the test liquid consisted of 2 g of Hostapal CV solution, 2.5 g of Lurantin-Lightfast-Turquoise Blue-GL to 1 l of completely demineralized water. After the test specimen has dried (hanging), the top of the fleece is examined and a grade of 0 for no wetting (test liquid completely drained off) to 5 for total wetting is assigned.
  • Examples 4 and 10 a nonwoven fabric was obtained after 5 washes is hydrophilic. These examples contained a sulfosuccinic acid ester in connection with colloidal silica. Without silica (Example 2) is even when using the same emulsifier no permanent hydrophilicity obtained. Other emulsifiers (Examples 5, 6) do not lead to the desired permanent hydrophilicity. Also polymeric additives (example 8) or higher amounts of Silicic acid in the absence of sulfosuccinic acid esters (example 9) do not lead to the desired properties.
  • Standard cellulose nonwovens (Whatman # 4; 100% cellulose), 35 to 50 cm long and 25 to 28 cm wide, were pulled through a 10% binder liquor (Acronal DS 2350 X), squeezed and then in a Mathis stenter dryer with gauze.
  • the liquor contained the additives listed in the table below.
  • the nonwovens were first impregnated in the padding with a 5% Al 2 (SO 4 ) 3 solution, squeezed and dried and only then soaked in the padding with binder and dried again.
  • the nonwovens obtained were subjected to an absorbency test. For this purpose, a 5 times washed and dried fleece strip (70 x 30 mm) with an immersion depth of about 5 mm was hung in the test liquid (see above) and after 30 s the rise height was noted. The penetration rate in the nonwoven was also measured. For this purpose, 0.1 ml of test liquid was placed on the front of 5 times washed and dried nonwoven fabric samples and the time was noted until the drop completely penetrated the nonwoven fabric. The results are shown in the table below. Vers. No. mineral.

Abstract

A flat hydrophilic textile (fleece) retains its hydrophilic character after multiple washings by treatment with colloidal dispersions of specific oxides and/or hydroxides in combination with specific wetting agents. The flat textile comprises a fiber structure in which the fibers are held together by a polymer binder, and the flat texture contains an oxide and/or hydroxide of Al, B, Si, Mg, Ti, and/or Zn in colloidal dispersion and a sulfosuccinate or sulfosuccinamate wetting agent. An Independent claim is included for the preparation of the textile by impregnating the fiber structure with a polymer binder dispersion, drying and optionally hardening, and (i) impregnation with a colloidal suspension of the above oxides and/or hydroxides, with a solution of a precursor of these oxides and/or hydroxides, inducement of a colloidal dispersion of the oxides and/or hydroxides, and (ii) impregnation of the structure with a sulfosuccinate or sulfosuccinamate.

Description

Die vorliegende Erfindung betrifft textile Flächengebilde, die ein Gefüge von Fasern umfassen, welche mittels eines polymeren Bindemittels miteinander verbunden sind (Vliesstoffe) und ein Verfahren zu ihrer Herstellung.The present invention relates to textile fabrics which a structure of fibers comprising, which by means of a polymer Binders are interconnected (nonwovens) and a Process for their production.

Zur Herstellung eines Vliesstoffs wird ein Gefüge von Fasern (Vlies) abgelegt, das anschließend verfestigt bzw. verklebt wird. Die Fasern können eine Vorzugsrichtung aufweisen oder ungerichtet sein. Zur Vliesherstellung sind verschiedene Verfahren bekannt, z.B. (1) die mechanische Vliesbildung aus Spinnfasern oder Filamenten; (2) die aerodynamische Vliesbildung aus Spinnfasern oder Filamenten; (3) die hydrodynamische Vliesbildung aus Spinnfasern oder Filamenten und (4) die elektrostatische Vliesbildung aus Feinstfasern oder Filamenten. Die auf diese Weise gewonnenen Vliese werden nach unterschiedlichen Verfahren zu Vliesstoffen verfestigt.A structure of fibers is used to produce a nonwoven (Fleece), which is then solidified or glued. The fibers can have a preferred direction or non-directional his. Various processes are known for producing nonwovens, e.g. (1) the mechanical formation of fleece from staple fibers or filaments; (2) aerodynamic web formation from staple fibers or filaments; (3) hydrodynamic web formation from staple fibers or filaments and (4) electrostatic web formation Fine fibers or filaments. The so obtained Nonwovens become nonwovens using different processes solidified.

Die größte Bedeutung haben nasse Bindeverfahren. Hierbei wird das Vlies mit einem wässrigen Bindemittel, z.B. einem Polymerlatex behandelt und anschließend, gegebenenfalls nach Entfernung von überschüssigem Bindemittel, getrocknet und gegebenenfalls gehärtet. Es gibt eine große Zahl weiterentwickelter Verfahren, die aber letztlich auf diesem Grundprinzip beruhen.Wet binding methods are of greatest importance. Here is the Fleece with an aqueous binder, e.g. a polymer latex treated and then, if necessary after removal of excess binder, dried and optionally hardened. There are a large number of advanced procedures that but ultimately based on this basic principle.

Vliesstoffe werden für eine große Zahl von Einsatzmöglichkeiten verwendet. So werden Vliesstoffe z.B. zunehmend als Putz- und Wischtücher, Spültücher und Servietten verwendet. Bei diesen Anwendungen ist es wichtig, daß z.B. verschüttete Flüssigkeiten, wie Milch, Kaffee, usw., beim Darüberwischen rasch und vollständig aufgesaugt und feuchte Oberflächen vollständig getrocknet werden. Die Geschwindigkeit und die Vollständigkeit, mit der Flüssigkeiten aufgesaugt werden, bestimmen die Gebrauchseigenschaften eines Putz- und Wischtuches und sind die Hauptkriterien für die Güte des Artikels.Nonwovens are used for a large number of applications used. For example, nonwovens are increasingly as cleaning and Wipes, dishcloths and napkins used. In these applications it is important that e.g. spilled liquids, such as milk, coffee, etc., quickly and completely when wiping over soaked up and completely dried on damp surfaces become. The speed and completeness with which Liquids are sucked up, determine the usage properties of a cleaning and wiping cloth and are the main criteria for the goodness of the item.

Ein Putztuch saugt Flüssigkeiten umso rascher auf, je schneller deren Transport auf der Faseroberfläche erfolgt. Eine hydrophile Oberfläche wird leicht und rasch von Wasser benetzt. Das Wasser verteilt sich sehr schnell über die gesamte Fläche des Vliesstoffes und das Wasser wird von der Kontaktstelle "abgesaugt". Hydrophobe Oberflächen werden dagegen nicht benetzt. Sie leiten die Flüssigkeit daher auch nicht weiter und sind für einen Einsatz als Putz- oder Wischtuch ungeeignet. Entscheidend für die Menge an Flüssigkeit, die aufgenommen werden kann, ist unter anderem auch das Quellverhalten der Faser. Ein hydrophobes Bindemittel, das die Faser weitgehend umhüllt, beeinträchtigt die Kinetik der Wasseraufnahme.A cleaning cloth absorbs liquids the quicker the faster their transport takes place on the fiber surface. A hydrophilic The surface is easily and quickly wetted by water. The water spreads very quickly over the entire surface of the nonwoven and the water is "sucked away" from the contact point. hydrophobic In contrast, surfaces are not wetted. You run the Liquid therefore also no further and are for one use unsuitable as cleaning cloth or wipe. Crucial for the crowd of liquid that can be absorbed is, among other things also the swelling behavior of the fiber. A hydrophobic binder that largely envelops the fiber affects the kinetics of the Water intake.

Zur Verbesserung der Wasseraufnahmeeigenschaften von Vliesstoffen werden bei deren Herstellung mitunter oberflächenaktive hydrophilierende Agentien, wie Emulgatoren, Tenside oder Netzmittel, eingesetzt. Hierdurch wird eine ausgezeichnete Anfangshydrophilie erreicht. Diese Vliesstoffe weisen aber den Nachteil auf, daß die hydrophilen Agentien durch Wasser oder andere wässrige Medien allmählich ausgewaschen werden. Nach mehrmaligem Wasserkontakt wird das Erzeugnis zunehmend hydrophober. Das Spül-, Putz- oder Wischtuch verliert somit nach mehrmaligem Auswaschen seine Fähigkeit, wässrige Flüssigkeiten rasch aufzusaugen. Das Tuch wird folglich unbrauchbar für die weitere Verwendung, und muß entsorgt werden, obgleich die mechanische Festigkeit des Tuchs für weitere Gebrauchszyklen noch ausreicht. Dies ist im Hinblick auf einen verantwortungsvollen Umgang mit Rohstoffen nachteilig.To improve the water absorption properties of nonwovens are sometimes surface-active hydrophilizing in their manufacture Agents such as emulsifiers, surfactants or wetting agents are used. This makes for excellent initial hydrophilicity reached. However, these nonwovens have the disadvantage that the hydrophilic agents through water or other aqueous media be washed out gradually. After repeated contact with water the product becomes increasingly hydrophobic. The flushing, cleaning or Wipe thus loses its ability to wash soak up aqueous liquids quickly. The cloth will consequently unusable for further use, and must be disposed of be, although the mechanical strength of the cloth for further Cycles of use are still sufficient. This is with regard to one responsible handling of raw materials disadvantageous.

Der vorliegenden Erfindung lag daher die Aufgabe zugrunde, ein hydrophiles textiles Flächengebilde bereitzustellen, dessen Hydrophilie auch nach mehrmaligem Auswaschen erhalten bleibt.The present invention was therefore based on the object To provide hydrophilic fabrics, its hydrophilicity is retained even after repeated washing.

Es wurde überraschenderweise gefunden, daß diese Aufgabe durch die Verwendung bestimmter Oxide und/oder Hydroxide in kolloiddisperser Verteilung in Verbindung mit bestimmten Netzmitteln gelöst werden kann.It was surprisingly found that this task was accomplished by the use of certain oxides and / or hydroxides in colloidally dispersed Distribution in connection with certain wetting agents solved can be.

Die vorliegende Erfindung betrifft daher ein textiles Flächengebilde, das ein Gefüge von Fasern umfasst, die mittels eines polymeren Bindemittels miteinander verbunden sind, und dadurch gekennzeichnet ist, daß das Flächengebilde ein Oxid und/oder Hydroxid von Al, B, Si, Mg, Ti und/oder Zn in kolloiddisperser Verteilung sowie ein unter Sulfosuccinaten und Sulfosuccinamaten ausgewähltes Netzmittel enthält.The present invention therefore relates to a textile fabric, which comprises a structure of fibers, which by means of a polymer Binder are interconnected, and characterized is that the fabric is an oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn in a colloidal dispersion and one selected from sulfosuccinates and sulfosuccinamates Contains wetting agents.

Die vorliegende Erfindung betrifft ferner ein Verfahren zur Herstellung eines textilen Flächengebildes, bei dem ein Gefüge von Fasern mit einer Dispersion eines polymeren Bindemittels imprägniert, getrocknet, und gegebenenfalls gehärtet wird, das dadurch gekennzeichnet ist, daß das Gefüge außerdem (i) mit einer kolloidalen Suspension eines Oxids und/oder Hydroxids von Al, B, Si, Mg, Ti und/oder Zn imprägniert wird oder mit der Lösung eines Vorläufers eines Oxids und/oder Hydroxids von Al, B, Si, Mg, Ti und/oder Zn imprägniert wird und die Bildung des Oxids und/oder Hydroxids in kolloiddisperser Verteilung induziert wird und (ii) das Gefüge mit einem unter Sulfosuccinaten und Sulfosuccinamaten ausgewählten Netzmittel imprägniert wird.The present invention further relates to a method of manufacture of a textile fabric, in which a structure of Impregnated fibers with a dispersion of a polymeric binder, dried, and optionally hardened, the result is characterized in that the structure also (i) with a colloidal Suspension of an oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn is impregnated or with a solution Precursor of an oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn is impregnated and the formation of the oxide and / or Hydroxide is induced in a colloidally disperse distribution and (ii) the structure with one among sulfosuccinates and sulfosuccinamates selected wetting agent is impregnated.

Ausführungen in der vorliegenden Beschreibung, die mit Bezug auf das erfindungsgemäße textile Flächengebilde erfolgen, gelten soweit angebracht auch für das erfindungsgemäße Verfahren und umgekehrt.Executions in the present description with reference to the textile fabrics according to the invention take place so far also appropriate for the method according to the invention and vice versa.

Vorzugsweise enthält das erfindungsgemäße textile Flächengebilde 1 - 20 Gew.-%, bezogen auf das Trockengewicht des polymeren Bindemittels, insbesondere 3 -15 Gew.-% und besonders bevorzugt 5 - 15 Gew.-%, Oxid und/oder Hydroxid von Al, B, Si, Mg, Ti und/oder Zn.The textile fabric according to the invention preferably contains 1 - 20% by weight, based on the dry weight of the polymeric binder, in particular 3-15% by weight and particularly preferably 5-15% by weight, oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn.

Das erfindungsgemäße textile Flächengebilde enthält vorzugsweise 1 - 20 Gew.-%, bezogen auf das Trockengewicht des polymeren Bindemittels, insbesondere 2 - 10 Gew.-%, Netzmittel.The textile fabric according to the invention preferably contains 1 - 20% by weight, based on the dry weight of the polymeric binder, in particular 2-10% by weight, wetting agent.

Der Begriff "Oxid und/oder Hydroxid von Al, B, Si, Mg, Ti und/oder Zn" soll für die Zwecke der vorliegenden Erfindung eine weitestgehende Bedeutung aufweisen. So sollen neben den einfachen Oxiden und Hydroxiden der angegebenen Elemente auch deren hydratisierte Formen mit wechselndem Wassergehalt und die Oxoanionensalze mit z.B. Alkalimetall- oder Erdalkalimetallkationen, z.B. die Silicate und Aluminate, umfasst sein. Ferner soll der Begriff Oxide und Hydroxide in unterschiedlichen Kondensationsstufen umfassen, z.B. die Insel-, Band- und Schichtsilikate, sowie gemischte Oxide und/oder Hydroxide. Bevorzugte Oxide und/oder Hydroxide sind Kieselsäure, Aluminiumoxid, Aluminiumhydroxid, Alumosilikate, z.B. Bentonite, Montmorillonite.The term "oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn" is intended to be a broad one for the purposes of the present invention Have meaning. So in addition to the simple Oxides and hydroxides of the specified elements also their hydrated Forms with changing water content and the oxoanion salts with e.g. Alkali metal or alkaline earth metal cations, e.g. the silicates and aluminates. Furthermore, the term Include oxides and hydroxides in different condensation stages, e.g. the island, ribbon and layered silicates, as well as mixed Oxides and / or hydroxides. Preferred oxides and / or hydroxides are silica, aluminum oxide, aluminum hydroxide, aluminosilicates, e.g. Bentonite, Montmorillonite.

Die erfindungsgemäßen textilen Flächengebilde enthalten ein unter Sulfosuccinaten und Sulfosuccinamaten ausgewähltes Netzmittel in gleichmäßig verteilter Form. Die verwendeten Netzmittel weisen insbesondere folgende allgemeine Strukturformel auf

Figure 00030001
in der M für ein Alkalimetall, insbesondere Natrium, oder ein Äquivalent eines Erdalkalimetalls oder Ammonium steht, welches mit 1 bis 4 C1- bis C4-Alkyl- oder C1- bis C4-Hydroxyalkylgruppen substituiert sein kann;

  • X und Y gleich oder verschieden sind und jeweils für O-(CnH2nO)m-R, (CnH2nO)m-NHCOR, OM, OH, oder NHR stehen, wobei wenigstens einer der Reste X und Y von OM oder OH verschieden ist, und R für gegebenenfalls verzweigtes C5- bis C18-Alkyl, C5- bis C18-Alkenyl, C5- bis C18-Cycloalkyl, (C1- bis C12-Alkyl)aryl oder Phenyl steht;
  • n für eine ganze Zahl von 2 bis 4 und
  • m für eine ganze Zahl von 0 bis 30 steht.
    • The textile fabrics according to the invention contain a wetting agent selected from sulfosuccinates and sulfosuccinamates in a uniformly distributed form. The wetting agents used have the following general structural formula
    Figure 00030001
    in which M represents an alkali metal, in particular sodium, or an equivalent of an alkaline earth metal or ammonium, which may be substituted by 1 to 4 C 1 to C 4 alkyl or C 1 to C 4 hydroxyalkyl groups;
  • X and Y are the same or different and each represents O- (C n H 2n O) m -R, (C n H 2n O) m -NHCOR, OM, OH, or NHR, at least one of the radicals X and Y is different from OM or OH, and R is optionally branched C 5 to C 18 alkyl, C 5 to C 18 alkenyl, C 5 to C 18 cycloalkyl, (C 1 to C 12 alkyl) aryl or phenyl;
  • n for an integer from 2 to 4 and
  • m represents an integer from 0 to 30.

    • Besonders gut bewährt haben sich Sulfobernsteinsäurediester, bei denen die zur Veresterung verwendeten Alkohole eine Kettenlänge von 4 bis 8 C-Atomen aufweisen, z.B. Natrium-di(ethylhexyl)sulfosuccinat.Sulfosuccinic diesters have proven to be particularly useful which the alcohols used for the esterification have a chain length of 4 to 8 carbon atoms, e.g. Sodium di (ethylhexyl) sulfosuccinate.

    Hinsichtlich der verwendeten Fasern unterliegt die Erfindung keinen wesentlichen Einschränkungen. Es sind alle Faserarten geeignet, die gegenwärtig zur Herstellung von Vliesstoffen verwendet werden, z.B. Polypropylen-, Polyester-, Polyamidfasern, Zellulosefasern, wie Viskosefasern, Zweikomponenten-Fasern, z.B. Polyester-Copolyester-, Polypropylen-Polyethylen-, Polyester-Polyamid-, Polyester-Polypropylen-, und Polyamid-6-Polyamid-6,6-Fasern. Weitere geeignete Fasern sind Polyacrylnitril-, Polyimid-, Polytetrafluorethylen- und Poly(phenylensulfid)fasern, mineralische Fasern oder Glasfasern und halbsynthetische Fasern, wie Acetatfasern. Polypropylenfasern, Polyesterfasern und Zellulosefasern und Mischfasern der genannten Materialien sind bevorzugt.The invention is not subject to any of the fibers used significant restrictions. All types of fibers are suitable currently used in the manufacture of nonwovens e.g. Polypropylene, polyester, polyamide fibers, cellulose fibers, such as viscose fibers, two-component fibers, e.g. Polyester copolyester, Polypropylene-polyethylene, polyester-polyamide, Polyester-polypropylene and polyamide-6-polyamide-6,6 fibers. Other suitable fibers are polyacrylonitrile, polyimide, Polytetrafluoroethylene and poly (phenylene sulfide) fibers, mineral Fibers or glass fibers and semi-synthetic fibers such as acetate fibers. Polypropylene fibers, polyester fibers and cellulose fibers and mixed fibers of the materials mentioned are preferred.

    Es können alle üblicherweise verwendeten polymeren Bindemittel eingesetzt werden. Hierzu zählen insbesondere die Polyacrylatdispersionen, z.B. auf der Basis von C1- bis C4-Alkyl(meth)acrylaten, (Meth)acrylsäure und/oder (Meth)Acrylamid. Amidhaltige Polymere oder Copolymere können mit NN-Methylolverbindungen, wie Harnstoff-Formaldehyd- oder Melamin-Formaldehydharzen vernetzt werden. Eine innere Vernetzung erfolgt beim Einverleiben von N-Methylol(meth)acrylamid. Weiterhin sind Kautschuklatices, wie z.B. synthetische Styrol-Butadienkautschukke (SBR) und Acrylnitril-Butadien-Kautschuk (NBR), Polyvinylesterdispersionen, gegebenenfalls copolymerisiert mit Ethylen und/oder Vinylchlorid, wie z.B. Copolymere von Vinylacetat und Ethylen oder Vinylacetat, Vinylchlorid und Ethylen, sowie Polyvinylalkohole geeignet. Weiter lassen sich Polyurethandispersionen sowie Aminoplast- und Phenoplast-Vorkondensate anführen. Bevorzugt ist die Verwendung eines Bindemittels, das ein Polymerisat von Monomeren umfasst, die unter C1 bis C4 Alkyl(meth)acrylaten, (Meth)acrylsäure, (Meth)acrylamid, N-Methylol(meth)acrylamid, Styrol, Butadien, (Meth)acrylnitril, C1 bis C6-Alkansäurevinylestern, Vinylchlorid, Ethylen und Vinylalkohol ausgewählt sind. Die Auftragsmenge an Bindemittel, ausgedrückt als trockenes Bindemittel, bezogen auf das Gesamtgewicht des gebundenen Vliesstoffes, beträgt im Allgemeinen 10 bis 40 Gew.-%, vorzugsweise etwa 20% Gew.-%.All commonly used polymeric binders can be used. These include in particular the polyacrylate dispersions, for example based on C 1 -C 4 -alkyl (meth) acrylates, (meth) acrylic acid and / or (meth) acrylamide. Amide-containing polymers or copolymers can be crosslinked with NN-methylol compounds, such as urea-formaldehyde or melamine-formaldehyde resins. Internal crosslinking takes place when N-methylol (meth) acrylamide is incorporated. Rubber latices, such as synthetic styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR), polyvinyl ester dispersions, optionally copolymerized with ethylene and / or vinyl chloride, such as copolymers of vinyl acetate and ethylene or vinyl acetate, vinyl chloride and ethylene, and also polyvinyl alcohols are also suitable suitable. Polyurethane dispersions and aminoplast and phenoplast precondensates can also be mentioned. Preference is given to the use of a binder which comprises a polymer of monomers which, under C 1 to C 4, alkyl (meth) acrylates, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, styrene, butadiene, ( Meth) acrylonitrile, C 1 to C 6 alkanoic acid vinyl esters, vinyl chloride, ethylene and vinyl alcohol are selected. The application amount of binder, expressed as dry binder, based on the total weight of the bonded nonwoven, is generally 10 to 40% by weight, preferably about 20% by weight.

    Es ist von kritischer Bedeutung für die vorliegende Erfindung, daß das Oxid und/oder Hydroxid von Al, B, Si, Mg, Ti und/oder Zn im erfindungsgemäßen Vliesstoff in kolloiddisperser Verteilung vorliegt. Mit nichtkolloidalen, gröberen Teilchen, wie sie gelegentlich als Antiblockier-Additive oder andere Zuschlagstoffe verwendet werden, wird die angestrebte Wirkung nicht erreicht. "Kolloiddispers" soll bedeuten, daß die Mehrzahl der Teilchen, z.B. mehr als 90 Gew.-%, des Oxids und/oder Hydroxids eine Größe von < 1 µm, insbesondere < 0,1 µm aufweisen. Die kolloiddisperse Verteilung läßt sich im Rahmen der vorliegenden Erfindung z.B. erreichen, indem man von einer kolloidalen Suspension des Oxids und/oder Hydroxids, z.B. einem Sol, wie einem Hydrosol, oder einem Gel ausgeht oder aber die Bildung des Oxids und/oder Hydroxids in kolloiddisperser Form z.B. als Gel, im Vlies induziert.It is critical to the present invention that the oxide and / or hydroxide of Al, B, Si, Mg, Ti and / or Zn in the nonwoven fabric according to the invention in a colloidally disperse distribution is present. With non-colloidal, coarser particles, as they occasionally do as anti-blocking additives or other additives the intended effect is not achieved. "Colloidal disperse" is intended to mean that the majority of the particles, e.g. more than 90% by weight of the oxide and / or hydroxide one size of <1 µm, in particular <0.1 µm. The colloidal disperse Distribution can be within the scope of the present invention e.g. achieve by using a colloidal suspension of the oxide and / or hydroxide, e.g. a sol, such as a hydrosol, or one Gel starts or the formation of the oxide and / or hydroxide in colloidal form e.g. as a gel, induced in the fleece.

    Zur Imprägnierung des Vlieses mit der Bindemitteldispersion sind alle gängigen Verfahren der Imprägnierung, z.B. die Imprägnierung mit der Imprägnieranlage oder im Foulard, geeignet. Soweit das Oxid und/oder Hydroxid in Gegenwart des polymeren Bindemittels eine stabile kolloidale Suspension bildet, ist es zweckmäßig, das Oxid und/oder Hydroxid in die Bindemitteldispersion einzuarbeiten. Auf diese Weise können z.B. kolloidale Kieselsäuren verarbeitet werden. Kolloidale Dispersionen bestimmter Oxide und/oder Hydroxide lassen sich nicht in situ in der Bindemitteldispersion herstellen. So neigen z.B. Al3+-Salze dazu, die Dispersion zu koagulieren bzw. es tritt eine Koagulation beim Versuch ein, die Al3+-Salze durch Zugabe einer Base, z.B. von Ammoniak, in Al(OH)3 umzuwandeln. In diesen Fällen ist es zweckmäßig, das Vlies mit einer kolloidalen Suspension, vorzugsweise einer frisch hergestellten kolloidalen Suspension, in der Form eines Sols oder Gels, zu imprägnieren und zu trocknen und anschließend mit dem polymeren Bindemittel zu imprägnieren. Andererseits ist es möglich, das Vlies mit der Lösung eines Vorläufers des Oxids und/oder Hydroxids zu imprägnieren und die Bildung des Oxids und/oder Hydroxids im Vlies zu induzieren. So kann das Vlies z.B. mit einer Lösung von Al3+-Ionen, z.B. einer Al2(SO4)3-Lösung oder einer Al(NO3)3-Lösung, getränkt und vorzugsweise getrocknet werden. Anschließend wird das Vlies mit der Bindemitteldispersion imprägniert. Der neutrale bis leicht alkalische pH-Wert der Dispersion führt zu einer Umwandlung der Al3+-Ionen zu Al(OH)3. Gegebenenfalls kann der Bindemitteldispersion eine pH-regulierende Substanz, beispielsweise ein Puffer, zugesetzt werden, um einen neutralen bis leicht alkalischen pH-Wert, z.B. im Bereich von 6 bis 9, einzustellen.All common methods of impregnation, for example impregnation with the impregnation system or in the foulard, are suitable for impregnating the nonwoven with the binder dispersion. If the oxide and / or hydroxide forms a stable colloidal suspension in the presence of the polymeric binder, it is expedient to incorporate the oxide and / or hydroxide into the binder dispersion. In this way, for example, colloidal silicas can be processed. Colloidal dispersions of certain oxides and / or hydroxides cannot be produced in situ in the binder dispersion. For example, Al 3+ salts tend to coagulate the dispersion or coagulation occurs when an attempt is made to convert the Al 3+ salts into Al (OH) 3 by adding a base, for example ammonia. In these cases, it is expedient to impregnate and dry the fleece with a colloidal suspension, preferably a freshly produced colloidal suspension, in the form of a sol or gel, and then to impregnate it with the polymeric binder. On the other hand, it is possible to impregnate the fleece with the solution of a precursor of the oxide and / or hydroxide and to induce the formation of the oxide and / or hydroxide in the fleece. For example, the fleece can be impregnated with a solution of Al 3+ ions, for example an Al 2 (SO 4 ) 3 solution or an Al (NO 3 ) 3 solution, and preferably dried. The fleece is then impregnated with the binder dispersion. The neutral to slightly alkaline pH of the dispersion leads to a conversion of the Al 3+ ions to Al (OH) 3 . If necessary, a pH-regulating substance, for example a buffer, can be added to the binder dispersion in order to establish a neutral to slightly alkaline pH, for example in the range from 6 to 9.

    Das Vlies oder der Vliesstoff könnte ferner mit einer Wasserglaslösung, d.h. Natriumorthosilikatlösung, getränkt werden, wobei anschließend durch Behandlung mit verdünnter Mineralsäure, z.B. Salzsäure, kolloidale Kieselsäure erzeugt werden kann. Ein weiteres Beispiel ist die Behandlung mit einer wässrigen Lösung von Borax (Na2B4O7 · 10 H2O) mit anschließender Trocknung.The fleece or the nonwoven fabric could also be impregnated with a water glass solution, ie sodium orthosilicate solution, after which colloidal silica can be produced by treatment with dilute mineral acid, for example hydrochloric acid. Another example is treatment with an aqueous solution of borax (Na 2 B 4 O 7 .10 H 2 O) followed by drying.

    Die Imprägnierung des Vlieses oder Vliesstoffes mit der kolloidalen Suspension des Oxids/Hydroxids bzw. die Imprägnierung mit der Lösung des Vorläufers und die Induzierung der Oxid/Hydroxidbildung können zu einem beliebigen Zeitpunkt während der Herstellung des textilen Flächengebildes erfolgen. Es ist bevorzugt, daß sie vor oder gleichzeitig mit der Imprägnierung mit dem Bindemittel erfolgen.The impregnation of the fleece or nonwoven with the colloidal Suspension of the oxide / hydroxide or the impregnation with the Solution of the precursor and induction of oxide / hydroxide formation can be at any time during manufacture of the textile fabric. It is preferred that they before or simultaneously with the impregnation with the binder respectively.

    Die Imprägnierung des Vlieses oder Vliesstoffes mit dem Netzmittel kann zu einem beliebigen Zeitpunkt während der Herstellung des erfindungsgemäßen textilen Flächengebildes erfolgen. Im Allgemeinen ist es zweckmäßig, die Imprägnierung mit dem Netzmittel gleichzeitig mit der Bindemittel-Imprägnierung vorzunehmen. Hierzu wird das Netzmittel einfach zu der wässrigen Bindemitteldispersion gegeben.The impregnation of the fleece or nonwoven fabric with the wetting agent can be at any time during manufacture of the fabric according to the invention take place. In general it is advisable to impregnate with the wetting agent to be carried out simultaneously with the impregnation of the binder. For this purpose, the wetting agent simply becomes the aqueous binder dispersion given.

    Die Erfindung wird nun durch die folgenden Beispiele näher veranschaulicht.The invention is now illustrated in more detail by the following examples.

    Beispiele 1 bis 10Examples 1 to 10

    Polyester-Zellwoll-Vliese (70PES/30ZW; 1,7 dtex; Faserlänge 38 mm; 30 g/m2) einer Länge von 35 bis 50 cm und einer Breite von 25 bis 28 cm wurden in einer Imprägnier- und Absauganlage in Längsrichtung über ein Endlos-PES-Siebband durch eine 25 %-ige Bindemittelflotte und über eine Absaugvorrichtung geführt. Bei der verwendeten Bindemitteldispersion handelte es sich um Acronal DS 2350 X ™ (Polyacrylatdispersion auf der Basis von Butylacrylat und Acrylnitril). Die Bandgeschwindigkeit betrug 1 bis 2 m pro min. Über die verstellbare Stärke der Absaugung wurde der Naßauftrag auf etwa 160% eingestellt, was einem Trockenauftrag von etwa 40% entspricht. Die Bindemittelflotte enthielt die in der nachstehenden Tabelle angegebenen Zusatzstoffe (Gew.-%, bezogen auf das Trockengewicht des Bindemittels). Die imprägnierten Vliese wurden auf das Band eines Mathis-Siebbandtrockners Typ TH aufgelegt, gegen Verrutschen gesichert und 2 min lang bei 150°C getrocknet. Die Oberseite des jeweiligen Vlieses wurde gekennzeichnet, und durch Wiegen wurde die Auftragsmenge bestimmt.Polyester cellulose fleeces (70PES / 30ZW; 1.7 dtex; fiber length 38 mm; 30 g / m 2 ) a length of 35 to 50 cm and a width of 25 to 28 cm were lengthways in an impregnation and suction system an endless PES sieve belt through a 25% binder liquor and over a suction device. The binder dispersion used was Acronal DS 2350 X ™ (polyacrylate dispersion based on butyl acrylate and acrylonitrile). The belt speed was 1 to 2 m per min. The wet application was set to approximately 160% via the adjustable strength of the suction, which corresponds to a dry application of approximately 40%. The binder liquor contained the additives listed in the table below (% by weight, based on the dry weight of the binder). The impregnated nonwovens were placed on the belt of a Mathis sieve belt dryer type TH, secured against slipping and dried at 150 ° C. for 2 minutes. The top of each fleece was marked and the quantity applied was determined by weighing.

    Die so erhaltenen Vliesstoffe wurden unmittelbar und nach fünfmaligem Waschen einem Benetzungstest unterzogen. Das Waschen geschah, indem der Vliesstoff in einem 5 l Eimer mit Leitungswasser unter Wasser mit der Hand etwa 15 mal ausgedrückt (ausgewrungen), dann in ein Handtuch eingewickelt und darin trockengewrungen wurde. Dieser Vorgang wurde 5 mal wiederholt.The nonwovens thus obtained were immediately and after five times Wash subjected to a wetting test. The washing happened by placing the nonwoven in a 5 liter bucket of tap water expressed under water by hand about 15 times (wrung out), then wrapped in a towel and wrung dry in it has been. This process was repeated 5 times.

    Zur quantitativen Bestimmung der Hydrophilie wurde der farbige Ablauftest herangezogen. Dieser Test läuft im Wesentlichen folgendermaßen ab: Auf den schräg eingespannten Vliesstoff wird eine definierte Menge eingefärbtes Wasser aufgebracht. Je nach Hydrophilie läuft das Wasser ab oder dringt mehr oder weniger schnell in den Vliesstoff ein. Dadurch werden charakteristische Farbflekken, z.B. kreisrund für schnelles Eindringen in den Vliesstoff bzw. schmal und länglich für langsames Eindringen und bevorzugtes Ablaufen, erhalten. Die Beurteilungen werden nach einer Notenskala zugeordnet.For the quantitative determination of the hydrophilicity, the colored Run test used. This test basically works as follows ab: On the diagonally clamped nonwoven, a defined amount of colored water applied. Depending on the hydrophilicity the water runs off or penetrates more or less quickly into the nonwoven. Characteristic color spots, e.g. circular for quick penetration into the nonwoven or narrow and elongated for slow penetration and preferred Expire, get. The assessments are based on a grading scale assigned.

    Zur Durchführung der Prüfung wird ein Prüfkörper der Größe von 21 x 5 cm in einen Rahmen eingespannt, der eine Neigung von 30 Grad gegenüber der Horizontalen beschreibt. Die im Trockner oben liegende Seite weist bei dieser Prüfung nach unten. Mittels einer Pipette werden 0,5 ml Testflüssigkeit aus einer Höhe von 10 mm und einem Abstand zum oberen Vliesrand von 30 mm aufgebracht. Die Testflüssigkeit bestand aus 2 g Hostapal CV-Lösung, 2,5 g Lurantin-Lichtecht-Türkisblau-GL auf 1 l vollentsalztes Wasser. Nach Trocknung des Prüfkörpers (hängend) wird die Vliesoberseite begutachtet und ein Notenwert von 0 für keine Benetzung (Testflüssigkeit vollständig abgelaufen) bis 5 für totale Benetzung zugeteilt. Die Ergebnisse sind in der nachstehenden Tabelle angegeben. farbiger Ablauftest Vers. Nr. mineral. Additiv Emulgator vor dem Waschen nach 5 mal Waschen 1 - - 0-1 0-1 2 - 3,0% Na-di(2-ethylhexyl) sulfosuccinat 4 0-1 3 5% Kieselsäure - 0 0 4 5% Kieselsäure 3,0% Na-di(2-ethylhexyl) sulfosuccinat 5 5 5 5% Kieselsäure 3% Dodecylbenzolsulfonat 5 1-2 6 5% Kieselsäure 5% Na-Alkylnaphthalinsulfonsäure 0-1 0-1 7 5% Kieselsäure 5% Na-Alkylnaphthalinsulfonsäure 0-1 0-1 8 5% Kieselsäure 3% Ammonium-polyacrylat 2 0-1 9 10% Kieselsäure - 0 0 10 10% Kieselsäure 3,0% Na-di(2-ethylhexyl) sulfosuccinat 5 5 To carry out the test, a test specimen measuring 21 x 5 cm is clamped in a frame that describes an inclination of 30 degrees with respect to the horizontal. The side at the top in the dryer faces down during this test. Using a pipette, 0.5 ml of test liquid is applied from a height of 10 mm and a distance from the upper fleece edge of 30 mm. The test liquid consisted of 2 g of Hostapal CV solution, 2.5 g of Lurantin-Lightfast-Turquoise Blue-GL to 1 l of completely demineralized water. After the test specimen has dried (hanging), the top of the fleece is examined and a grade of 0 for no wetting (test liquid completely drained off) to 5 for total wetting is assigned. The results are shown in the table below. colored run test Vers. No. mineral. additive emulsifier before washing after washing 5 times 1 - - 0-1 0-1 2 - 3.0% Na di (2-ethylhexyl) sulfosuccinate 4 0-1 3 5% silica - 0 0 4 5% silica 3.0% Na di (2-ethylhexyl) sulfosuccinate 5 5 5 5% silica 3% dodecylbenzenesulfonate 5 1-2 6 5% silica 5% Na alkylnaphthalenesulfonic acid 0-1 0-1 7 5% silica 5% Na alkylnaphthalenesulfonic acid 0-1 0-1 8th 5% silica 3% ammonium polyacrylate 2 0-1 9 10% silica - 0 0 10 10% silica 3.0% Na di (2-ethylhexyl) sulfosuccinate 5 5

    Aus der Tabelle ist ersichtlich, daß nur bei den Beispielen 4 und 10 ein Vliesstoff erhalten wurde, der nach 5 maligem Waschen noch hydrophil ist. Diese Beispiele enthielten einen Sulfobernsteinsäureester in Verbindung mit kolloidaler Kieselsäure. Ohne Kieselsäure (Beispiel 2) wird selbst bei Verwendung desselben Emulgators keine permanente Hydrophilie erhalten. Andere Emulgatoren (Beispiel 5, 6) führen nicht zur gewünschten permanenten Hydrophilie. Auch polymere Additive (Beispiel 8) oder höhere Mengen an Kieselsäure in Abwesenheit von Sulfobernsteinsäureestern (Beispiel 9) führen nicht zu den angestrebten Eigenschaften.From the table it can be seen that only in Examples 4 and 10 a nonwoven fabric was obtained after 5 washes is hydrophilic. These examples contained a sulfosuccinic acid ester in connection with colloidal silica. Without silica (Example 2) is even when using the same emulsifier no permanent hydrophilicity obtained. Other emulsifiers (Examples 5, 6) do not lead to the desired permanent hydrophilicity. Also polymeric additives (example 8) or higher amounts of Silicic acid in the absence of sulfosuccinic acid esters (example 9) do not lead to the desired properties.

    Beispiele 11 bis 18Examples 11 to 18

    Standard-Zellstoff-Vliese (Whatman #4; 100% Zellstoff) einer Länge von 35 bis 50 cm und einer Breite von 25 bis 28 cm wurden im Foulard durch eine 10%ige Bindemittelflotte (Acronal DS 2350 X) gezogen, abgequetscht und anschließend in einem Mathis-Spannrahmentrockner mit Ablagegaze getrocknet. Die Flotte enthielt die in der nachstehenden Tabelle angegebenen Zusatzstoffe. Bei den Beispielen 13 und 14 wurden die Vliese zunächst im Foulard mit einer 5 %igen Al2(SO4)3-Lösung getränkt, abgequetscht und getrocknet und erst dann im Foulard mit Bindemittel getränkt und erneut getrocknet.Standard cellulose nonwovens (Whatman # 4; 100% cellulose), 35 to 50 cm long and 25 to 28 cm wide, were pulled through a 10% binder liquor (Acronal DS 2350 X), squeezed and then in a Mathis stenter dryer with gauze. The liquor contained the additives listed in the table below. In Examples 13 and 14, the nonwovens were first impregnated in the padding with a 5% Al 2 (SO 4 ) 3 solution, squeezed and dried and only then soaked in the padding with binder and dried again.

    Die erhaltenen Vliesstoffe wurden einem Saugfähigkeitstest unterzogen. Hierzu wurde ein 5 mal gewaschener und getrockneter Vliesstreifen (70 x 30 mm) mit einer Eintauchtiefe von etwa 5 mm in die Testflüssigkeit (s.o.) gehängt und nach 30 s deren Steighöhe notiert. Außerdem wurde die Penetrationsgeschwindigkeit im Vliesstoff gemessen. Hierzu wurden 0,1 ml Testflüssigkeit auf die Vorderseite von 5 mal gewaschenen und getrockneten Vliesstoffproben aufgesetzt und die Zeit notiert, bis der Tropfen ganz in den Vliesstoff eingedrungen ist. Die Ergebnisse sind in der nachstehenden Tabelle angegeben. Vers. Nr. mineral. Additiv Emulgator Steighöhe in mm Penetration (min) 11 - - 0 keine 12 - 3,0% Na-di(2-ethylhexyl) sulfosuccinat *1 9 6 13 Al2O3 aus Al2(SO4)3 - 0 keine 14 Al2O3 aus Al2(SO4)3 3,0% Na-di(2-ethylhexyl) sulfosuccinat *1 11,5 1 15 5% Kieselsäure 3,0% Na-di(2-ethylhexyl) sulfosuccinat *1 11 sofort 16 10% Sipern.D 10 3,0% Na-di(2-ethylhexyl) sulfosuccinat *1 7 29 17 10% China Clay 3,0% Na-di(2-ethylhexyl) sulfosuccinat *1 9 8 18 10% Gelbs.kreide 3,0% Na-di(2-ethylhexyl) sulfosuccinat *1 13 5 The nonwovens obtained were subjected to an absorbency test. For this purpose, a 5 times washed and dried fleece strip (70 x 30 mm) with an immersion depth of about 5 mm was hung in the test liquid (see above) and after 30 s the rise height was noted. The penetration rate in the nonwoven was also measured. For this purpose, 0.1 ml of test liquid was placed on the front of 5 times washed and dried nonwoven fabric samples and the time was noted until the drop completely penetrated the nonwoven fabric. The results are shown in the table below. Vers. No. mineral. additive emulsifier Rise height in mm Penetration (min) 11 - - 0 no 12 - 3.0% Na di (2-ethylhexyl) sulfosuccinate * 1 9 6 13 Al 2 O 3 from Al 2 (SO 4 ) 3 - 0 no 14 Al 2 O 3 from Al 2 (SO 4 ) 3 3.0% Na di (2-ethylhexyl) sulfosuccinate * 1 11.5 1 15 5% silica 3.0% Na di (2-ethylhexyl) sulfosuccinate * 1 11 immediately 16 10% Sipern.D 10 3.0% Na di (2-ethylhexyl) sulfosuccinate * 1 7 29 17 10% china clay 3.0% Na di (2-ethylhexyl) sulfosuccinate * 1 9 8th 18 10% yellow chalk 3.0% Na di (2-ethylhexyl) sulfosuccinate * 1 13 5

    Aus der Tabelle ist ersichtlich, daß nur die Kombination von mineralischem Füllstoff (Aluminiumoxid/hydroxid bzw. Kieselsäure; Versuche 14, 15) mit Sulfobernsteinsäureester zur gewünschten permanenten Hydrophilie führt. Die Komponenten alleine (Versuche 12, 13) sind hierzu nicht geeignet. Die Beispiele mit nicht kolloidalen mineralischen Zusätzen (Beispiel 16, 17 und 18) zeigen kritisch die Bedeutung der kolloiddispersen Verteilung.From the table it can be seen that only the combination of mineral Filler (aluminum oxide / hydroxide or silica; Experiments 14, 15) with sulfosuccinic acid ester to the desired permanent hydrophilicity. The components alone (attempts 12, 13) are not suitable for this. The non-colloidal examples mineral additives (Examples 16, 17 and 18) show critical of the importance of the colloidally disperse distribution.

    Claims (12)

    1. A textile fabric comprising a web of fibers joined together by means of a polymeric binder, said fabric comprising an oxide and/or hydroxide of Al, B, Si, Mg, Ti and/or Zn in a state of colloidally disperse subdivision and a wetting agent selected from sulfosuccinates and sulfosuccinamates.
    2. A textile fabric as claimed in claim 1, comprising 1 - 20% by weight of oxide and/or hydroxide, based on the dry weight of said polymeric binder.
    3. A textile fabric as claimed in claim 1 or 2, comprising 1 - 20% by weight of wetting agent, based on the dry weight of said polymeric binder.
    4. A textile fabric as claimed in any of claims 1 to 3, wherein said oxide and/or hydroxide is selected from the group consisting of silica, aluminum oxide, aluminum hydroxide and alumosilicates.
    5. A textile fabric as claimed in any of the preceding claims, wherein said sulfosuccinate and/or sulfosuccinamate contains one or two alkyl groups of from 4 to 8 carbon atoms.
    6. A textile fabric as claimed in any of the preceding claims, wherein said fibers are selected from the group consisting of polypropylene fibers, polyester fibers and cellulosic fibers.
    7. A textile fabric as claimed in any of the preceding claims, wherein said binder comprises an addition polymer of monomers selected from the group consisting of C1-C4-alkyl (meth)acrylates, (meth)acrylic acid, (meth)acrylamide, N-methylol(meth)acrylamide, styrene, butadiene, (meth)acrylonitrile, vinyl C1-C6-alkanoates, vinyl chloride, ethylene and vinyl alcohol.
    8. A process for producing a textile fabric by impregnating a web of fibers with a dispersion of a polymeric binder and drying and optionally curing the impregnated web, which comprises further impregnating said web with (i) a colloidal suspension of an oxide and/or hydroxide of Al, B, Si, Mg, Ti and/or Zn or a solution of a precursor of an oxide and/or hydroxide of Al, B, Si, Mg, Ti and/or Zn and inducing the formation of the oxide and/or hydroxide in a state of colloidally disperse subdivision and (ii) a wetting agent selected from sulfosuccinates and sulfosuccinamates.
    9. A process as claimed in claim 8, wherein said colloidal suspension of said oxide and/or hydroxide is present in said dispersion of said polymeric binder.
    10. A process as claimed in claim 9, wherein said colloidal suspension is a suspension of colloidal silica.
    11. A process as claimed in claim 8, wherein said precursor of an oxide and/or hydroxide is a solution comprising Al3+ ions.
    12. A process as claimed in claim 11, wherein said inducing of said formation of said oxide and/or hydroxide is effected simultaneously with said impregnating with said dispersion of said polymeric binder.
    EP99114691A 1998-07-28 1999-07-27 Textile fabrics Expired - Lifetime EP0976866B1 (en)

    Applications Claiming Priority (2)

    Application Number Priority Date Filing Date Title
    DE19833920A DE19833920A1 (en) 1998-07-28 1998-07-28 Textile fabrics
    DE19833920 1998-07-28

    Publications (2)

    Publication Number Publication Date
    EP0976866A1 EP0976866A1 (en) 2000-02-02
    EP0976866B1 true EP0976866B1 (en) 2004-11-03

    Family

    ID=7875564

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP99114691A Expired - Lifetime EP0976866B1 (en) 1998-07-28 1999-07-27 Textile fabrics

    Country Status (5)

    Country Link
    EP (1) EP0976866B1 (en)
    AT (1) ATE281552T1 (en)
    CA (1) CA2278946A1 (en)
    DE (2) DE19833920A1 (en)
    ES (1) ES2232051T3 (en)

    Cited By (10)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US8940089B2 (en) 2007-08-03 2015-01-27 Knauf Insulation Sprl Binders
    US9040652B2 (en) 2005-07-26 2015-05-26 Knauf Insulation, Llc Binders and materials made therewith
    US9309436B2 (en) 2007-04-13 2016-04-12 Knauf Insulation, Inc. Composite maillard-resole binders
    US9416248B2 (en) 2009-08-07 2016-08-16 Knauf Insulation, Inc. Molasses binder
    US9447281B2 (en) 2007-01-25 2016-09-20 Knauf Insulation Sprl Composite wood board
    US9492943B2 (en) 2012-08-17 2016-11-15 Knauf Insulation Sprl Wood board and process for its production
    US9493603B2 (en) 2010-05-07 2016-11-15 Knauf Insulation Sprl Carbohydrate binders and materials made therewith
    US9505883B2 (en) 2010-05-07 2016-11-29 Knauf Insulation Sprl Carbohydrate polyamine binders and materials made therewith
    US11846097B2 (en) 2010-06-07 2023-12-19 Knauf Insulation, Inc. Fiber products having temperature control additives
    US11945979B2 (en) 2018-03-27 2024-04-02 Knauf Insulation, Inc. Composite products

    Families Citing this family (12)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10153950A1 (en) 2001-11-06 2003-05-22 Bayer Ag Water vapor permeable coating composite
    US20100086726A1 (en) 2007-01-25 2010-04-08 Roger Jackson Mineral fibre board
    DK2108006T3 (en) 2007-01-25 2020-12-21 Knauf Insulation Gmbh BINDERS AND MATERIALS MADE THEREFORE
    CA2834816C (en) 2011-05-07 2020-05-12 Knauf Insulation Liquid high solids binder composition
    GB201206193D0 (en) 2012-04-05 2012-05-23 Knauf Insulation Ltd Binders and associated products
    CA2892900C (en) 2012-12-05 2020-08-11 Benedicte Pacorel Method for manufacturing an article comprising a collection of matter bound by a cured binder
    CA2938154C (en) 2014-02-07 2022-11-01 Knauf Insulation, Inc. Uncured articles with improved shelf-life
    GB201408909D0 (en) 2014-05-20 2014-07-02 Knauf Insulation Ltd Binders
    GB201517867D0 (en) 2015-10-09 2015-11-25 Knauf Insulation Ltd Wood particle boards
    GB201610063D0 (en) 2016-06-09 2016-07-27 Knauf Insulation Ltd Binders
    GB201701569D0 (en) 2017-01-31 2017-03-15 Knauf Insulation Ltd Improved binder compositions and uses thereof
    GB201804908D0 (en) 2018-03-27 2018-05-09 Knauf Insulation Ltd Binder compositions and uses thereof

    Family Cites Families (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3657003A (en) * 1970-02-02 1972-04-18 Western Electric Co Method of rendering a non-wettable surface wettable
    US5432000A (en) * 1989-03-20 1995-07-11 Weyerhaeuser Company Binder coated discontinuous fibers with adhered particulate materials
    BR9406745A (en) * 1993-06-02 1996-03-12 Minnesota Mining & Mfg Absorbent non-woven article and process for its preparation
    EP0753567A1 (en) * 1995-07-14 1997-01-15 The Procter & Gamble Company Softening through the wash compositions

    Cited By (17)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US9260627B2 (en) 2005-07-26 2016-02-16 Knauf Insulation, Inc. Binders and materials made therewith
    US9464207B2 (en) 2005-07-26 2016-10-11 Knauf Insulation, Inc. Binders and materials made therewith
    US9434854B2 (en) 2005-07-26 2016-09-06 Knauf Insulation, Inc. Binders and materials made therewith
    US9040652B2 (en) 2005-07-26 2015-05-26 Knauf Insulation, Llc Binders and materials made therewith
    US9447281B2 (en) 2007-01-25 2016-09-20 Knauf Insulation Sprl Composite wood board
    US9309436B2 (en) 2007-04-13 2016-04-12 Knauf Insulation, Inc. Composite maillard-resole binders
    US9039827B2 (en) 2007-08-03 2015-05-26 Knauf Insulation, Llc Binders
    US8940089B2 (en) 2007-08-03 2015-01-27 Knauf Insulation Sprl Binders
    US8979994B2 (en) 2007-08-03 2015-03-17 Knauf Insulation Sprl Binders
    US9469747B2 (en) 2007-08-03 2016-10-18 Knauf Insulation Sprl Mineral wool insulation
    US11946582B2 (en) 2007-08-03 2024-04-02 Knauf Insulation, Inc. Binders
    US9416248B2 (en) 2009-08-07 2016-08-16 Knauf Insulation, Inc. Molasses binder
    US9493603B2 (en) 2010-05-07 2016-11-15 Knauf Insulation Sprl Carbohydrate binders and materials made therewith
    US9505883B2 (en) 2010-05-07 2016-11-29 Knauf Insulation Sprl Carbohydrate polyamine binders and materials made therewith
    US11846097B2 (en) 2010-06-07 2023-12-19 Knauf Insulation, Inc. Fiber products having temperature control additives
    US9492943B2 (en) 2012-08-17 2016-11-15 Knauf Insulation Sprl Wood board and process for its production
    US11945979B2 (en) 2018-03-27 2024-04-02 Knauf Insulation, Inc. Composite products

    Also Published As

    Publication number Publication date
    DE19833920A1 (en) 2000-02-03
    DE59910972D1 (en) 2004-12-09
    ATE281552T1 (en) 2004-11-15
    EP0976866A1 (en) 2000-02-02
    ES2232051T3 (en) 2005-05-16
    CA2278946A1 (en) 2000-01-28

    Similar Documents

    Publication Publication Date Title
    EP0976866B1 (en) Textile fabrics
    DE3140784C2 (en)
    DE2849386C2 (en)
    DE60036509T2 (en) Moisturizing and donating polymers and compositions made therefrom
    DE69814419T2 (en) CLEANING CLOTH IMPREGNATED WITH CLEANING AGENT
    DE2141861C2 (en) Bonded nonwoven nonwoven fabric and process for its manufacture
    DE69621075T3 (en) Process for improving the flow of liquids in nonwovens, and disposable absorbent articles containing the nonwovens
    DE102005037113A1 (en) Use of a thermally curable aqueous composition as a binder for substrates
    CH654573A5 (en) (1- (2-benzoxazolyl, 2-benzothiazolyl and 2-indolyl) hydrazino) -ALKANNITRILDERIVATE.
    EP1577436A1 (en) Roofing materials
    DE2117999A1 (en)
    DE08858416T1 (en) MINERAL ARTIFICIAL FIBER FOR THREE-DIMENSIONAL ARMING OF A CEMENT PRODUCT
    DE2141862A1 (en) Method of applying a synthetic resin binder to a nonwoven fabric
    DE112006003498T5 (en) Substrate with photocatalytic constituents and activated carbon constituents and method of preparation
    EP0666349B1 (en) Process to manufacture a synthetic nonwoven substrate and use of this substrate
    DE2900771C2 (en) Decorative laminate
    DE3429613A1 (en) Binder for webs made of synthetic fleece
    DE3202122A1 (en) METHOD FOR STRENGTHENING FIBERBUILDINGS BY MEANS OF AQUEOUS PLASTIC DISPERSIONS
    DE102013008984A1 (en) cleaning cloth
    DE60027507T2 (en) Fire-retardant for textiles and method for refractory of textiles
    DE1943813A1 (en) Process for the dirt-repellent finishing of textiles
    DE2152596C2 (en) Process for the production of a nonwoven fibrous sheetlike structure bonded by chemical means with high water vapor absorption capacity and good thermal insulation properties
    DE3507154C2 (en)
    DE2441277C3 (en) Process for sizing yarns containing cellulose fibers
    DE3001075C2 (en) Method for making a needle felt carpet

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    17P Request for examination filed

    Effective date: 20000720

    AKX Designation fees paid

    Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041103

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041103

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20041103

    REG Reference to a national code

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    REF Corresponds to:

    Ref document number: 59910972

    Country of ref document: DE

    Date of ref document: 20041209

    Kind code of ref document: P

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: GERMAN

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050203

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050203

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: TRGR

    GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

    Effective date: 20050224

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2232051

    Country of ref document: ES

    Kind code of ref document: T3

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050727

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050727

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050727

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050731

    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20050804

    ET Fr: translation filed
    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    BERE Be: lapsed

    Owner name: *BASF A.G.

    Effective date: 20050731

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050403

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20100830

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: SE

    Payment date: 20100728

    Year of fee payment: 12

    Ref country code: IT

    Payment date: 20100729

    Year of fee payment: 12

    Ref country code: FR

    Payment date: 20100812

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: GB

    Payment date: 20100802

    Year of fee payment: 12

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: DE

    Payment date: 20100930

    Year of fee payment: 12

    REG Reference to a national code

    Ref country code: SE

    Ref legal event code: EUG

    GBPC Gb: european patent ceased through non-payment of renewal fee

    Effective date: 20110727

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: ST

    Effective date: 20120330

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20120201

    Ref country code: FR

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110801

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R119

    Ref document number: 59910972

    Country of ref document: DE

    Effective date: 20120201

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: IT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110727

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110727

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110728

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20130605

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20110728