EP1597425B1 - Method for hydrophobing textile materials - Google Patents

Method for hydrophobing textile materials Download PDF

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Publication number
EP1597425B1
EP1597425B1 EP04706158A EP04706158A EP1597425B1 EP 1597425 B1 EP1597425 B1 EP 1597425B1 EP 04706158 A EP04706158 A EP 04706158A EP 04706158 A EP04706158 A EP 04706158A EP 1597425 B1 EP1597425 B1 EP 1597425B1
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EP
European Patent Office
Prior art keywords
organic
inorganic solid
dicarboxylic acid
particulate form
solids
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EP04706158A
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German (de)
French (fr)
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EP1597425A1 (en
Inventor
Harald Keller
Jürgen Reichert
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BASF SE
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BASF SE
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    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • D—TEXTILES; PAPER
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • 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
    • D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M15/33—Esters containing fluorine
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • the present invention relates to a process for finishing textile materials by treatment with at least one aqueous liquor containing at least one organic polymer serving as a binder and at least one organic or inorganic solid in particulate form having an average particle diameter (median, number average). in the range of 1 nm to 350 nm, and at least one emulsifier selected from copolymers of ethylene and at least one ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid or at least one anhydride of an ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid, wherein the or organic or inorganic solids in the liquor in a proportion of at least 5.5 g / l.
  • Textile equipment is a field of growing economic importance. It is particularly interesting to equip textiles with water and dirt repellent. Modern measures make use of the so-called lotus effect® in some cases and give textiles a water-repellent behavior by applying a rough surface.
  • WO 96/04123 describes self-cleaning surfaces that have an artificial surface structure, which has elevations and depressions, wherein the structure is characterized in particular by their structural parameters.
  • the structures are produced, for example, by embossing a structure onto a thermoplastically deformable hydrophobic material or by applying Teflon powder to a surface treated with UHU®.
  • UHU® thermoplastically deformable hydrophobic material
  • Teflon powder Teflon powder
  • EP-A 0 933 388 For example, methods for the production of structured surfaces are known in which a negative mold is first produced by photolithography, this mold is used to emboss a plastic film and then the hydrophobicized embossed plastic film is fluorinated with alkylsilanes.
  • WO 02/84013 it is proposed to hydrophobicize fibers of, for example, polyester by passing them through a decaline bath heated to 80 ° C. in which 1% hydrophobic silica gel Aerosil® 8200 has been suspended.
  • WO 02/84016 it is proposed to hydrophobicize polyester fabric by pulling it through a bath of heated to 50 ° C DMSO (dimethyl sulfoxide) in which 1% hydrophobic silica gel Aeroperi® 8200 was suspended.
  • DMSO dimethyl sulfoxide
  • WO 01/75216 It is proposed to provide textile fibers and fabrics repellent to water and dirt by providing them with a two-component layer, one of which is a dispersant and the other, for example, a colloid.
  • a two-component layer one of which is a dispersant and the other, for example, a colloid.
  • finishing layers are prepared in which the colloids are anisotropically distributed in the dispersant, whereby accumulation of the colloids is observed at the interface between the finish layer and the surrounding surface.
  • the process uses such equipment fleets containing up to 5 g / l Aerosil 812 S.
  • textile materials are to be understood as meaning fibers, rovings, yarn, twine on the one hand, and textile fabrics on the other hand, such as, for example, woven goods, knitted fabrics, nonwovens and clothing.
  • textile fabrics which are used for example for the production of textile in the outdoor area. Examples include sails, umbrellas and umbrellas, tarpaulins, tarpaulins, tablecloths, awning fabrics and furniture covers, for example, chairs, swings or benches called.
  • Textile materials in the context of the present invention may consist of different materials. May include natural fibers and synthetic fibers and mixed fibers. Examples of natural fibers are silk, wool and cotton. Synthetic fibers include, by way of example, polyamide, polyester, polypropylene, polyacrylonitrile, polyethylene terephthalate and viscose. Also let modified natural fibers coated according to the method of the invention, for example, cellulose acetate.
  • the inventive method is based on at least one aqueous liquor.
  • an aqueous liquor is to be understood as meaning those liquors which may contain at least 5% by weight of water.
  • aqueous liquors contain at least 25% by weight of water, more preferably at least 50% by weight and most preferably at least 75% by weight.
  • the maximum water content is 99 wt .-%, preferably 97 wt .-%, particularly preferably 95 wt .-%.
  • Aqueous liquors used according to the invention may contain, in addition to water, organic solvents, for example methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers.
  • Organic solvents may constitute from 1 to 50% by weight, preferably from 2 to 25% by weight, of the aqueous liquor used according to the invention.
  • At least one of the liquors used in the process according to the invention contains at least one organic polymer which serves as a binder.
  • the effect of a binder may, for example, be such that the organic polymer forms a film and bonds the particles together and to the textile material to be coated.
  • At least one organic polymer is polymers or copolymers of ethylenically unsaturated hydrophobic monomers having a solubility in water of less than 1 g / l as determined at 25 ° C.
  • hydrophobic monomers constitute at least 50% by weight, preferably at least 75% by weight of the copolymer.
  • Preferred monomers are selected from the groups of C 2 -C 24 -olefins, in particular ⁇ -olefins having 2 to 24 C-atoms, for example ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene , 1-dodecene, 1-hexadecene or 1-octadecene; Vinylaromatics, for example styrene, ⁇ -methylstyrene, cis-stilbene, trans-stilbene, diolefins such as 1,3-butadiene, cyclopentadiene, chloroprene or isoprene, C 5 -C 18 -cycloolefins such as cyclopentene, cyclohexene, norbornene, dimeric cyclopentadiene, Vinyl esters of linear or branched C 1 -C 20 -alkanecarboxylic acids,
  • Halogenated monomers include chlorinated olefins such as vinyl chloride and vinylidene chloride.
  • halogenated monomers are fluorine-containing olefins such as, for example, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C 3 -C 11 -carboxylic acids, such as, for example, in US Pat US 2,592,069 and US 2,732,370 describe (meth) acrylic esters of fluorinated or perfluorinated alcohols, such as, for example, fluorinated or perfluorinated C 3 -C 14 -alkyl alcohols, for example (meth) acrylate esters of HO-CH 2 -CH 2 -CF 3 , HO-CH 2 -CH 2 -C 2 F 5 , HO-CH 2 -CH 2 -nC 3 F 7 , HO-CH 2 -CH 2 -iso-C 3 F 7 , HO-CH 2 -CH 2 -
  • copolymers are copolymers of (meth) acrylic acid esters of fluorinated or perfluorinated C 3 -C 12 -alkyl alcohols, for example HO-CH 2 -CH 2 -CF 3 , HO-CH 2 -CH 2 -C 2 F 5 , HO-CH 2 -CH 2 -nC 3 F 7 , HO-CH 2 -CH 2 -iso-C 3 F 7 , HO-CH 27 CH 2 -nC 4 F 9 , HO-CH 2 -CH 2 -nC 5 F 11 , HO -CH 2 -CH 2 -nC 6 F 13 , HO-CH 2 -CH 2 -nC 7 F 15 ; with (meth) acrylic acid esters of non-halogenated C 1 -C 20 -alcohols, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate,
  • fluorinated polymers are, for example, in DE 199 120 810 disclosed.
  • R 3 is selected from C 1 -C 18 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • C 6 -C 14 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl C 3 -C 12 cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl or Si (CH 3 ) 3 .
  • R 1 is defined as above.
  • n is an integer in the range of 0 to 6, especially 1 to 2;
  • m is an integer in the range of 2 to 10,000, especially up to 100.
  • polyethers such as, for example, polyethylene glycol, polypropylene glycol, polybutylene glycols, polytetrahydrofuran
  • Polycaprolactone polycarbonates, polyvinylbutyral, partially aromatic polyesters of aliphatic or aromatic dicarboxylic acids and / or aliphatic or aromatic dialcohols
  • polyesters composed of aliphatic dialcohols having 2 to 18 C atoms, such as, for example, ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, 1.8 Octanediol or bisphenol A, and aliphatic dicarboxylic acids having 3 to 18 C atoms such as succinic acid, clutaric acid, adipic acid and ⁇ , ⁇ -decanedicarboxylic acid; Polyester, composed of terephthalic acid and aliphatic dialcohols having 2 to 18 carbon atoms such as
  • polyesters can be terminated, for example, with monoalcohols, for example 4 to 12 C atoms, for example n-butanol, n-hexanol, n-octanol, n-decanol or n-dodecanol.
  • monoalcohols for example 4 to 12 C atoms, for example n-butanol, n-hexanol, n-octanol, n-decanol or n-dodecanol.
  • polyesters may be terminated, for example, with monocarboxylic acids such as, for example, stearic acid.
  • melamine-formaldehyde resins melamine-formaldehyde resins
  • urea-formaldehyde resins N, N-dimethylol-4,5-dihydroxyethyleneureas, which may be etherified with C 1 -C 5 -alcohols.
  • the molecular weight of the organic polymer or polymers can be chosen within wide ranges.
  • the weight average molecular weight may range from 1000 to 10,000,000 g / mol, preferably from 2,500 to 5,000,000 g / mol, determined by at least one of the following methods: light scattering, gel permeation chromatography (GPC), viscometry. If one uses a polymer from the group of polyolefins, for example polyethylene, polypropylene or polyisobutene and copolymers of ethylene with propylene, butylene or 1-hexene, the molecular weight is advantageously in the range of 30,000 to 5,000,000 g / mol.
  • the breadth of the molecular weight distribution is not critical per se and can range from 1.1 to 20. It is usually in the range of 2 to 10.
  • the proportion of the organic polymer (s) described above may be at least 0.1 g / l of the liquor, preferably at least 1 g / l and more preferably at least 10 g / l.
  • the maximum proportion is, for example, 500 g / l, preferably 250 g / l and particularly preferably 100 g / l.
  • the organic polymer (s) is not soluble in the liquor, wherein insoluble in the context of organic polymers in the sense of the present invention means that less than 1 g / l is soluble in the liquor at room temperature, preferably less as 0.9 g / l.
  • At least two different organic polymers are used.
  • At least one organic polymer may be present in the form of particles having an average particle diameter of 0.1 to 50 ⁇ m, preferably 0.5 to 30 ⁇ m and particularly preferably up to 20 ⁇ m (median value, number average).
  • At least one of the aqueous liquors used in the process according to the invention contains at least one hydrophobic solid in particulate form, which is different from the polymer or polymers described above, in a proportion of at least 5.5 g / l, preferably at least 7 g / l, more preferably at least 10 g / l. If it is desired to use a mixture of at least two hydrophobic solids in particulate form, then preferably at least one is present in a proportion of at least 5.5 g / l.
  • the maximum proportion of the hydrophobic solid (s) in particulate form may be a total of 150 g / l.
  • the hydrophobic solid in particulate Form may be inorganic or organic in nature, preferably it is inorganic.
  • suitable materials are polyethylene, polypropylene, polyisobutylene and polystyrene and copolymers thereof with each other or with one or more other olefins such as styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleimide , A preferred polyethylene or polypropylene, for example, in EP-A 0 761 696 described.
  • Particularly suitable materials are inorganic materials, in particular solid inorganic oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 of the Periodic Table of the Elements, for example calcium oxide, silicon dioxide or aluminum oxide, calcium carbonate, calcium sulfate or calcium silicate, with aluminum oxide and silicon dioxide being preferred.
  • Particularly preferred is silica in its modification as silica gel.
  • Very particular preference is given to pyrogenic silica gels.
  • Solid inorganic oxides can be thermally rendered hydrophobic by heating to 400 to 800 ° C or preferably by physisorbed or chemisorbed organic or organometallic compounds.
  • particles are reacted before the coating step, for example, with organometallic compounds which contain at least one functional group, for example alkyllithium compounds such as methyllithium, n-butylithium or n-hexyllithium; or silanes such as hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes such as trimethylchlorosilane or dichlorodimethylsilane.
  • organometallic compounds which contain at least one functional group
  • alkyllithium compounds such as methyllithium, n-butylithium or n-hexyllithium
  • silanes such as hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes such as trimethylchlorosilane or dichlorodimethylsilane.
  • Hydrophobic in the context of the hydrophobic solid (s) in particulate form is understood to mean that its solubility is below 1 g / l, preferably below 0.3 g / l, determined at room temperature.
  • Inorganic solids may preferably be porous in nature.
  • the porous structure is best characterized by the BET surface area, measured according to DIN 66131.
  • Inorganic solids used may preferably have a BET surface area in the range from 5 to 1000 m 2 / g, preferably from 10 to 800 m 2 / g and particularly preferably from 20 to 500 m 2 / g.
  • At least one of the hydrophobic solids is in particulate form.
  • the mean particle diameter (median value, number average) is at least 1 nm, preferably at least 3 nm and particularly preferably at least 6 nm.
  • the maximum particle diameter (median value, number average) is 350 nm, preferably 100 nm.
  • the weight ratio of organic polymer to organic or inorganic solid in particulate form is generally 9: 1 to 1: 9, preferably 4: 1 to 1.4 and more preferably 7: 3 to 4: 6.
  • At least one of the hydrophobic solids is present in the form of spherical particles, which should include those particulate solids, of which at least 75 wt .-%, preferably at least 90 wt .-% in spherical form and other particles in granular form.
  • At least one of the hydrophobic solids may form agglomerates.
  • agglomerates which may consist of 2 to several thousand primary particles and may in turn have spherical shape
  • the information on the shape and size of the particles refer to the primary particles.
  • the aqueous liquor used in the process according to the invention comprises at least one emulsifier selected from copolymers of ethylene and at least one ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid or at least one anhydride of an ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid, Maleic acid, fumaric acid, methylenemalonic acid, maleic anhydride, itaconic anhydride.
  • emulsifier selected from copolymers of ethylene and at least one ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid or at least one anhydride of an ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid, Maleic acid, fumaric acid, methylenemalonic acid, maleic anhydride, itaconic anhydride.
  • the carboxyl groups may be partially or preferably completely neutralized, for example with alkali metal ions, alkaline earth metal ions, ammonium or amines, for example amines such as triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethyldiisopropylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N - (n-butyl) diethanolamine or N, N-dimethylethanolamine.
  • alkali metal ions alkaline earth metal ions
  • ammonium or amines for example amines such as triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethyldiisopropylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N - (n-butyl) diethanolamine or N, N-d
  • the proportion of emulsifier in the liquor can be chosen within wide limits and can be 0.1 to 100 g / l, preferably 0.2 to 10 g / l.
  • the process according to the invention is carried out by treating textile material with at least one aqueous liquor. It is also possible to carry out a plurality of treatment steps with similar or different liquors.
  • the process according to the invention is carried out by first treating the textile to be treated with a liquor containing at least one organic polymer which serves as a binder. and further includes an organic or preferably inorganic solid in particulate form followed by further treatment with a new liquor containing the organic polymer but no further organic or inorganic solid in particulate form.
  • the process according to the invention is carried out by first treating the textile to be treated with a liquor which contains at least one organic polymer which serves as binder and furthermore an organic or preferably inorganic solid in particulate form, and then join another treatment with a new fleet that is another organic Contains polymer, but no further organic or inorganic solid in particulate form.
  • the process according to the invention is carried out by first treating the textile to be treated with a liquor which contains at least one organic polymer and furthermore an organic or preferably inorganic solid in particulate form and then a further treatment with a followed by a new liquor, which contains no further polymer, but the inorganic solid used in the first step in particulate form.
  • the temperature for carrying out the method according to the invention is not critical per se.
  • the liquor temperature may be in the range of 10 to 60 ° C, preferably 15 to 30 ° C.
  • the process parameters of the process according to the invention can be chosen such that the process according to the invention usually results in a liquor pickup of from 25% by weight to 85% by weight, preferably from 40 to 70% by weight.
  • the method according to the invention can be carried out in conventional machines which are used for finishing textiles, for example foulards.
  • Foulards with vertical textile infeed which contain as an essential element two rollers pressed against each other through which the textile is guided, are preferred. Above the rollers, the liquid is filled in and wets the textile. The pressure squeezes off the textile and ensures a constant application.
  • the speed of textile infeed of the foulards in one embodiment of the present invention is 1 to 40 m / min, preferably 1 to 30 m / min.
  • the treated textile can be dried by methods customary in the textile industry.
  • temper After the treatment according to the invention, it is possible to temper, continuously or discontinuously.
  • the duration of tempering can be chosen within wide limits. Usually, one can over the duration of about 10 seconds to about 30 minutes, in particular 30 seconds to 5 minutes annealing.
  • To carry out a heat treatment is heated to temperatures of up to 180 ° C, preferably up to 150 ° C. Of course, it is necessary to adjust the tempering temperature to the sensitivity of the fabric.
  • Suitable method for annealing is for example a hot air drying.
  • the textile material prior to the treatment according to the invention, is provided with an adhesive layer.
  • an adhesive layer For this you can use a so-called primer.
  • the application of a primer is preferred if one desires to equip synthetic fibers.
  • polymers on the textile material to be treated can be applied as an adhesive layer, for example, one or more polymers on the textile material to be treated, wherein the polymer synthesis can also be carried out on the textile material.
  • Particularly suitable polymers are those polymers which have crosslinked or crosslinkable groups, for example natural or synthetic polymers having free hydroxyl groups, carbonyl groups, primary or secondary amino groups or thiol groups.
  • suitable polymers are lignin, polysaccharides, polyvinyl alcohol and polyethyleneimine.
  • Crosslinking can be achieved, for example, by subsequent reaction with, for example, isocyanates, dimethylolurea or N, N-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU).
  • Other particularly preferred crosslinkers are melamine-formaldehyde resins, which may be etherified with methanol.
  • 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% of the textile are saponified in polyesters or polyamides to be treated by partial saponification with strong alkalis such as aqueous sodium hydroxide or potassium hydroxide.
  • Another object of the present invention are textile materials, equipped by the method according to the invention.
  • equipping the inventive textiles are provided with one or more layers.
  • the textile materials of the invention show particularly good dirt and water-repellent behavior. Furthermore, textile materials of the invention show very good mechanical strength.
  • the solid (s) used is or isotropic or substantially isotropically distributed over the finish layer, i. no concentration is detected in the boundary layer between the finish layer and the surrounding atmosphere.
  • the textiles according to the invention contain 0.5 to 50 g / m 2 layer, preferably 1 to 20 g / m 2 and particularly preferably 1.5 to 10 g / m 2 .
  • Another object of the present invention are aqueous liquors for finishing textile materials, containing at least one organic polymer which serves as a binder, and at least one organic or inorganic solid in particulate form with an average particle diameter (median, number average) in the range of 1 nm to 350 nm, wherein the organic or inorganic solids in the liquor in a proportion of at least 5.5 g / l.
  • the liquors of the invention may contain further components, for example one or more organic solvents or one or more emulsifiers.
  • Another object of the present invention is the use of the liquors of the invention for finishing textile materials.
  • the preparation process of the invention can be carried out usually at temperatures from room temperature to about 100 ° C, with room temperature being preferred.
  • the production process according to the invention generally comprises a homogenization step, for example by mechanical or pneumatic stirring, shaking, ultrasound treatment or a combination thereof. In some cases, however, one can do without the Homogenisier suits.
  • the order of addition of the components can be chosen arbitrarily in principle. So you can, for example, first prepare a water and solvent-free mixture of polymer and organic or inorganic solid and then disperse the dry mixture in organic solvent or mixture of water and organic solvent or in water.
  • formulations are first prepared which contain organic polymer, organic or inorganic solid in particulate form, optionally one or more organic solvents and optionally one or more emulsifiers and optionally water.
  • a liquor of the invention by diluting the formulation with water. It is preferred that the formulations according to the invention contain a maximum of 15% by weight, preferably about 0.1 to 10% by weight, particularly preferably up to 5% by weight of water.
  • the formulations of the invention may also be anhydrous.
  • Another object of the present invention are formulations containing organic polymer, organic or inorganic solid in particulate form, optionally one or more organic solvents and optionally one or more emulsifiers and optionally water, wherein the proportion of water about 0.1 to 10 wt .-%, preferably up to 5 wt .-% is.
  • Example 1.1 Production of the fleet 1.1
  • Example 1.2 Production of the fleet 1.2
  • Example 1.4 Production of the fleet 1.4
  • a polyester fabric having a basis weight of 220 g / m 2 was treated with Fleet 1.1 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. Subsequently, the treated polyester fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyester fabric 2.1 was obtained.
  • a polyamide fabric having a weight per unit area of 160 g / m 2 was treated with liquor 1.1 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 65%. The application speed was 2 m / min. Subsequently, the treated polyamide fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyamide fabric 2.2 was obtained.
  • a polyacrylic fabric having a basis weight of 295 g / m 2 was treated with Fleet 1.1 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 50%. The application speed was 2 m / min. Subsequently, the treated polyacrylic fabric was dried at 120 ° C on a tenter. The final temper took place over a period of 3 min at 150 ° C under circulating air. The treated polyacrylic fabric 2.3 was obtained.
  • a polyester fabric having a weight per unit area of 220 g / m 2 was treated with Fleece 1.2 on a padder (manufacturer: Mathis, type no. HVF12085).
  • the contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%.
  • the application speed was 2 m / min.
  • the treated polyester fabric was dried at 120 ° C on a tenter.
  • the final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air.
  • the treated polyester fabric 2.4 was obtained.
  • a polyamide fabric having a weight per unit area of 160 g / m 2 was treated with Fleece 1.2 on a padder (manufacturer Mathis, type no. HVF12085).
  • the contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 65%.
  • the application speed was 2 m / min.
  • the treated polyamide fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air.
  • the treated polyamide fabric 2.5 was obtained.
  • a polyacrylic fabric having a basis weight of 295 g / m 2 was treated with liquor 1.2 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 50%. The application speed was 2 m / min. Subsequently, the treated polyacrylic fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyacrylic fabric 2.6 was obtained.
  • the textile sample to be tested according to the invention was tensioned manually and fixed with needles on a flat wooden board whose inclination could be adjusted continuously from 1 ° to 90 °. Then, with the help of a cannula from a height of 10 mm, individual drops of water were dropped onto the textile sample. The drops had a mass of 4.7 mg. By gradually lowering the angle of inclination, the angle of inclination was determined at which the drops just bared and no adhesion was observed. The results are shown in Table 1.
  • Table 1 Inclination angle sample Inclination angle [°] 2.1 5 2.2 3 2.3 6 2.4 7 2.5 6 2.6 8th

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Abstract

Process for finishing textile materials involves treatment with aqueous liquor(s) (I) containing organic polymer(s) (II) and not less than 5.5 g/l particulate (in)organic solid(s) (III). Independent claims are also included for the following: (1) (I) per se; (2) production of (I) by mixing (II), (III), water, optionally organic solvent(s) and optionally other components, so that the (III) concentration is not less than 5.5 g/l; (3) formulation (IV) containing (II), (III), optionally organic solvent(s), optionally emulsifier(s) and 0-15 wt.% water.

Description

Die vorliegende Erfindung betrifft ein Verfahren zur Ausrüstung von textilen Materialien durch Behandlung mit mindestens einer wässrigen Flotte, die mindestens ein organisches Polymer enthält, das als Bindemittel dient, und mindestens einen organischen oder anorganischen Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser (Median, Zahlenmittel) im Bereich von 1 nm bis 350 nm, und mindestens einem Emulgator, ausgewählt aus Copolymerisaten von Ethylen und mindestens einer α,β-ungesättigten Mono- oder Dicarbonsäure oder mindestens einem Anhydrid einer α,β-ungesättigten Mono- oder Dicarbonsäure, wobei der oder die organischen oder anorganischen Feststoffe in der Flotte in einem Anteil von mindestens 5,5 g/l vorliegen.The present invention relates to a process for finishing textile materials by treatment with at least one aqueous liquor containing at least one organic polymer serving as a binder and at least one organic or inorganic solid in particulate form having an average particle diameter (median, number average). in the range of 1 nm to 350 nm, and at least one emulsifier selected from copolymers of ethylene and at least one α, β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α, β-unsaturated mono- or dicarboxylic acid, wherein the or organic or inorganic solids in the liquor in a proportion of at least 5.5 g / l.

Die Ausrüstung von Textilien ist ein Arbeitsgebiet mit wachsender wirtschaftlicher Bedeutung. Besonders interessant ist es, Textilien wasser- und schmutzabweisend auszurüsten. Moderne Maßnahmen bedienen sich in einigen Fällen des sogenannten Lotus-Effekts® und verleihen Textilien durch das Aufbringen einer rauen Oberfläche ein wasserabweisendes Verhalten.Textile equipment is a field of growing economic importance. It is particularly interesting to equip textiles with water and dirt repellent. Modern measures make use of the so-called lotus effect® in some cases and give textiles a water-repellent behavior by applying a rough surface.

WO 96/04123 beschreibt selbstreinigende Oberflächen, die eine künstliche Oberflächenstruktur besitzen, welche Erhebungen und Vertiefungen aufweist, wobei die Struktur insbesondere durch ihre Strukturparameter gekennzeichnet ist. Die Herstellung der Strukturen erfolgt beispielsweise durch Aufprägen einer Struktur auf ein thermoplastisch verformbares hydrophobes Material oder durch Aufbringen von Teflonpulver auf eine mit UHU® behandelte Fläche. Aus US 3,354,022 sind ähnlich hergestellte Wasser abweisende Flächen bekannt. WO 96/04123 describes self-cleaning surfaces that have an artificial surface structure, which has elevations and depressions, wherein the structure is characterized in particular by their structural parameters. The structures are produced, for example, by embossing a structure onto a thermoplastically deformable hydrophobic material or by applying Teflon powder to a surface treated with UHU®. Out US 3,354,022 Similarly prepared water repellent surfaces are known.

Aus EP-A 0 933 388 sind Verfahren zur Herstellung von strukturierten Oberflächen bekannt, bei denen man zunächst durch Photolithographie eine Negativform herstellt, mit dieser Form eine Kunststofffolie prägt und anschließend die geprägte Kunststofffolie mit fluorierten Alkylsilanen hydrophobiert.Out EP-A 0 933 388 For example, methods for the production of structured surfaces are known in which a negative mold is first produced by photolithography, this mold is used to emboss a plastic film and then the hydrophobicized embossed plastic film is fluorinated with alkylsilanes.

Die oben beschriebenen Methoden sind jedoch zur Schmutz und Wasser abweisenden Ausrüstung von Textilien ungeeignet.However, the methods described above are unsuitable for the dirt and water repellent finishing of textiles.

In WO 02/84013 wird vorgeschlagen, Fasern beispielsweise aus Polyester dadurch zu hydrophobieren, dass man sie durch ein auf 80°C erhitztes Bad aus Decalin, in dem 1% hydrophobiertes Kieselgel Aerosil® 8200 suspendiert wurde, hindurchzieht.In WO 02/84013 For example, it is proposed to hydrophobicize fibers of, for example, polyester by passing them through a decaline bath heated to 80 ° C. in which 1% hydrophobic silica gel Aerosil® 8200 has been suspended.

In WO 02/84016 wird vorgeschlagen, Polyestergewebe dadurch zu hydrophobieren, dass man es durch ein Bad aus auf 50°C erwärmtes DMSO (Dimethylsulfoxid), in dem 1% hydrophobiertes Kieselgel Aeroperi® 8200 suspendiert wurde, hindurchzieht.In WO 02/84016 it is proposed to hydrophobicize polyester fabric by pulling it through a bath of heated to 50 ° C DMSO (dimethyl sulfoxide) in which 1% hydrophobic silica gel Aeroperi® 8200 was suspended.

Beiden Methoden zur Hydrophobierung ist gemeinsam, dass das Lösemittel so gewählt wird, dass die Fasern partiell gelöst werden. Dazu ist es erforderlich, dass man große Mengen an organischem Lösemittel einsetzt, was in vielen Fällen unerwünscht ist. Außerdem kann durch Behandlung mit organischen Lösemitteln die mechanische Festigkeit der Fasern beeinflusst werden.Both methods of hydrophobing have in common that the solvent is chosen so that the fibers are partially dissolved. For this it is necessary to use large amounts of organic solvent, which is undesirable in many cases. In addition, by treatment with organic solvents, the mechanical strength of the fibers can be influenced.

In WO 01/75216 wird vorgeschlagen, textile Fasern und Flächengebilde dadurch Wasser und Schmutz abweisend auszurüsten, dass man sie mit einer Zwei-Komponenten-Schicht versieht, von denen eine ein Dispersionsmittel und die andere beispielsweise ein Kolloid ist. Durch das in WO 01/75216 beschriebene Ausrüstungsverfahren werden Ausrüstungsschichten hergestellt, bei denen die Kolloide anisotrop im Dispersionsmittel verteilt sind, wobei man eine Anreicherung der Kolloide an der Grenzfläche zwischen Ausrüstungsschicht und umgebender Oberfläche beobachtet. Das Verfahren wendet dabei solche Ausrüstungsflotten an, die bis zu 5 g/l Aerosil 812 S enthalten.In WO 01/75216 It is proposed to provide textile fibers and fabrics repellent to water and dirt by providing them with a two-component layer, one of which is a dispersant and the other, for example, a colloid. Through the in WO 01/75216 In the finishing process described, finishing layers are prepared in which the colloids are anisotropically distributed in the dispersant, whereby accumulation of the colloids is observed at the interface between the finish layer and the surrounding surface. The process uses such equipment fleets containing up to 5 g / l Aerosil 812 S.

Durch das in WO 01/75216 beschriebene Verfahren ausgerüstete Textilien weisen jedoch in vielen Fällen eine nicht zufrieden stellende mechanische Belastbarkeit auf.Through the in WO 01/75216 however, in many cases, textiles finished in the described manner have unsatisfactory mechanical strength.

Es bestand daher die Aufgabe, ein Verfahren zur Ausrüstung von textilen Materialien zur Verfügung zu stellen, das die oben aufgezeigten Nachteile nicht aufweist und gleichzeitig sehr gute Wasser- und Schmutz abweisende Wirkung aufweist. Es bestand weiterhin die Aufgabe, Schmutz und Wasser abweisende Textilien bereitzustellen. Weiterhin bestand die Aufgabe, Flotten zur Schutz und Wasser abweisenden Ausrüstung von textilen Materialien zur Verfügung zu stellen.It was therefore an object to provide a method for finishing textile materials, which does not have the above-mentioned disadvantages and at the same time has very good water and dirt repellent effect. It was also the task of providing dirt and water repellent textiles. Another object was to provide fleets for the protection and water-repellent finishing of textile materials.

Demgemäß wurde das einganges definierte Verfahren gefunden.Accordingly, the eingangs defined method was found.

Unter textilen Materialien sind im Sinne der vorliegenden Erfindung Fasern, Vorgarn, Garn, Zwirn einerseits und textile Flächengebilde andererseits wie beispielsweise Webwaren, Maschenwaren, Vliese und Bekleidungsstücke zu verstehen. Besonders bevorzugt sind textile Flächengebilde, die beispielsweise zur Herstellung von Textil im Außenbereich verwendet werden. Beispielhaft seien Segel, Sonnen- und Regenschirme, Planen, Zeltbahnen, Tischdecken, Markisenstoffe und Möbelbespannungen beispielsweise für Stühle, Schaukeln oder Bänke genannt.For the purposes of the present invention, textile materials are to be understood as meaning fibers, rovings, yarn, twine on the one hand, and textile fabrics on the other hand, such as, for example, woven goods, knitted fabrics, nonwovens and clothing. Particularly preferred are textile fabrics, which are used for example for the production of textile in the outdoor area. Examples include sails, umbrellas and umbrellas, tarpaulins, tarpaulins, tablecloths, awning fabrics and furniture covers, for example, chairs, swings or benches called.

Textile Materialien im Sinne der vorliegenden Erfindung können aus unterschiedlichen Stoffen bestehen. Genannt seien Naturfasern und Synthesefasern sowie Mischfasern. Unter Naturfasern seien beispielsweise Seide, Wolle und Baumwolle genannt. Unter Synthesefasern seien beispielhaft Polyamid, Polyester, Polypropylen, Polyacrylnitril, Polyethylenterephthalat und Viskose genannt. Auch modifizierte Naturfasern lassen sich nach dem erfindungsgemäßen Verfahren beschichten, beispielsweise Celluloseacetat.Textile materials in the context of the present invention may consist of different materials. May include natural fibers and synthetic fibers and mixed fibers. Examples of natural fibers are silk, wool and cotton. Synthetic fibers include, by way of example, polyamide, polyester, polypropylene, polyacrylonitrile, polyethylene terephthalate and viscose. Also let modified natural fibers coated according to the method of the invention, for example, cellulose acetate.

Das erfindungsgemäße Verfahren geht aus von mindestens einer wässrigen Flotte. Unter wässriger Flotte im Sinne der vorliegenden Erfindung sind solche Flotten zu verstehen, die mindestens 5 Gew.-% Wasser enthalten können. Bevorzugt enthalten wässrige Flotten mindestens 25 Gew.-% Wasser, besonders bevorzugt mindestens 50 Gew.-% und ganz besonders bevorzugt mindestens 75 Gew.-%. Der maximale Wassergehalt beträgt 99 Gew.-%, bevorzugt 97 Gew.-%, besonders bevorzugt 95 Gew.-%.The inventive method is based on at least one aqueous liquor. For the purposes of the present invention, an aqueous liquor is to be understood as meaning those liquors which may contain at least 5% by weight of water. Preferably, aqueous liquors contain at least 25% by weight of water, more preferably at least 50% by weight and most preferably at least 75% by weight. The maximum water content is 99 wt .-%, preferably 97 wt .-%, particularly preferably 95 wt .-%.

Erfindungsgemäß eingesetzte wässrige Flotten können neben Wasser organische Lösemittel enthalten, beispielsweise Methanol, Ethanol, Isopropanol, Aceton, Methylethylketon, Methylisobutylketon, Ethylenglykol-mono-n-Butylether, Ethylenglykol-mono-iso-Butylether, Essigsäure, n-Butanol, iso-Butanol, n-Hexanol und Isomere, n-Octanol und Isomere, n-Dodecanol und Isomere. Organische Lösemittel können 1 bis 50 Gew.-%, bevorzugt 2 bis 25 Gew.-% der erfindungsgemäß eingesetzten wässrigen Flotte ausmachen.Aqueous liquors used according to the invention may contain, in addition to water, organic solvents, for example methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol monoisobutyl ether, acetic acid, n-butanol, isobutanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers. Organic solvents may constitute from 1 to 50% by weight, preferably from 2 to 25% by weight, of the aqueous liquor used according to the invention.

Mindestens eine der im erfindungsgemäßen Verfahren eingesetzten Flotten enthält mindestens ein organisches Polymer, das als Bindemittel dient. Die Wirkung eines Bindemittels kann beispielsweise dergestalt erfolgen, dass das organische Polymer einen Film bildet und die Partikel miteinander und mit dem zu beschichtenden textilen Material verbindet.At least one of the liquors used in the process according to the invention contains at least one organic polymer which serves as a binder. The effect of a binder may, for example, be such that the organic polymer forms a film and bonds the particles together and to the textile material to be coated.

In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei mindestens einem organischen Polymeren um Polymere oder Copolymere von ethylenisch ungesättigten hydrophoben Monomeren, die in Wasser eine Löslichkeit von weniger als 1 g/l haben, bestimmt bei 25°C. In Copolymeren machen hydrophobe Monomere mindestens 50 Gew.-%, bevorzugt mindestens 75 Gew.-% des Copolymers aus.In one embodiment of the present invention, at least one organic polymer is polymers or copolymers of ethylenically unsaturated hydrophobic monomers having a solubility in water of less than 1 g / l as determined at 25 ° C. In copolymers, hydrophobic monomers constitute at least 50% by weight, preferably at least 75% by weight of the copolymer.

Bevorzugte Monomere sind gewählt aus den Gruppen der C2-C24-Olefine, insbesondere α-Olefine mit 2 bis 24 C-Atomen, beispielsweise Ethylen, Propylen, 1-Buten, Isobuten, 1-Hexen, 1-Octen, 1-Decen, 1-Dodecen, 1-Hexadecen oder 1-Octadecen;
Vinylaromaten, beispielsweise Styrol, a-Methylstyrol, cis-Stilben, trans-Stilben, Diolefine wie beispielsweise 1,3-Butadien, Cyclopentadien, Chloropren oder Isopren, C5-C18-Cycloolefine wie beispielsweise Cyclopenten, Cyclohexen, Norbornen, dimeres Cyclopentadien,
Vinylester von linearen oder verzweigten C1-C20-Alkancarbonsäuren wie beispielsweise Vinylacetat, Vinylpropionat, Vinyl-n-butyrat, Vinyl-n-hexanoat, Vinyl-n-octanoat, Vinyllaurat und Vinylstearat,
(Meth)acrylsäureester von C1-C20-Alkoholen, beispielsweise Methyl(meth)acrylat, Ethyl-(meth)acrylat, n-Propyl(meth)acrylat, iso-Propyl(meth)acrylat, n-Butyl(meth)acrylat, iso-Butyl(meth)acrylat), tert.-Butyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, n-Octyl(meth)-acrylat, n-Decyl(meth)acrylat, n-Dodecyl(meth)acrylat, n-Eicosyl(meth)acrylat und ganz besonders bevorzugt aus den Gruppen der halogenierten Monomere und der Monomere mit Siloxangruppen.Preferred monomers are selected from the groups of C 2 -C 24 -olefins, in particular α-olefins having 2 to 24 C-atoms, for example ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-octene, 1-decene , 1-dodecene, 1-hexadecene or 1-octadecene;
Vinylaromatics, for example styrene, α-methylstyrene, cis-stilbene, trans-stilbene, diolefins such as 1,3-butadiene, cyclopentadiene, chloroprene or isoprene, C 5 -C 18 -cycloolefins such as cyclopentene, cyclohexene, norbornene, dimeric cyclopentadiene,
Vinyl esters of linear or branched C 1 -C 20 -alkanecarboxylic acids, such as, for example, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl n-hexanoate, vinyl n-octanoate, vinyl laurate and vinyl stearate,
(Meth) acrylic esters of C 1 -C 20 -alcohols, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate , iso-butyl (meth) acrylate), tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-eicosyl (meth) acrylate, and most preferably from the groups of the halogenated monomers and the monomers with siloxane groups.

Zu halogenierten Monomeren gehören chlorierte Olefine wie beispielsweise Vinylchlorid und Vinylidenchlorid.Halogenated monomers include chlorinated olefins such as vinyl chloride and vinylidene chloride.

Ganz besonders bevorzugte halogenierte Monomere sind fluorhaltige Olefine wie beispielsweise Vinylidenfluorid, Trifluorchlorethylen, Tetrafluorethylen, Hexafluorpropylen, Vinylester von fluorierten oder perfluorierten C3-C11-Carbonsäuren wie beispielsweise in US 2,592,069 und US 2,732,370 beschrieben (Meth)acrylsäureester von fluorierten oder perfluorierten Alkoholen wie beispielsweise fluorierten oder perfluorierten C3-C14-Alkylalkoholen, beispielsweise (Meth)acrylatsäureeester von HO-CH2-CH2-CF3, HO-CH2-CH2-C2F5, HO-CH2-CH2-n-C3F7, HO-CH2-CH2-iso-C3F7, HO-CH2-CH2-n-C4F9, HO-CH2-CH2-n-C6F13, HO-CH2-CH2-n-C8F17, HO-CH2-CH2-n-C10F21, HO-CH2-CH2-n-C12F25, beschrieben beispielsweise in US 2,642,416 , US 3,239,557 , BR 1,118,007 , US 3,462,296 .Very particularly preferred halogenated monomers are fluorine-containing olefins such as, for example, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C 3 -C 11 -carboxylic acids, such as, for example, in US Pat US 2,592,069 and US 2,732,370 describe (meth) acrylic esters of fluorinated or perfluorinated alcohols, such as, for example, fluorinated or perfluorinated C 3 -C 14 -alkyl alcohols, for example (meth) acrylate esters of HO-CH 2 -CH 2 -CF 3 , HO-CH 2 -CH 2 -C 2 F 5 , HO-CH 2 -CH 2 -nC 3 F 7 , HO-CH 2 -CH 2 -iso-C 3 F 7 , HO-CH 2 -CH 2 -nC 4 F 9 , HO-CH 2 -CH 2 -nC 6 F 13 , HO-CH 2 -CH 2 -nC 8 F 17 , HO-CH 2 -CH 2 -nC 10 F 21 , HO-CH 2 -CH 2 -nC 12 F 25 , described for example in US 2,642,416 . US 3,239,557 . BR 1,118,007 . US 3,462,296 ,

Auch Copolymere von beispielsweise Glycidyl(meth)acrylat mit Estern der Formel I

Figure imgb0001
in denen die Variablen wie folgt definiert sind:

R1
Wasserstoff, CH3, C2H5,
R2
CH3, C2H5,
x
eine ganze Zahl im Bereich von 4 bis 12, ganz besonders bevorzugt 6 bis 8
y
eine ganze Zahl im Bereich von 1 bis 11, bevorzugt 1 bis 6,
oder Glycidy(meth)acrylat mit Vinylestern von fluorierten Carbonsäuren sind geeignet.Also copolymers of, for example, glycidyl (meth) acrylate with esters of the formula I.
Figure imgb0001
 where the variables are defined as follows:
R 1
Hydrogen, CH 3 , C 2 H 5 ,
R 2
CH 3 , C 2 H 5 ,
x
an integer in the range of 4 to 12, most preferably 6 to 8
y
an integer in the range of 1 to 11, preferably 1 to 6,
or glycidyl (meth) acrylate with vinyl esters of fluorinated carboxylic acids are suitable.

Weitere geeignete Copolymere sind Copolymerisate von (Meth)acrylsäureestern fluorierter oder perfluorierter C3-C12-Alkylalkohole wie beispielsweise HO-CH2-CH2-CF3, HO-CH2-CH2-C2F5, HO-CH2-CH2-n-C3F7, HO-CH2-CH2-iso-C3F7, HO-CH27CH2-n-C4F9, HO-CH2-CH2-n-C5F11, HO-CH2-CH2-n-C6F13, HO-CH2-CH2-n-C7F15; mit (Meth)acrylsäureestern nicht-halogenierter C1-C20-Alkohole, beispielsweise Methyl(meth)acrylat, Ethyl(meth)acrylat, n-Butyl(meth)acrylat, n-Propyl(meth)acrylat, 2-Ethylhexyl(meth)acrylat, n-Octyl(meth)acrylat, n-Decyl(meth)acrylat, n-Dodecyl-(meth)acrylat, n-Eicosyl(meth)acrylat.Further suitable copolymers are copolymers of (meth) acrylic acid esters of fluorinated or perfluorinated C 3 -C 12 -alkyl alcohols, for example HO-CH 2 -CH 2 -CF 3 , HO-CH 2 -CH 2 -C 2 F 5 , HO-CH 2 -CH 2 -nC 3 F 7 , HO-CH 2 -CH 2 -iso-C 3 F 7 , HO-CH 27 CH 2 -nC 4 F 9 , HO-CH 2 -CH 2 -nC 5 F 11 , HO -CH 2 -CH 2 -nC 6 F 13 , HO-CH 2 -CH 2 -nC 7 F 15 ; with (meth) acrylic acid esters of non-halogenated C 1 -C 20 -alcohols, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, n-propyl (meth) acrylate, 2-ethylhexyl (meth ) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, n-eicosyl (meth) acrylate.

Eine Übersicht über geeignete fluorierte Polymere und Copolymere findet sich beispielsweise in M. Lewin et al., Chemical Processing of Fibers and Fabrics, Part B, 2. Band, Marcel Dekker, New York (1984), Seite S. 172 ff. und S. 178 -182 .An overview of suitable fluorinated polymers and copolymers can be found for example in Lewin, M., et al., Chemical Processing of Fibers and Fabrics, Part B, Volume 2, Marcel Dekker, New York (1984), pp. 172 ff., And pp. 178-182 ,

Weitere geeignete fluorierte Polymere sind beispielsweise in DE 199 120 810 offengelegt.Further suitable fluorinated polymers are, for example, in DE 199 120 810 disclosed.

Aus der Gruppe der Olefine mit Siloxangruppen seien beispielsweise Olefine der allgemeinen Formeln II a bis II c

Figure imgb0002
Figure imgb0003
Figure imgb0004
 genannt, in denen die Variablen wie folgt definiert sind:
R3 ist gewählt aus
C1-C18-Alkyl, beispielsweise Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, iso-Heptyl, n-Octyl, n-Nonyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octadecyl; bevorzugt C1-C6-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, besonders bevorzugt C1-C4-Alkyl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl und ganz besonders Methyl.
C6-C14-Aryl, beispielsweise Phenyl, 1-Naphthyl, 2-Naphthyl, 1-Anthryl, 2-Anthryl, 9-Anthryl, 1-Phenanthryl, 2-Phenanthryl, 3-Phenanthryl, 4-Phenanthryl und 9-Phenanthryl, bevorzugt Phenyl, 1-Naphthyl und 2-Naphthyl, besonders bevorzugt Phenyl C3-C12-Cycloalkyl, beispielsweise Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl oder Si(CH3)3.From the group of olefins with siloxane groups, for example, olefins of the general formulas II a to II c
Figure imgb0002
Figure imgb0003
Figure imgb0004
 in which the variables are defined as follows:
R 3 is selected from
C 1 -C 18 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl; preferably C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, more preferably C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl , n-butyl, iso-butyl, sec-butyl and tert-butyl and most especially methyl.
C 6 -C 14 aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl C 3 -C 12 cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl or Si (CH 3 ) 3 .

R1 ist wie oben stehend definiert.
n ist eine ganze Zahl im Bereich von 0 bis 6, insbesondere 1 bis 2;
m ist eine ganze Zahl im Bereich von 2 bis 10.000, insbesondere bis 100.R 1 is defined as above.
n is an integer in the range of 0 to 6, especially 1 to 2;
m is an integer in the range of 2 to 10,000, especially up to 100.

Weiterhin sind geeignete Polymere: Polyether wie beispielsweise Polyethylenglykol, Polypropylenglykol, Polybutylenglykole, Polytetrahydrofuran;
Polycaprolacton, Polycarbonate, Polyvinylbutyral,
teilaromatische Polyester aus aliphatischen oder aromatischen Dicarbonsäuren und/oder aliphatischen oder aromatischen Dialkoholen, z.B. Polyester, aufgebaut aus aliphatischen Dialkoholen mit 2 bis 18 C-Atomen wie beispielsweise Ethylenglykol, Propandiol, 1,4-Butandiol, 1,6-Hexandiol, 1,8-Octandiol oder Bisphenol A, und aliphatischen Dicarbonsäuren mit 3 bis 18 C-Atomen wie beispielsweise Bernsteinsäure, Clutarsäure, Adipinsäure und α,ω-Decandicarbonsäure; Polyester, aufgebaut aus Terephthalsäure und aliphatischen Dialkoholen mit 2 bis 18 C-Atomen wie beispielsweise Ethylenglykol, Propandiol, 1,4-Butandiol, 1,6-Hexandiol oder 1,8-Octandiol.Further suitable polymers are: polyethers such as, for example, polyethylene glycol, polypropylene glycol, polybutylene glycols, polytetrahydrofuran;
Polycaprolactone, polycarbonates, polyvinylbutyral,
partially aromatic polyesters of aliphatic or aromatic dicarboxylic acids and / or aliphatic or aromatic dialcohols, for example polyesters, composed of aliphatic dialcohols having 2 to 18 C atoms, such as, for example, ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol, 1.8 Octanediol or bisphenol A, and aliphatic dicarboxylic acids having 3 to 18 C atoms such as succinic acid, clutaric acid, adipic acid and α, ω-decanedicarboxylic acid; Polyester, composed of terephthalic acid and aliphatic dialcohols having 2 to 18 carbon atoms such as ethylene glycol, propanediol, 1,4-butanediol, 1,6-hexanediol or 1,8-octanediol.

Vorstehend genannte Polyester können beispielsweise mit Monoalkoholen wie beispielsweise 4 bis 12 C-Atomen terminiert sein, beispielsweise n-Butanol, n-Hexanol, n-Octanol, n-Decanol oder n-Dodecanol.The abovementioned polyesters can be terminated, for example, with monoalcohols, for example 4 to 12 C atoms, for example n-butanol, n-hexanol, n-octanol, n-decanol or n-dodecanol.

Vorstehend genannte Polyester können beispielsweise mit Monocarbonsäuren wie beispielsweise Stearinsäure terminiert sein.The abovementioned polyesters may be terminated, for example, with monocarboxylic acids such as, for example, stearic acid.

Weitere geeignete Polymere sind Melamin-Formaldehyd-Harze, Harnstoff-Formaldehyd-Harze, N,N-Dimethylol-4,5-dihydroxyethylenharnstoffe, die mit C1-C5-Alkoholen verethert sein können.Further suitable polymers are melamine-formaldehyde resins, urea-formaldehyde resins, N, N-dimethylol-4,5-dihydroxyethyleneureas, which may be etherified with C 1 -C 5 -alcohols.

Das Molekulargewicht des oder der organischen Polymeren lässt sich in weiten Bereichen wählen. Das Molekulargewicht (Gewichtsmittel) kann im Bereich von 1000 bis 10.000.000 g/mol, vorzugsweise im Bereich von 2500 bis 5.000.000 g/mol liegen, ermittelt nach mindestens einer der folgenden Methoden: Lichtstreuung, Gelpermeationschromatographie (GPC), Viskosimetrie. Wenn man ein Polymer aus der Gruppe der Polyolefine einsetzt, beispielsweise Polyethylen, Polypropylen oder Polyisobuten sowie Copolymere von Ethylen mit Propylen, Butylen oder 1-Hexen, so liegt das Molekulargewicht vorteilhaft im Bereich von 30.000 bis 5.000.000 g/mol.The molecular weight of the organic polymer or polymers can be chosen within wide ranges. The weight average molecular weight may range from 1000 to 10,000,000 g / mol, preferably from 2,500 to 5,000,000 g / mol, determined by at least one of the following methods: light scattering, gel permeation chromatography (GPC), viscometry. If one uses a polymer from the group of polyolefins, for example polyethylene, polypropylene or polyisobutene and copolymers of ethylene with propylene, butylene or 1-hexene, the molecular weight is advantageously in the range of 30,000 to 5,000,000 g / mol.

Die Breite der Molekulargewichtsverteilung ist an sich unkritisch und kann im Bereich von 1,1 bis 20 liegen. Üblicherweise liegt sie im Bereich von 2 bis 10.The breadth of the molecular weight distribution is not critical per se and can range from 1.1 to 20. It is usually in the range of 2 to 10.

In einer Ausführungsform der vorliegenden Erfindung kann der Anteil des oder der oben beschriebenen organischen Polymere bei mindestens 0,1 g/l der Flotte liegen, bevorzugt mindestens 1 g/l und besonders bevorzugt bei mindestens 10 g/l. Der maximale Anteil liegt beispielsweise bei 500 g/l, bevorzugt bei 250 g/l und besonders bevorzugt bei 100 g/l.In one embodiment of the present invention, the proportion of the organic polymer (s) described above may be at least 0.1 g / l of the liquor, preferably at least 1 g / l and more preferably at least 10 g / l. The maximum proportion is, for example, 500 g / l, preferably 250 g / l and particularly preferably 100 g / l.

In einer Ausführungsform der vorliegenden Erfindung ist das oder die organischen Polymere in der Flotte nicht löslich, wobei nicht löslich im Zusammenhang mit organischen Polymeren im Sinne der vorliegenden Erfindung bedeutet, dass bei Zimmertemperatur weniger als 1 g/l in der Flotte löslich sind, bevorzugt weniger als 0,9 g/l.In one embodiment of the present invention, the organic polymer (s) is not soluble in the liquor, wherein insoluble in the context of organic polymers in the sense of the present invention means that less than 1 g / l is soluble in the liquor at room temperature, preferably less as 0.9 g / l.

In einer Ausführungsform der vorliegenden Erfindung setzt man mindestens zwei verschiedene organische Polymere ein.In one embodiment of the present invention, at least two different organic polymers are used.

In einer Ausführungsform der vorliegenden Erfindung kann mindestens ein organisches Polymer in Form von Partikeln mit einem mittleren Korndurchmesser von 0,1 bis 50 µm, bevorzugt 0,5 bis 30 µm und besonders bevorzugt bis 20 µm vorliegen (Medianwert, Zahlenmittel).In one embodiment of the present invention, at least one organic polymer may be present in the form of particles having an average particle diameter of 0.1 to 50 μm, preferably 0.5 to 30 μm and particularly preferably up to 20 μm (median value, number average).

Mindestens eine der im erfindungsgemäßen Verfahren eingesetzte wässrige Flotte enthält mindestens einen hydrophoben Feststoff in partikulärer Form, der von dem oder den oben beschriebenen Polymeren verschieden ist, und zwar in einem Anteil von mindestens 5,5 g/l, bevorzugt mindestens 7 g/l, besonders bevorzugt mindestens 10 g/l. Wünscht man ein Gemisch von mindestens zwei hydrophoben Feststoffen in partikulärer Form einzusetzen, so liegt vorzugsweise mindestens einer in einem Anteil von mindestens 5,5 g/l vor. Der maximale Anteil des oder der hydrophoben Feststoffe in partikulärer Form kann bei insgesamt 150 g/l liegen. Der hydrophobe Feststoff in partikulärer Form kann anorganischer oder organischer Natur sein, bevorzugt ist er anorganisch.At least one of the aqueous liquors used in the process according to the invention contains at least one hydrophobic solid in particulate form, which is different from the polymer or polymers described above, in a proportion of at least 5.5 g / l, preferably at least 7 g / l, more preferably at least 10 g / l. If it is desired to use a mixture of at least two hydrophobic solids in particulate form, then preferably at least one is present in a proportion of at least 5.5 g / l. The maximum proportion of the hydrophobic solid (s) in particulate form may be a total of 150 g / l. The hydrophobic solid in particulate Form may be inorganic or organic in nature, preferably it is inorganic.

Beispiele für geeignete Materialien sind Polyethylen, Polypropylen, Polyisobutylen und Polystyrol sowie Copolymere derselben miteinander oder mit einem oder mehreren weiteren Olefinen wie beispielsweise Styrol, Methylacrylat, Ethylacrylat, Methylmethacrylat, Butylacrylat, Butylmethacrylat, 2-Ethylhexylacrylat, 2-Ethylhexylmethacrylat, Maleinsäureanhydrid oder N-Methylmaleinimid. Ein bevorzugtes Polyethylen oder Polypropylen wird beispielsweise in EP-A 0 761 696 beschrieben.Examples of suitable materials are polyethylene, polypropylene, polyisobutylene and polystyrene and copolymers thereof with each other or with one or more other olefins such as styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleimide , A preferred polyethylene or polypropylene, for example, in EP-A 0 761 696 described.

Besonders geeignete Materialien sind anorganische Materialien, insbesondere feste anorganische Oxide, Carbonate, Phosphate, Silikate oder Sulfate der Gruppen 3 bis 14 des Periodensystems der Elemente, beispielsweise Calciumoxid, Siliziumdioxid oder Aluminiumoxid, Calciumcarbonat, Calciumsulfat oder Calciumsilikat, wobei Aluminiumoxid und Siliziumdioxid bevorzugt sind. Besonders bevorzugt ist Siliziumdioxid in seiner Modifikation als Kieselgel. Ganz besonders bevorzugt sind pyrogene Kieselgele. Feste anorganische Oxide können thermisch durch Erhitzen auf 400 bis 800°C oder bevorzugt durch physisorbierte oder chemisorbierte organische oder metallorganische Verbindungen hydrophobiert werden. Dazu setzt man Partikel vor dem Beschichtungsschritt beispielsweise mit metallorganischen Verbindungen um, die wenigstens eine funktionelle Gruppe enthalten, beispielsweise Alkyl-Lithiumverbindungen wie Methyllithium, n-Butylithium oder n-Hexyllithium; oder Silane wie beispielsweise Hexamethyldisilazan, Octyltrimethoxysilan und insbesondere halogenierte Silane wie Trimethylchlorsitan oder Dichlordimethylsilan.Particularly suitable materials are inorganic materials, in particular solid inorganic oxides, carbonates, phosphates, silicates or sulfates of groups 3 to 14 of the Periodic Table of the Elements, for example calcium oxide, silicon dioxide or aluminum oxide, calcium carbonate, calcium sulfate or calcium silicate, with aluminum oxide and silicon dioxide being preferred. Particularly preferred is silica in its modification as silica gel. Very particular preference is given to pyrogenic silica gels. Solid inorganic oxides can be thermally rendered hydrophobic by heating to 400 to 800 ° C or preferably by physisorbed or chemisorbed organic or organometallic compounds. For this purpose, particles are reacted before the coating step, for example, with organometallic compounds which contain at least one functional group, for example alkyllithium compounds such as methyllithium, n-butylithium or n-hexyllithium; or silanes such as hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes such as trimethylchlorosilane or dichlorodimethylsilane.

Unter hydrophob wird im Zusammenhang mit dem oder den hydrophoben Feststoffen in partikulärer Form verstanden, dass seine Löslichkeit unter 1 g/l liegt, bevorzugt unter 0,3 g/l, bestimmt bei Zimmertemperatur.Hydrophobic in the context of the hydrophobic solid (s) in particulate form is understood to mean that its solubility is below 1 g / l, preferably below 0.3 g / l, determined at room temperature.

Anorganische Feststoffe können vorzugsweise poröser Natur sein. Die poröse Struktur lässt sich am besten durch die BET-Oberfläche, gemessen nach DIN 66131, charakterisieren. Eingesetzte anorganische Feststoffe können bevorzugt eine BET-Oberfläche im Bereich von 5 bis 1000 m2/g, bevorzugt von 10 bis 800 m2/g und besonders bevorzugt von 20 bis 500 m2/g.Inorganic solids may preferably be porous in nature. The porous structure is best characterized by the BET surface area, measured according to DIN 66131. Inorganic solids used may preferably have a BET surface area in the range from 5 to 1000 m 2 / g, preferably from 10 to 800 m 2 / g and particularly preferably from 20 to 500 m 2 / g.

In einer Ausführungsform der vorliegenden Erfindung liegt mindestens einer der hydrophoben Feststoffe in partikulärer Form vor. Der mittlere Partikeldurchmesser (Medianwert, Zahlenmittel) liegt bei mindestens 1 nm, bevorzugt mindestens 3 nm und besonders bevorzugt mindestens 6 nm. Der maximale Partikeldurchmesser (Medianwert, Zahlenmittel) liegt bei 350 nm, bevorzugt bei 100 nm. Zur Messung des Partikeldurchmessers kann man sich gängiger Methoden bedienen wie beispielsweise Transmissionselektronenmikroskopie.In one embodiment of the present invention, at least one of the hydrophobic solids is in particulate form. The mean particle diameter (median value, number average) is at least 1 nm, preferably at least 3 nm and particularly preferably at least 6 nm. The maximum particle diameter (median value, number average) is 350 nm, preferably 100 nm. For measuring the particle diameter One can use common methods such as transmission electron microscopy.

Das Gewichtsverhältnis organisches Polymer zu organischem oder anorganischem Feststoff in partikulärer Form beträgt im Allgemeinen 9:1 bis 1:9, bevorzugt 4:1 bis 1.4 und besonders bevorzugt 7:3 bis 4:6.The weight ratio of organic polymer to organic or inorganic solid in particulate form is generally 9: 1 to 1: 9, preferably 4: 1 to 1.4 and more preferably 7: 3 to 4: 6.

In einer Ausführungsform der vorliegenden Erfindung liegt mindestens einer der hydrophoben Feststoffe in Form sphärischer Partikel vor, wobei damit solche partikuläre Feststoffe umfasst sein sollen, von denen mindestens 75 Gew.-%, bevorzugt mindestens 90 Gew.-% in sphärischer Form und weitere Partikel in granulärer Form vorliegen.In one embodiment of the present invention, at least one of the hydrophobic solids is present in the form of spherical particles, which should include those particulate solids, of which at least 75 wt .-%, preferably at least 90 wt .-% in spherical form and other particles in granular form.

In einer Ausführungsform der vorliegenden Erfindung kann mindestens einer der hydrophoben Feststoffe Agglomerate bilden. Beim Vorliegen eines oder mehrerer hydrophober Feststoffe in Form von Agglomeraten, die aus 2 bis mehreren tausend Primärpartikeln bestehen können und ihrerseits sphärische Form aufweisen können, beziehen sich die Angaben auf Form und Größe der Partikel auf die Primärpartikel.In one embodiment of the present invention, at least one of the hydrophobic solids may form agglomerates. In the presence of one or more hydrophobic solids in the form of agglomerates, which may consist of 2 to several thousand primary particles and may in turn have spherical shape, the information on the shape and size of the particles refer to the primary particles.

Im erfindungsgemäßen Verfahren eingesetzte wässrige Flotte enthält mindestens einen Emulgator, gewählt aus Copolymerisaten von Ethylen und mindestens einer α,β-ungesättigten Mono- oder Dicarbonsäure oder mindestens einem Anhydrid einer α,β-ungesättigten Mono- oder Dicarbonsäure, beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure, Methylenmalonsäure, Maleinsäureanyhdrid, Itaconsäureanhydrid. Die Carboxylgruppen können partiell oder vorzugsweise vollständig neutralisiert sein, beispielsweise mit Alkalimetallionen, Erdalkalimetallionen, Ammonium oder Aminen, beispielsweise Amine wie Triethylamin, Diethylamin, Ethylamin, Trimethylamin, Dimethylamin, Methylamin, Ethyldiisopropylamin, Ethanolamin, Diethanolamin, Triethanolamin, N-Methyl-diethanolamin, N-(n-Butyl)diethanolamin oder N,N-Dimethylethanolamin.The aqueous liquor used in the process according to the invention comprises at least one emulsifier selected from copolymers of ethylene and at least one α, β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α, β-unsaturated mono- or dicarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid, Maleic acid, fumaric acid, methylenemalonic acid, maleic anhydride, itaconic anhydride. The carboxyl groups may be partially or preferably completely neutralized, for example with alkali metal ions, alkaline earth metal ions, ammonium or amines, for example amines such as triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethyldiisopropylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N - (n-butyl) diethanolamine or N, N-dimethylethanolamine.

Der Anteil an Emulgator in der Flotte lässt sich in weiten Grenzen wählen und kann 0,1 bis 100 g/l betragen, bevorzugt 0,2 bis 10 g/l.The proportion of emulsifier in the liquor can be chosen within wide limits and can be 0.1 to 100 g / l, preferably 0.2 to 10 g / l.

Das erfindungsgemäße Verfahren führt man so durch, dass man textiles Material mit mindestens einer wässrigen Flotte behandelt Dabei ist es auch möglich, mehrere Behandlungsschritte mit gleichartigen oder verschiedenen Flotten durchzuführen.The process according to the invention is carried out by treating textile material with at least one aqueous liquor. It is also possible to carry out a plurality of treatment steps with similar or different liquors.

In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren so durch, dass man das zu behandelnde Textil zunächst mit einer Flotte behandelt, die mindestens ein organisches Polymer enthält, das als Bindemittel dient, und weiterhin einen organischen oder bevorzugt anorganischen Feststoff in partikulärer Form und anschließend eine weitere Behandlung mit einer neuen Flotte anschließt, die das organische Polymer enthält, aber keinen weiteren organischen oder anorganischen Feststoff in partikulärer Form.In one embodiment of the present invention, the process according to the invention is carried out by first treating the textile to be treated with a liquor containing at least one organic polymer which serves as a binder. and further includes an organic or preferably inorganic solid in particulate form followed by further treatment with a new liquor containing the organic polymer but no further organic or inorganic solid in particulate form.

In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren so durch, dass man das zu behandelnde Textil zunächst mit einer Flotte behandelt, die mindestens ein organisches Polymer enthält, das als Bindemittel dient, und weiterhin einen organischen oder bevorzugt anorganischen Feststoff in partikulärer Form, und anschließend eine weitere Behandlung mit einer neuen Flotte anschließt, die ein anderes organisches Polymer enthält, aber keinen weiteren organischen oder anorganischen Feststoff in partikulärer Form.In one embodiment of the present invention, the process according to the invention is carried out by first treating the textile to be treated with a liquor which contains at least one organic polymer which serves as binder and furthermore an organic or preferably inorganic solid in particulate form, and then join another treatment with a new fleet that is another organic Contains polymer, but no further organic or inorganic solid in particulate form.

In einer Ausführungsform der vorliegenden Erfindung führt man das erfindungsgemäße Verfahren so durch, dass man das zu behandelnde Textil zunächst mit einer Flotte behandelt, die mindestens ein organisches Polymer enthält und weiterhin einen organischen oder bevorzugt anorganischen Feststoff in partikulärer Form und anschließend eine weitere Behandlung mit einer neuen Flotte anschließt, die kein weiteres Polymer enthält, aber den bereits im ersten Schritt eingesetzten anorganischen Feststoff in partikulärer Form.In one embodiment of the present invention, the process according to the invention is carried out by first treating the textile to be treated with a liquor which contains at least one organic polymer and furthermore an organic or preferably inorganic solid in particulate form and then a further treatment with a followed by a new liquor, which contains no further polymer, but the inorganic solid used in the first step in particulate form.

Die Temperatur zur Durchführung des erfindungsgemäßen Verfahrens ist an sich unkritisch. Die Flottentemperatur liegt kann im Bereich von 10 bis 60°C liegen, bevorzugt 15 bis 30°C.The temperature for carrying out the method according to the invention is not critical per se. The liquor temperature may be in the range of 10 to 60 ° C, preferably 15 to 30 ° C.

Die Verfahrensparameter des erfindungsgemäßen Verfahrens kann man so wählen, dass durch das erfindungsgemäße Verfahren üblicherweise eine Flottenaufnahme von 25 Gew.-% bis 85 Gew.-%, bevorzugt 40 bis 70 Gew.-% resultiert.The process parameters of the process according to the invention can be chosen such that the process according to the invention usually results in a liquor pickup of from 25% by weight to 85% by weight, preferably from 40 to 70% by weight.

Das erfindungsgemäße Verfahren kann in gängigen Maschinen durchgeführt werden, die für die Ausrüstung von Textilien eingesetzt werden, beispielsweise Foulards. Bevorzugt sind Foulards mit senkrechtem Textileinzug, die als wesentliches Element zwei aufeinandergepresste Rollen enthalten, durch die das Textil geführt wird. Oberhalb der Rollen ist die Flüssigkeit eingefüllt und benetzt das Textil. Durch den Druck wird das Textil abgequetscht und ein konstanter Auftrag gewährleistet.The method according to the invention can be carried out in conventional machines which are used for finishing textiles, for example foulards. Foulards with vertical textile infeed, which contain as an essential element two rollers pressed against each other through which the textile is guided, are preferred. Above the rollers, the liquid is filled in and wets the textile. The pressure squeezes off the textile and ensures a constant application.

Die Geschwindigkeit des Textileinzugs der Foulards beträgt in einer Ausführungsform der vorliegenden Erfindung 1 bis 40 m/mim, bevorzugt 1 bis 30 m/min.The speed of textile infeed of the foulards in one embodiment of the present invention is 1 to 40 m / min, preferably 1 to 30 m / min.

Im Anschluss an die erfindungsgemäße Behandlung kann man das behandelte Textil nach in der Textilindustrie üblichen Methoden trocknen.After the treatment according to the invention, the treated textile can be dried by methods customary in the textile industry.

Im Anschluss an die erfindungsgemäße Behandlung kann man tempern, und zwar kontinuierlich oder diskontinuierlich. Die Dauer der Temperung kann man in weiten Grenzen wählen. Üblicherweise kann man über die Dauer von etwa 10 Sekunden bis etwa 30 Minuten, insbesondere 30 Sekunden bis 5 Minuten tempern. Zur Durchführung einer Temperung erhitzt man auf Temperaturen von bis zu 180°C, bevorzugt bis zu 150°C. Natürlich ist es erforderlich, die Temperatur der Temperung an die Empfindlichkeit des Gewebes anzupassen.After the treatment according to the invention, it is possible to temper, continuously or discontinuously. The duration of tempering can be chosen within wide limits. Usually, one can over the duration of about 10 seconds to about 30 minutes, in particular 30 seconds to 5 minutes annealing. To carry out a heat treatment is heated to temperatures of up to 180 ° C, preferably up to 150 ° C. Of course, it is necessary to adjust the tempering temperature to the sensitivity of the fabric.

Geeignete Methode zur Temperung ist beispielsweise eine Heißlufttrocknung.Suitable method for annealing is for example a hot air drying.

In einer Ausführungsform der vorliegenden Erfindung versieht man das textile Material vor der erfindungsgemäßen Behandlung mit einer Haftschicht. Dazu kann man einen sogenannten Primer einsetzen. Die Aufbringung eines Primers ist bevorzugt, wenn man Synthesefasern auszurüsten wünscht.In one embodiment of the present invention, prior to the treatment according to the invention, the textile material is provided with an adhesive layer. For this you can use a so-called primer. The application of a primer is preferred if one desires to equip synthetic fibers.

In einer Ausführungsform der vorliegenden Erfindung lässt sich als Haftschicht beispielsweise ein oder mehrere Polymere auf das zu behandelnde textile Material aufbringen, wobei die Polymersynthese auch auf dem textilen Material durchgeführt werden kann. Besonders gut geeignete Polymere sind solche Polymere, die vernetzte oder zur Vernetzung fähige Gruppen aufweisen, beispielsweise natürliche oder synthetische Polymeren mit freien Hydroxylgruppen, Carbonylgruppen, primären oder sekundären Aminogruppen oder Thiolgruppen. Beispiele für gut geeignete Polymere sind Lignin, Polysaccharide, Polyvinylalkohol und Polyethylenimin. Eine Vernetzung kann beispielsweise durch anschließende Umsetzung mit beispielsweise Isocyanaten, Dimethylolharnstoff oder N,N-Dimethylol-4,5-Dihydroxyethylenharnstoff (DMDHEU) gelingen. Andere besonders bevorzugte Vernetzer sind Melamin-Formaldehyd-Harze, die mit Methanol verethert sein können.In one embodiment of the present invention can be applied as an adhesive layer, for example, one or more polymers on the textile material to be treated, wherein the polymer synthesis can also be carried out on the textile material. Particularly suitable polymers are those polymers which have crosslinked or crosslinkable groups, for example natural or synthetic polymers having free hydroxyl groups, carbonyl groups, primary or secondary amino groups or thiol groups. Examples of suitable polymers are lignin, polysaccharides, polyvinyl alcohol and polyethyleneimine. Crosslinking can be achieved, for example, by subsequent reaction with, for example, isocyanates, dimethylolurea or N, N-dimethylol-4,5-dihydroxyethyleneurea (DMDHEU). Other particularly preferred crosslinkers are melamine-formaldehyde resins, which may be etherified with methanol.

In einer anderen Ausführungsform werden bei zu behandelnden Polyestern oder Polyamiden durch partielle Verseifung mit starken Alkalien wie wässriger Natronlauge oder Kalilauge 0,01 bis 1 Gew.-%, bevorzugt 0,1 bis 0,5 Gew.-% des Textils verseift.In another embodiment, 0.01 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% of the textile are saponified in polyesters or polyamides to be treated by partial saponification with strong alkalis such as aqueous sodium hydroxide or potassium hydroxide.

Ein weiterer Gegenstand der vorliegenden Erfindung sind textile Materialien, ausgerüstet nach dem erfindungsgemäßen Verfahren. Durch das erfindungsgemäße Ausrüsten werden die erfindungsgemäßen Textilien mit einer oder mehreren Schichten versehen. Die erfindungsgemäßen textilen Materialien zeigen besonders gutes Schmutz und Wasser abweisendes Verhalten. Weiterhin zeigen erfindungsgemäße textile Materialien sehr gute mechanische Belastbarkeit. In den erfindungsgemäß beschichteten textilen Materialien ist der oder sind die eingesetzten Feststoffe isotrop oder weitgehend isotrop über die Ausrüstungsschicht verteilt, d.h. man stellt keine Konzentration in der Grenzschicht zwischen Ausrüstungsschicht und umgebender Atmosphäre fest.Another object of the present invention are textile materials, equipped by the method according to the invention. By equipping the inventive textiles are provided with one or more layers. The textile materials of the invention show particularly good dirt and water-repellent behavior. Furthermore, textile materials of the invention show very good mechanical strength. In the textile materials coated according to the invention, the solid (s) used is or isotropic or substantially isotropically distributed over the finish layer, i. no concentration is detected in the boundary layer between the finish layer and the surrounding atmosphere.

In einer Ausführungsform enthalten die erfindungsgemäßen Textilien 0,5 bis 50 g/m2 Schicht, bevorzugt 1 bis 20 g/m2 und besonders bevorzugt 1,5 bis 10 g/m2.In one embodiment, the textiles according to the invention contain 0.5 to 50 g / m 2 layer, preferably 1 to 20 g / m 2 and particularly preferably 1.5 to 10 g / m 2 .

Ein weiterer Gegenstand der vorliegenden Erfindung sind wässrigen Flotten zur Ausrüstung von textilen Materialien, enthaltend mindestens ein organisches Polymer, das als Bindemittel dient, und mindestens einen organischen oder anorganischen Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser (Median, Zahlenmittel) im Bereich von 1 nm bis 350 nm, wobei der oder die organischen oder anorganischen Feststoffe in der Flotte in einem Anteil von mindestens 5,5 g/l vorliegen. Die erfindungsgemäßen Flotten können weitere Komponenten enthalten, beispielsweise ein oder mehrere organische Lösemittel oder einen oder mehrere Emulgatoren.Another object of the present invention are aqueous liquors for finishing textile materials, containing at least one organic polymer which serves as a binder, and at least one organic or inorganic solid in particulate form with an average particle diameter (median, number average) in the range of 1 nm to 350 nm, wherein the organic or inorganic solids in the liquor in a proportion of at least 5.5 g / l. The liquors of the invention may contain further components, for example one or more organic solvents or one or more emulsifiers.

Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung der erfindungsgemäßen Flotten zur Ausrüstung von textilen Materialien.Another object of the present invention is the use of the liquors of the invention for finishing textile materials.

Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung wässriger Flotten, im Folgenden auch erfindungsgemäßes Herstellungsverfahren genannt. Das erfindungsgemäße Herstellungsverfahren umfasst das Vermischen der folgenden Komponenten:

  • mindestens ein organisches Polymer, das als Bindemittel dient,
  • mindestens einen organischen oder anorganischen Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser (Median, Zahlenmittel) im Bereich von 1 nm bis 350 nm,
  • mindestens einem Emulgator, ausgewählt aus Copolymerisaten von Ethylen und mindestens einer α,β-ungesättigten Mono- oder Dicarbonsäure oder mindestens einem Anhydrid einer α,β-ungesättigten Mono- oder Dicarbonsäure,
  • Wasser und
  • gegebenenfalls ein oder mehrere organische Lösemittel,
  • und gegebenenfalls weitere Komponenten, beispielsweise einen oder mehrere Emulgatoren,
  • wobei die Menge an organischem oder anorganischem Feststoff in partikulärer Form so gewählt wird, dass er in der wässrigen Flotte in einem Anteil von mindestens 5,5 g/l vorliegt.
Another object of the present invention is a process for the preparation of aqueous liquors, hereinafter also mentioned according to the invention manufacturing process. The production process according to the invention comprises the mixing of the following components:
  • at least one organic polymer serving as a binder,
  • at least one organic or inorganic solid in particulate form having an average particle diameter (median, number average) in the range from 1 nm to 350 nm,
  • at least one emulsifier selected from copolymers of ethylene and at least one α, β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α, β-unsaturated mono- or dicarboxylic acid,
  • water and
  • optionally one or more organic solvents,
  • and optionally further components, for example one or more emulsifiers,
  • wherein the amount of organic or inorganic solid in particulate form is chosen so that it is present in the aqueous liquor in a proportion of at least 5.5 g / l.

Das erfindungsgemäße Herstellverfahren kann man üblicherweise bei Temperaturen von Raumtemperatur bis etwa 100°C durchführen, wobei Raumtemperatur bevorzugt ist.The preparation process of the invention can be carried out usually at temperatures from room temperature to about 100 ° C, with room temperature being preferred.

Das erfindungsgemäße Herstellverfahren umfasst in der Regel einen Homogenisierschritt, beispielsweise durch mechanisches oder pneumatisches Rühren, Schütteln, Ultraschallbehandlung oder eine Kombination derselben. In einigen Fällen kann man jedoch auf den Homogenisierschritt verzichten.The production process according to the invention generally comprises a homogenization step, for example by mechanical or pneumatic stirring, shaking, ultrasound treatment or a combination thereof. In some cases, however, one can do without the Homogenisierschritt.

Die Reihenfolge der Zugabe der Komponenten kann im Prinzip beliebig gewählt werden. So kann man beispielsweise zunächst eine wasser- und lösemittelfreie Mischung aus Polymer und organischem oder anorganischem Feststoff herstellen und anschließend die trockene Mischung in organischem Lösemittel oder Gemisch aus Wasser und organischem Lösemittel oder in Wasser dispergieren.The order of addition of the components can be chosen arbitrarily in principle. So you can, for example, first prepare a water and solvent-free mixture of polymer and organic or inorganic solid and then disperse the dry mixture in organic solvent or mixture of water and organic solvent or in water.

In einer Ausführungsform des erfindungsgemäßen Herstellungsverfahrens stellt man zunächst Formulierungen her, die organisches Polymer, organischen oder anorganischen Feststoff in partikulärer Form, gegebenenfalls einen oder mehrere organische Lösemittel und gegebenenfalls einen oder mehrere Emulgatoren sowie gegebenenfalls Wasser enthält. Vor der Durchführung der erfindungsgemäßen Behandlung von textilen Materialien stellt man dann eine erfindungsgemäße Flotte her, indem man die Formulierung mit Wasser verdünnt. Es ist bevorzugt, dass die erfindungsgemäßen Formulierungen maximal 15 Gew.-%, bevorzugt etwa 0,1 bis 10 Gew.-%, besonders bevorzugt bis 5 Gew.-% Wasser enthalten. Die erfindungsgemäßen Formulierungen können auch wasserfrei sein.In one embodiment of the preparation process according to the invention, formulations are first prepared which contain organic polymer, organic or inorganic solid in particulate form, optionally one or more organic solvents and optionally one or more emulsifiers and optionally water. Before carrying out the treatment according to the invention of textile Materials are then prepared a liquor of the invention by diluting the formulation with water. It is preferred that the formulations according to the invention contain a maximum of 15% by weight, preferably about 0.1 to 10% by weight, particularly preferably up to 5% by weight of water. The formulations of the invention may also be anhydrous.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Formulierungen, die organisches Polymer, organischen oder anorganischen Feststoff in partikulärer Form, gegebenenfalls einen oder mehrere organische Lösemittel und gegebenenfalls einen oder mehrere Emulgatoren sowie gegebenenfalls Wasser enthalten, wobei der Anteil an Wasser etwa 0,1 bis 10 Gew.-%, bevorzugt bis 5 Gew.-% beträgt.Another object of the present invention are formulations containing organic polymer, organic or inorganic solid in particulate form, optionally one or more organic solvents and optionally one or more emulsifiers and optionally water, wherein the proportion of water about 0.1 to 10 wt .-%, preferably up to 5 wt .-% is.

Die Erfindung wird durch Beispiele erläutert.The invention will be illustrated by examples.

Beispiel 1: Herstellung von erfindungsgemäßen FlottenExample 1: Preparation of Inventive Fleets Beispiel 1.1: Herstellung der Flotte 1.1Example 1.1: Production of the fleet 1.1

In einem Kolben wurden unter mechanischem Rühren gemischt:

  • 883,5 ml entmineralisiertes Wasser,
  • 62,4 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-%
  • CH2=C(CH3)COO-CH2-CH2-n-C8F17 mit Mn 3000 g/mol (Gelpermeationschromatographie),
  • 15,6 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, Mw: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin, pH-Wert zwischen 8,5 und 9,5,
  • und 25,2 g Isopropanol.
In a flask were mixed with mechanical stirring:
  • 883.5 ml of demineralised water,
  • 62.4 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 10% by weight of methacrylic acid and 90% by weight
  • CH 2 = C (CH 3 ) COO-CH 2 -CH 2 -nC 8 F 17 with M n 3000 g / mol (gel permeation chromatography),
  • 15.6 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 20% by weight of acrylic acid, 80% by weight of ethylene, M w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine, pH Value between 8.5 and 9.5,
  • and 25.2 g of isopropanol.

Anschließend wurden 13,3 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m2/g, bestimmt nach DIN 66131, Primärpartikeldurchmesser: 10 nm (Medianwert, Zahlenmittel) zugegeben und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte 1.1.Subsequently, 13.3 g of fumed silica modified with dimethylsiloxane groups having a BET surface area of 225 m 2 / g, determined to DIN 66131, primary particle diameter: 10 nm (median value, number average) were added and dispersed for 10 minutes (Ultraturrax stirrer). The aqueous liquor was obtained 1.1.

Beispiel 1.2: Herstellung der Flotte 1.2Example 1.2: Production of the fleet 1.2

In einem Kolben wurden unter mechanischem Rühren gemischt:

  • 899,5 ml entmineralisiertes Wasser,
  • 52,4 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-%
  • CH2=C(CH3)COO-CH2-CH2-n-C6F13 mit Mn 2900 g/mol (Gelpermeationschromatographie),
  • 14,6 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, Mw: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin, pH-Wert zwischen 8,5 und 9,5,
  • und 25,2 g Isopropanol.
In a flask were mixed with mechanical stirring:
  • 899.5 ml of demineralised water,
  • 52.4 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 10% by weight of methacrylic acid and 90% by weight
  • CH 2 = C (CH 3 ) COO-CH 2 -CH 2 -nC 6 F 13 with M n 2900 g / mol (gel permeation chromatography),
  • 14.6 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 20% by weight of acrylic acid, 80% by weight of ethylene, M w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine, pH Value between 8.5 and 9.5,
  • and 25.2 g of isopropanol.

Anschließend wurden 8,3 g mit Trimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 200 m2/g, bestimmt nach DIN 66131 zugegeben, Primärpartikelgröße: 10 nm (Medianwert, Zahlenmittel),
und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte 1.2.Subsequently, 8.3 g of fumed silica modified with trimethylsiloxane groups having a BET surface area of 200 m 2 / g, determined in accordance with DIN 66131, were added, primary particle size: 10 nm (median value, number average),
and dispersed for 10 minutes (Ultraturrax stirrer). The aqueous liquor was obtained 1.2.

Beispiel 1.3 Herstellung der Flotte 1.3Example 1.3 Production of the fleet 1.3

In einem Kolben wurden unter mechanischem Rühren gemischt:

  • 884,5 ml entmineralisiertes Wasser,
  • 66,3 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-%
  • CH2=C(CH3)COO-CH2-CH2-n-C8F17 mit Mn 3000 g/mol (Gelpermeationschromatographie),
  • 13,8 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, Mw: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin, pH-Wert zwischen 8,5 und 9,5,
  • und 30,2 g Isopropanol unter mechanischem Rühren gemischt.
In a flask were mixed with mechanical stirring:
  • 884.5 ml of demineralized water,
  • 66.3 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 10% by weight of methacrylic acid and 90% by weight
  • CH 2 = C (CH 3 ) COO-CH 2 -CH 2 -nC 8 F 17 with M n 3000 g / mol (gel permeation chromatography),
  • 13.8 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 20% by weight of acrylic acid, 80% by weight of ethylene, M w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine, pH Value between 8.5 and 9.5,
  • and 30.2 g of isopropanol mixed with mechanical stirring.

Anschließend wurden 5,2 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m2/g, bestimmt nach DIN 66131, Primärpartikeldurchmesser: 10 nm (Medianwert, Zahlenmittel) zugegeben und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte 1.3.Subsequently, 5.2 g of fumed silica modified with dimethylsiloxane groups having a BET surface area of 225 m 2 / g, determined to DIN 66131, primary particle diameter: 10 nm (median value, number average) were added and dispersed for 10 minutes (Ultraturrax stirrer). The aqueous liquor was obtained 1.3.

Beispiel 1.4: Herstellung der Flotte 1.4Example 1.4: Production of the fleet 1.4

In einem Kolben wurden unter mechanischem Rühren gemischt:

  • 886,3 ml entmineralisiertes Wasser,
  • 20,8 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-%
  • CH2=C(CH3)COO-CH2-CH2-n-C6F13 mit Mn 3000 g/mol (Gelpermeationschromatographie),
  • 57 g einer wässrigen Dispersion (20 Gew.-% Feststoffgehalt) eines statistischen Copolymers aus 20 Gew.-% Acrylsäure, 80 Gew.-% Ethylen, Mw: 20.000 g/mol, neutralisiert mit N,N-Dimethylethanolamin, pH-Wert zwischen 8,5 und 9,5,
  • und 28,4 g Isopropanol.
In a flask were mixed with mechanical stirring:
  • 886.3 ml of demineralized water,
  • 20.8 g of an aqueous dispersion (20% by weight solids content) of a random copolymer of 10% by weight of methacrylic acid and 90% by weight
  • CH 2 = C (CH 3 ) COO-CH 2 -CH 2 -nC 6 F1 3 with M n 3000 g / mol (gel permeation chromatography),
  • 57 g of an aqueous dispersion (20 wt .-% solids content) of a random copolymer of 20 wt .-% acrylic acid, 80 wt .-% ethylene, M w : 20,000 g / mol, neutralized with N, N-dimethylethanolamine, pH between 8.5 and 9.5,
  • and 28.4 g of isopropanol.

Anschließend wurden 7,5 g mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m2/g, bestimmt nach DIN 66131 zugegeben, Primärpartikelgröße: 10 nm (Medianwert, Zahlenmittel),
und 10 Minuten dispergiert (Ultraturrax-Rührer). Man erhielt die wässrige Flotte 1.4.Subsequently, 7.5 g of dimethylsiloxane-modified fumed silica having a BET surface area of 225 m 2 / g, determined in accordance with DIN 66131, were added, primary particle size: 10 nm (median value, number average),
and dispersed for 10 minutes (Ultraturrax stirrer). The aqueous liquor was obtained 1.4.

Beispiel 2 Ausrüstung von TextilExample 2 Equipment of textile Beispiel 2.1.Example 2.1.

Ein Polyestergewebe mit einem Flächengewicht von 220 g/m2 wurde mit Flotte 1.1 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 60%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyestergewebe bei 120°C auf einem Spannrahmen getrocknet. Die abschließende Temperung erfolgte über einen Zeitraum von 3 min bei 150°C unter Umluft. Man erhielt das behandelte Polyestergewebe 2.1.A polyester fabric having a basis weight of 220 g / m 2 was treated with Fleet 1.1 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. Subsequently, the treated polyester fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyester fabric 2.1 was obtained.

Beispiel 2.2.Example 2.2.

Ein Polyamidgewebe mit einem Flächengewicht von 160 g/m2 wurde mit Flotte 1.1 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 65%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyamidgewebe bei 120°C auf einem Spannrahmen getrocknet. Die abschließende Temperung erfolgte über einen Zeitraum von 3 min bei 150°C unter Umluft. Man erhielt das behandelte Polyamidgewebe 2.2.A polyamide fabric having a weight per unit area of 160 g / m 2 was treated with liquor 1.1 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 65%. The application speed was 2 m / min. Subsequently, the treated polyamide fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyamide fabric 2.2 was obtained.

Beispiel 2.3.Example 2.3.

Ein Polyacrylgewebe mit einem Flächengewicht von 295 g/m2 wurde mit Flotte 1.1 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 50%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyacrylgewebe bei 120°C auf einem Spannrahmen getrocknet. Die abschließende Temperung erfolgte über einen Zeitraum von 3 min bei 150°C unter Umluft. Man erhielt das behandelte Polyacrylgewebe 2.3.A polyacrylic fabric having a basis weight of 295 g / m 2 was treated with Fleet 1.1 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 50%. The application speed was 2 m / min. Subsequently, the treated polyacrylic fabric was dried at 120 ° C on a tenter. The final temper took place over a period of 3 min at 150 ° C under circulating air. The treated polyacrylic fabric 2.3 was obtained.

Beispiel 2.4.Example 2.4.

Ein Polyestergewebe mit einem Flächengewicht von 220 g/m2 wurde mit Flotte 1.2 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 60%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyestergewebe bei 120°C auf einem Spannrahmen getrocknet. Die abschließende Temperung erfolgte über einen Zeitraum von 3 min bei 150°C unter Umluft. Man erhielt das behandelte Polyestergewebe 2.4.A polyester fabric having a weight per unit area of 220 g / m 2 was treated with Fleece 1.2 on a padder (manufacturer: Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 60%. The application speed was 2 m / min. Subsequently, the treated polyester fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyester fabric 2.4 was obtained.

Beispiel 2.5.Example 2.5.

Ein Polyamidgewebe mit einem Flächengewicht von 160 g/m2 wurde mit Flotte 1.2 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 65%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyamidgewebe bei 120°C auf einem Spannrahmen getrocknet. Die abschließende Temperung erfolgte über einen Zeitraum von 3 min bei 150°C unter Umluft. Man erhielt das behandelte Polyamidgewebe 2.5.A polyamide fabric having a weight per unit area of 160 g / m 2 was treated with Fleece 1.2 on a padder (manufacturer Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 65%. The application speed was 2 m / min. Subsequently, the treated polyamide fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyamide fabric 2.5 was obtained.

Beispiel 2.6.Example 2.6.

Ein Polyacrylgewebe mit einem Flächengewicht von 295 g/m2 wurde mit Flotte 1.2 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,6 bar. Es resultierte eine Flottenaufnahme von 50%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyacrylgewebe bei 120°C auf einem Spannrahmen getrocknet. Die abschließende Temperung erfolgte über einen Zeitraum von 3 min bei 150°C unter Umluft. Man erhielt das behandelte Polyacrylgewebe 2.6.A polyacrylic fabric having a basis weight of 295 g / m 2 was treated with liquor 1.2 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rollers was 2.6 bar. This resulted in a fleet intake of 50%. The application speed was 2 m / min. Subsequently, the treated polyacrylic fabric was dried at 120 ° C on a tenter. The final heat treatment was carried out over a period of 3 min at 150 ° C under circulating air. The treated polyacrylic fabric 2.6 was obtained.

3. Untersuchung der erfindungsgemäß behandelten Textilproben auf Wasser abweisende Wirkung3. Investigation of the invention treated textile samples to water-repellent effect

Die zu untersuchende erfindungsgemäß behandelte Textilprobe wurde manuell gespannt und mit Nadeln auf einem ebenen Holzbrett fixiert, dessen Neigung stufenlos von 1° bis 90° eingestellt werden konnte. Dann ließ man mit Hilfe einer Kanüle aus einer Höhe von 10 mm einzelne Wassertropfen auf die Textilprobe fallen. Die Tropfen hatten eine Masse von 4,7 mg. Durch schrittweises Senken des Neigungswinkels wurde der Neigungswinkel bestimmt, bei dem die Tropfen gerade noch abperlten und keine Adhäsion zu beobachten war. Die Ergebnisse finden sich in Tabelle 1. Tabelle 1: Neigungswinkel Probe Neigungswinkel [°] 2.1 5 2.2 3 2.3 6 2.4 7 2.5 6 2.6 8 The textile sample to be tested according to the invention was tensioned manually and fixed with needles on a flat wooden board whose inclination could be adjusted continuously from 1 ° to 90 °. Then, with the help of a cannula from a height of 10 mm, individual drops of water were dropped onto the textile sample. The drops had a mass of 4.7 mg. By gradually lowering the angle of inclination, the angle of inclination was determined at which the drops just bared and no adhesion was observed. The results are shown in Table 1. Table 1: Inclination angle sample Inclination angle [°] 2.1 5 2.2 3 2.3 6 2.4 7 2.5 6 2.6 8th

Claims (11)

  1. A process for finishing textile materials by treatment with at least one aqueous liquor which comprises at least one organic polymer which serves as a binder and at least one organic or inorganic solid in particulate form having a median (number average) particle diameter in the range from 1 nm to 350 nm, and at least one emulsifier selected from copolymers of ethylene and at least one α,β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α,β-unsaturated mono- or dicarboxylic acid, wherein the organic or inorganic solid or solids are present in the liquor in a fraction of at least 5.5 g/l.
  2. The process according to claim 1, wherein the or at least one of the organic or inorganic solids is hydrophobic.
  3. The process according to either of claims 1 and 2 wherein the textile surface is provided with a bonding layer prior to said treatment.
  4. The process according to any of claims 1 to 3 wherein the solid or solids is or are one or more inorganic solids.
  5. The process according to any of claims 1 to 4 wherein the organic or inorganic solid or solids are present in the liquor in a fraction of at least 7 g/l.
  6. The process according to any of claims 1 to 5 wherein the organic or inorganic solid or solids have a particle diameter (median value, number average) in the range from 1 to 350 nm.
  7. Textile materials finished according to a process according to claims 1 to 6.
  8. Aqueous liquors comprising at least one organic polymer which serves as a binder and at least one organic or inorganic solid in particulate form having a median (number average) particle diameter in the range from 1 nm to 350 nm, and at least one emulsifier selected from copolymers of ethylene and at least one α,β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α,β-unsaturated mono- or dicarboxylic acid, wherein the organic or inorganic solid or solids are present in the liquor in a fraction of at least 5.5 g/l.
  9. A process for preparing aqueous liquors according to claim 8 by mixing the following components:
    at least one organic polymer which serves as a binder,
    at least one organic or inorganic solid in particulate form having a median (number average) particle diameter in the range from 1 nm to 350 nm,
    at least one emulsifier selected from copolymers of ethylene and at least one α,β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α,β-unsaturated dicarboxylic acid,
    water, and
    if appropriate one or more organic solvents,
    and if appropriate further components,
    wherein the amount of organic or inorganic solid in particulate form is chosen such that the organic or inorganic solid in particulate form is present in the aqueous liquor in a fraction of at least 5.5 g/l.
  10. The use of formulations for preparing aqueous liquors according to claim 8,
    wherein the formulations comprise
    at least one organic polymer which serves as a binder,
    at least one organic or inorganic solid in particulate form having a median (number average) particle diameter in the range from 1 nm to 350 nm,
    if appropriate one or more organic solvents,
    one or more emulsifiers selected from copolymers of ethylene and at least one α,β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α,β-unsaturated dicarboxylic acid
    and also if appropriate water and the water fraction is not more than 15% by weight.
  11. Formulations comprising
    at least one organic polymer which serves as a binder,
    at least one organic or inorganic solid in particulate form having a median (number average) particle diameter in the range from 1 nm to 350 nm,
    if appropriate one or more organic solvents,
    one or more emulsifiers selected from copolymers of ethylene and at least one α,β-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α,β-unsaturated dicarboxylic acid,
    and also if appropriate water, wherein the water fraction is not more than 15% by weight.
EP04706158A 2003-02-18 2004-01-29 Method for hydrophobing textile materials Expired - Lifetime EP1597425B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10306893A DE10306893A1 (en) 2003-02-18 2003-02-18 Process for finishing textile material to impart water and soil repellence to e.g. natural, modified and/or synthetic fibers, yarn (precursor), thread or fabric, uses organic polymer and particulate (in)organic solid in aqueous medium
DE10306893 2003-02-18
PCT/EP2004/000776 WO2004074568A1 (en) 2003-02-18 2004-01-29 Method for hydrophobing textile materials

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EP1597425B1 true EP1597425B1 (en) 2010-12-01

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WO (1) WO2004074568A1 (en)

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EP1597425A1 (en) 2005-11-23
DE10306893A1 (en) 2004-08-26
ES2356143T3 (en) 2011-04-05
DE502004011953D1 (en) 2011-01-13
JP4531039B2 (en) 2010-08-25
US20100305256A1 (en) 2010-12-02
US20060174418A1 (en) 2006-08-10
WO2004074568A1 (en) 2004-09-02
ATE490369T1 (en) 2010-12-15
US7790238B2 (en) 2010-09-07
US7955518B2 (en) 2011-06-07
JP2006518012A (en) 2006-08-03

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