EP2122042A1 - Method for the production of a coated textile - Google Patents

Method for the production of a coated textile

Info

Publication number
EP2122042A1
EP2122042A1 EP08707879A EP08707879A EP2122042A1 EP 2122042 A1 EP2122042 A1 EP 2122042A1 EP 08707879 A EP08707879 A EP 08707879A EP 08707879 A EP08707879 A EP 08707879A EP 2122042 A1 EP2122042 A1 EP 2122042A1
Authority
EP
European Patent Office
Prior art keywords
condensation product
textile
alkyl
chch
aqueous liquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP08707879A
Other languages
German (de)
French (fr)
Inventor
Ralf NÖRENBERG
Wolfram Badura
Sylvia Von Krog
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP07100838A external-priority patent/EP1947233A1/en
Application filed by BASF SE filed Critical BASF SE
Priority to EP08707879A priority Critical patent/EP2122042A1/en
Publication of EP2122042A1 publication Critical patent/EP2122042A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • 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
    • 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
    • D06M15/333—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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • the present invention relates to a process for producing a coated textile, characterized in that a textile substrate without prior application of a primer is treated with an aqueous liquor containing
  • hydrophobicizing fibers of polyester for example by allowing it to pass through a pulling heated to 80 0 C decalin bath in which 1% of hydrophobic silica Aerosil was suspended 8200th
  • a problem in many cases is to improve the adhesion of the particles on the textile in question, without which the dirt-repellent effect is not obtainable in the long run.
  • WO 2004/074568 and WO 2005/113883 propose to apply a so-called adhesive layer, for example with the aid of a so-called primer.
  • primers beat WO 2004/074568 and WO 2005/113883 in particular N, N-dimethylol-4,5-diethyleneurea (DMDHEU).
  • DMDHEU N, N-dimethylol-4,5-diethyleneurea
  • textiles or even textile materials are to be understood as fibers, rovings, yarn, twine on the one hand, and textile fabrics on the other hand, such as, for example, woven goods, knits, 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 or textile materials according to 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 modified natural fibers can be coated by the process according to the invention, for example cellulose acetate.
  • aqueous liquors are to be understood as meaning those liquors which, based on portions which are liquid at room temperature, may contain at least 5% by weight of water.
  • aqueous liquor contains at least 25 wt .-% water, more preferably at least 50 wt .-% and most preferably at least 75 wt .-%.
  • the maximum water content, based on proportions which are liquid at room temperature, is 100% by weight, preferably 97% by weight, particularly preferably 95% by weight.
  • aqueous liquors used according to the invention may contain organic solvents, for example methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-isobutyl ether, acetic acid, n Butanol, iso-butanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers.
  • organic solvents for example methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-isobutyl ether, acetic acid, n Butanol, iso-butanol
  • Organic solvents may constitute from 0.2 to 50% by weight, preferably from 0.5 to 35% by weight, of the aqueous liquor used according to the invention.
  • the aqueous liquor used in the process according to the invention comprises at least one solid in particulate form, also called solid (A) in the context of the present invention.
  • the proportion of solid (A) is at least 5.5 g / l of aqueous liquor, preferably at least 7 g / l, particularly preferably at least 10 g / l.
  • Solid (A) may be inorganic or organic in nature, preferably inorganic.
  • suitable solids (A) are polyethylene, polypropylene, polyisobutylene and polystyrene, and copolymers thereof with one another or with one or more further olefins, for example styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2- Ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleimide.
  • a preferred polyethylene or polypropylene is described, for example, in EP-A 0 761 696.
  • Particularly suitable solids (A) 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, aluminum oxide and silicon dioxide being preferred are.
  • 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 hydrophobicized by heating at 400 to 800 0 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-butyllithium or n-hexyllithium; or silanes such as, for example, 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-butyllithium or n-hexyllithium
  • silanes such as, for example, hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes, such as trimethylchlorosilane or dichlorodimethylsilane.
  • a mixture of hydrophobized solid inorganic oxide with corresponding non-hydrophobicized inorganic oxide is used, for example in proportions by weight of 100: 0 to 0: 100, preferably 99: 1 to 60: 40, particularly preferably 99: 1 to 80:20.
  • Hydrophobic in connection with the solid or solids (A) is understood to mean that its solubility in water is below 1 g / l, preferably below 0.3 g / l, determined at room temperature.
  • Solid (A) may have a contact angle of 90 ° or more with water, determined at room temperature.
  • Solids (A), when of inorganic material, may preferably be porous in nature.
  • the porous structure is best characterized by the BET surface area, measured according to DIN 66131.
  • Used solids (A) 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.
  • Solid (A) 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 500 nm, preferably 350 nm and particularly preferably 100 nm Measurement of the particle diameter can be used in common methods such as transmission electron microscopy.
  • At least one solid (A) is present in the form of spherical particles, which are intended to encompass those solids (A) of which at least 75% by weight, preferably at least 90% by weight, are present in spherical form and further particles may be in granular form.
  • At least one solid (A) may form aggregates and / or agglomerates.
  • a solid (A) in the form of aggregates and / or agglomerates which may consist of 2 to several thousand primary particles and in turn may 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 contains at least one hydrophobic polymer (B).
  • At least one hydrophobic polymer is a polymer or copolymer 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; Vinyl aromatics, for example styrene, ⁇ -methylstyrene, cis-stilbene, trans-stilbene, Diolefins such as, for example, 1,3-butadiene, cyclopentadiene, chloroprene or isoprene, C 5 -C 18 -cycloolefins such as, for example, cyclopentene, cyclohexene, norbornene, dimeric cyclopentadiene,
  • Vinyl esters of linear or branched C 1 -C 20 -alkanoic acids 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, isopropyl (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.
  • Hydrophobic polymers (B) which comprise at least one halogenated (co) monomer copolymerized are also referred to in the context of the present invention as halogenated (co) polymers (B).
  • Halogenated monomers include chlorinated olefins such as vinyl chloride and vinylidene chloride.
  • hydrophobic polymer (B) is a fluorinated (co) polymer.
  • halogenated monomers are fluorine-containing olefins such as, for example, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C3-Cn-carboxylic acids as described, for example, in US Pat. Nos. 2,592,069 and 2,732,370,
  • (Meth) acrylic esters of fluorinated or perfluorinated alcohols for example fluorinated or perfluorinated C 3 -C 4 -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 F7, HO-CH 2 -CH 2 HSO-C 3 F 7, HO-CH 2 -CH 2 -nC 4 F9, HO-CH 2 -CH 2 -N-C 6 Fi 3 , HO-CH 2 -CH 2 -nC 8 Fi7, HO-CH 2 -CH 2 -n-CioF 2 i, HO-CH 2 -CH 2 -n-Ci 2 F 25 , described for example in US 2,642,416, US 3,239,557, BR 1, 1 18,007, US 3,462,296.
  • copolymers of, for example, glycidyl (meth) acrylate with esters of the formula II are also copolymers of, for example, glycidyl (meth) acrylate with esters of the formula II
  • R 4 is hydrogen, CH 3 , C 2 H 5
  • R 5 is CH 3 , C 2 H 5
  • x is an integer in the range from 4 to 12
  • y is an integer in the range from 1 to 1 , preferably 1 to 6,
  • copolymers are copolymers of (meth) acrylklado or perfluoro C 3 -C 2 -alkyl alcohols such as 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 2 -CH 2 -nC 4 F 9, HO-CH 2 -CH 2 -nC 5 Fn, HO- CH 2 -CH 2 -nC 6 Fi 3 , HO-CH 2 -CH 2 -nC 7 Fi 5 ; 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
  • R 6 is selected from
  • C 1 -C 6 -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
  • C 6 -C 4 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
  • R 7 is methyl or hydrogen.
  • a is an integer in the range of 2 to 10,000, especially up to 100,
  • b is an integer in the range of 0 to 6, especially 1 to 2.
  • hydrophobic polymer (B) is different from solid (A), and preferably, hydrophobic polymer (B) is a preferably halogenated polymer (B), and particularly a fluorinated polymer.
  • the aqueous liquor used in the process according to the invention furthermore contains (C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol, also referred to in the context of the present invention as "condensation product (C)".
  • Amino-containing compounds are organic compounds having at least one, preferably at least two and more preferably exactly two or three primary amino groups per molecule. For example, it may be 1, 2-ethylenediamine or 1, 3-propylenediamine. Preference is given to choosing urea as amino group-containing compound.
  • Aldehydes are preferably aliphatic aldehydes such as acetaldehyde and especially formaldehyde.
  • Dialdehydes are preferably aliphatic dialdehydes, such as glutaraldehyde, succinic dialdehyde and in particular glyoxal.
  • condensation product (C) is a compound of general formula IV.
  • the condensation product (C) is a compound of the general formula I
  • Each R 1 is different or preferably the same and selected from
  • Ci-C ⁇ -alkyl branched or preferably unbranched, selected from 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, more preferably linear CrC 4 -AlkVl such as methyl, ethyl, n-propyl, and n-butyl,
  • R 2 is present - in each case different or preferably identical and selected from C 1 -C 6 -alkyl, branched or preferably unbranched, selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl , tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably linear C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, and n-butyl,
  • R 3 is selected from hydrogen and C 1 -C 20 -alkyl, preferably ethyl and in particular methyl.
  • the aqueous liquor used in the process according to the invention may contain one or more surface-active compounds (D) selected, for example, from the group of ionic and nonionic emulsifiers.
  • Suitable nonionic emulsifiers as surface-active compounds (D) are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C 4 -C 12) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80; Cs-C36).
  • Examples include the Lutensol ® brands of BASF Aktiengesellschaft.
  • Anionic emulsifiers suitable as surface-active compounds (D) are e.g. Alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C12-C18) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C4-C12 ), of alkylsulfonic acids (alkyl group: C12-C18) and of alkylarylsulfonic acids (alkyl group: Cg-ds).
  • alkyl sulfates alkyl radical: Cs to C12
  • sulfuric monoesters of ethoxylated alkanols degree of ethoxylation: 4 to 30, alkyl radical: C12-C18
  • ethoxylated alkylphenols degree of e
  • Suitable cationic emulsifiers are generally C ⁇ -Cis-alkyl, aralkyl or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts,
  • Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklareester, N-cetylpyridinium chloride, N-
  • N '- (lauryldimethyl) ethylenediamine dibromide Numerous other examples can be found in H. Stumblee, Tensid-Taschenbuch, Carl-Hanser-Verlag, Kunststoff, Vienna, 1981, and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
  • Particularly preferred cationic emulsifiers are alkoxylated fatty amines, in particular ethoxylated C 20 -C 20 fatty amines having a degree of ethoxylation of 2 to 12 on average.
  • emulsifiers are polymeric emulsifiers.
  • examples include copolymers of ethylene and at least one ⁇ , ß-unsaturated mono- or dicarboxylic acid or at least one anhydride of an ⁇ , ß-unsaturated mono- or dicarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, Methylenmalonklare, Maleinkladrid, 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-dimethyl
  • the proportion of surface-active compound (D) can be chosen within wide limits and can be zero to 100 g / l, preferably 0.2 to 10 g / l.
  • the aqueous liquor used in the process according to the invention may contain one or more additives (E).
  • additive (E) it is possible to use one or more wetting agents, by way of example alkyl polyglycosides, alkyl phosphonates, alkyl phenyl phosphonates, alkyl phosphates and alkyl phenyl phosphates.
  • additive (E) it is possible to use one or more defoamers (foam inhibitors); by way of example, liquid silicones, not ethoxylated or ethoxylated one or more times at room temperature, may be mentioned at room temperature.
  • thickening agents which may be of natural or synthetic origin, for example.
  • suitable synthetic thickeners are poly (meth) acrylic compounds, polycarboxylic acids, Polyethers, polyimines, polyamides such as polyacrylamide, and polyurethanes.
  • M w molecular weights in the range of 100,000 to 2,000,000 g / mol, where R 8 is methyl or preferably hydrogen.
  • thickening agents of natural origin include: agar-agar, carrageenan, modified starch and modified cellulose.
  • crosslinkers hardeners
  • crosslinkers are known, for example, from EP-A 0 486 881.
  • oxime-blocked isocyanates / diisocyanates / isocyanurates in particular butoxime-sealed diisocyanates and butoxime-blocked isocyanurates.
  • additive (E) one can use one or more leveling agents, for example ethylene glycol.
  • additive (E) one can use one or more aerating agents, for example one or more Guerbet alcohols, simply or up to ten times ethoxylated.
  • additive (E) it is possible to use polyvinyl acetate, polyvinyl alcohol or partially saponified polyvinyl acetate, in particular from 0.1 to 75 mol% partially saponified polyvinyl acetate. Further preferred additives (E) are mixtures of polyvinyl acetate or partially saponified polyvinyl acetate and polyvinyl alcohol.
  • additive (E) one can use weak acids or weak bases as pH regulators. Suitable examples are ammonium salts such as NH 4 Cl and (NH 4) SO 4 , furthermore suitable are carboxylic acids such as, for example, acetic acid or citric acid.
  • biocides are, for example, 1,2-benzisothiazolin-3-one ("BIT”) (commercially available as Proxel® brand from Avecia Lim.) And its alkali metal salts, other suitable biocides are 2-methyl 2H-isothiazol-3-one (“MIT”) and 5-chloro-2-methyl-2H- Isothiazol-3-one (“CIT”) Generally, 10 to 150 ppm of biocide is sufficient, based on aqueous liquor.
  • BIT 1,2-benzisothiazolin-3-one
  • MIT 2-methyl 2H-isothiazol-3-one
  • CIT 5-chloro-2-methyl-2H- Isothiazol-3-one
  • the aqueous liquor used in the process according to the invention contains: in the range of 5.5 to 150 g / l, preferably 6 to 25 g / l of solid (A), in the range of 10 to 60 g / 1, preferably 15 to 40 g / l of hydrophobic polymer (B), in the range of 50 to 150 g / l, preferably 60 to 120 g / l of condensation product (C), zero to 20 g / l, preferably 3 to 10 g / l of surface-active compound (D), in total from zero to a total of 150 g / l, preferably from 25 to 100 g / l of additives (E).
  • the rest is, for example, continuous phase.
  • the process according to the invention is carried out by treating textile material with the aqueous liquor.
  • primers are adhesion-promoting and / or hydrophilicizing (co) polymers or resins, such as N, N-dimethylol-4,5-diethyleneurea (DMDHEU).
  • the temperature for carrying out the method according to the invention is not critical per se.
  • the liquor temperature can be in the range of 10 to 80 ° C., preferably 15 to 60 ° C.
  • the liquor pickup can be chosen so that the liquefaction of the process according to the invention results from 25% by weight to 85% by weight, preferably from 30 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 treated textile can be dried by methods customary in the textile industry.
  • thermally Following the treatment according to the invention, it is possible to treat thermally, continuously or discontinuously.
  • the duration of the thermal treatment you can choose within wide limits. Typically, one can thermally treat for a period of about 10 seconds to about 30 minutes, more preferably 30 seconds to 5 minutes.
  • heating is carried out to temperatures of up to 180 ° C., preferably up to 150 ° C.
  • Suitable method for thermal treatment for example, a hot air drying.
  • textiles coated by the method according to the invention hereinafter also referred to as textile according to the invention.
  • the coating is arranged in a layer.
  • Textile according to the invention is distinguished not only by good fastnesses, such as, for example, rub fastnesses, but also very good dirt-repelling effect, low water permeability and high rigidity and low water permeability.
  • Textile according to the invention is particularly suitable for the production of textiles for outdoor use, for example for parasols and awnings, but also for covering furniture.
  • Another object of the present invention is the use of textile according to the invention as or for the production of awning fabrics, covering or tarpaulins.
  • Another object of the present invention are awning fabrics, covers or tarpaulin, prepared using textile according to the invention.
  • Another object of the present invention are aqueous liquors containing
  • (A) at least one solid in particulate form having a mean particle diameter in the range of 1 to 500 nm, also called solid (A) for short,
  • condensation product (C) at least one hydrophobic polymer, also called polymer (B) for short, (C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol, also referred to briefly as condensation product (C),
  • condensation product (C) is a condensation product of urea and at least one aldehyde or dialdehyde and optionally at least one alcohol.
  • hydrophobic polymer (B) is a fluorinated (co) polymer.
  • condensation product (C) is a compound of general formula IV.
  • condensation product (C) is a compound of general formula I.
  • each R 1 is different or the same and selected from hydrogen, C 1 -C 6 -alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -CVR 3 ,
  • Each R 2 is the same or different and selected from hydrogen, C 1 -C 6 -alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 and preferably (CH 2 CH 2 O) m R 3 , where m is an integer in the Range is 1 to 50, R 3 is selected from hydrogen and C 1 -C 20 -alkyl.
  • aqueous liquor of the invention contains:
  • liquors of the invention have a pH in the range from 2 to 9, preferably 3.5 to 7.5.
  • the liquor of the invention can be used particularly advantageously in the process according to the invention.
  • Another object of the present invention is a process for the preparation of aqueous liquors according to the invention, in the context of the present invention also called production process according to the invention.
  • the components solid (A), hydrophobic polymer (B), condensation product (C) and optionally surface-active compound (D) and optionally one or more additives (E) with each other and with Mixed water, for example by stirring.
  • the sequence of the components solid (A), hydrophobic polymer (B), condensation product (C) and optionally surface-active compound (D) and optionally one or more additives (E) is arbitrary. However, preference is given to using one or more of the components, in particular hydrophobic polymer (B) and condensation product (C), in a form premixed with water or a solvent.
  • the preparation process according to the invention can be carried out at any temperatures, in particular at temperatures in the range from 5 to 95.degree. Preference is given to room temperature.
  • Solid (A.1) fumed silica modified with dimethylsiloxane groups with a BET surface area of 225 m 2 / g, determined to DIN 66131, primary particle diameter: 10 nm (median value, number average)
  • Hydrophobic polymer (B.1) aqueous dispersion (30% by weight solids content) of a random copolymer of 10% by weight of methacrylic acid and 90% by weight with M n 2900 g / mol (gel permeation chromatography)
  • HOAc 60% by weight aqueous acetic acid
  • Butylglycol ethylene glycol n-butyl ether (butylglycol)
  • Table 1 Composition of aqueous liquors according to the invention
  • a polyester fabric having a weight per unit area of 220 g / m 2 was treated with an aqueous liquor according to the invention according to Tables 1 and 2 on a padder (manufacturer Fa. Mathis, type no. HVF12085).
  • the contact pressure of the rolls was 2.1 bar. This resulted in a fleet intake of 40%.
  • the application speed was 2 m / min.
  • the treated polyester fabric was dried for one minute at 120 0 C on a tenter.
  • the final thermal treatment was carried out over a period of one minute at 185 ° C under circulating air. Treated polyester fabrics PES.1 to PES.8 according to the invention were 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 2. Beading effect, absorption (water absorption) and passage (water permeability) refer to water. The water absorption was tested according to Bundesmann, DIN 53888.
  • the water column was determined according to DIN EN 2081 1.

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Abstract

Method for the treatment of textiles and method for the production of a coated textile, characterized in that a textile substrate is treated with an aqueous liquor without prior application of a primer. Said aqueous liquor contains (A) at least one suspended solid in particle form with an average particle diameter in the range of 1 to 500 nm, (B) at least one hydrophobic polymer, (C) at least one condensation product of at least one amino group-containing compound, and at least one aldehyde or dialdehyde, and optionally at least one alcohol.

Description

VERFAHREN ZUR HERSTELLUNG EINES BESCHICHTETEN TEXTILS METHOD FOR PRODUCING A COATED TEXTILE
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung eines beschichteten Textils, dadurch gekennzeichnet, dass man ein textiles Substrat ohne vorheriges Auf- bringen eines Primers behandelt mit einer wässrigen Flotte, enthaltendThe present invention relates to a process for producing a coated textile, characterized in that a textile substrate without prior application of a primer is treated with an aqueous liquor containing
(A) mindestens einem Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser im Bereich von 1 bis 500 nm,(A) at least one solid in particulate form having a mean particle diameter in the range of 1 to 500 nm,
(B) mindestens einem hydrophoben Polymer,(B) at least one hydrophobic polymer,
(C) mindestens einem Kondensationsprodukt von mindestens einer Aminogrup- penhaltigen Verbindung und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol.(C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol.
Seit einigen Jahren beschichtet man Textil mit partikulären Stoffen, um die Schmutz abweisenden Eigenschaften zu verbessern, siehe beispielsweise EP-A 1 283 296.For some years now, textiles have been coated with particulate matter in order to improve the soil-repelling properties, see, for example, EP-A 1 283 296.
In WO 02/84013 wird vorgeschlagen, Fasern beispielsweise aus Polyester dadurch zu hydrophobieren, dass man sie durch ein auf 800C erhitztes Bad aus Decalin, in dem 1 % hydrophobiertes Kieselgel Aerosil 8200 suspendiert wurde, hindurchzieht.In WO 02/84013 it is proposed to hydrophobicizing fibers of polyester for example by allowing it to pass through a pulling heated to 80 0 C decalin bath in which 1% of hydrophobic silica Aerosil was suspended 8200th
In WO 02/84016 wird vorgeschlagen, Polyestergewebe dadurch zu hydrophobieren, dass man es durch ein Bad aus auf 500C erwärmtem DMSO (Dimethylsulfoxid), in dem 1 % hydrophobiertes Kieselgel Aeroperl 8200 suspendiert wurde, hindurchzieht.In WO 02/84016 it is proposed to hydrophobize polyester fabric by allowing, through pulling it through a bath of 0 to 50 C heated DMSO (dimethyl sulfoxide), was in the 1% hydrophobic silica Aeroperl suspended 8200th
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.
Um den Gebrauch von großen Mengen an organischen Lösungsmitteln zu vermeiden, wird vorgeschlagen, dass man das betreffende Textil mit einer vorzugsweise wässrigen Formulierung behandelt, die Partikel enthält, die mit Hilfe eines oder mehrerer Dispergiermittel dispergiert werden, siehe beispielsweise WO 2004/074568 und WO 2005/113883.In order to avoid the use of large amounts of organic solvents, it is proposed to treat the textile in question with a preferably aqueous formulation containing particles which are dispersed with the aid of one or more dispersing agents, see, for example, WO 2004/074568 and WO 2005 / 113,883th
Ein Problem ist in vielen Fällen, die Haftung der Partikel auf dem betreffenden Textil zu verbessern, ohne die die Schmutz abweisende Wirkung auf die Dauer nicht zu erhalten ist.A problem in many cases is to improve the adhesion of the particles on the textile in question, without which the dirt-repellent effect is not obtainable in the long run.
Zur Verbesserung der Haftung schlagen WO 2004/074568 und WO 2005/113883 vor, eine sogenannte Haftschicht, beispielsweise mit Hilfe eines sogenannten Primers aufzubringen. Als Primer schlagen WO 2004/074568 und WO 2005/113883 insbesondere N, N-Dimethylol-4,5-diethylenharnstoff (DMDHEU) vor. Diese Haftschicht soll separat aufgetragen werden, und zwar vor dem Aufbringen der Partikel.To improve the adhesion, WO 2004/074568 and WO 2005/113883 propose to apply a so-called adhesive layer, for example with the aid of a so-called primer. As primers beat WO 2004/074568 and WO 2005/113883 in particular N, N-dimethylol-4,5-diethyleneurea (DMDHEU). This adhesive layer should be applied separately, before the particles are applied.
Es bestand jedoch die Aufgabe, die im Stand der Technik vorgeschlagene Verfahren weiter zu verbessern.However, the object was to further improve the method proposed in the prior art.
Dementsprechend wurde das eingangs definierte Verfahren gefunden.Accordingly, the method defined above was found.
Unter Textil oder auch textilen Materialien sind im Rahmen der vorliegenden Erfindung beispielsweise 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, textiles or even textile materials are to be understood as fibers, rovings, yarn, twine on the one hand, and textile fabrics on the other hand, such as, for example, woven goods, knits, 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.
Textil bzw. 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 ge- nannt. 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 or textile materials according to 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 modified natural fibers can be coated by the process according to the invention, for example cellulose acetate.
Das erfindungsgemäße Verfahren geht aus von einer wässrigen Flotte. Unter wässri- ger Flotte im Sinne der vorliegenden Erfindung sind solche Flotten zu verstehen, die, bezogen auf bei Zimmertemperatur flüssige Anteile, mindestens 5 Gew.-% Wasser enthalten können. Bevorzugt enthält wässrige Flotte mindestens 25 Gew.-% Wasser, besonders bevorzugt mindestens 50 Gew.-% und ganz besonders bevorzugt mindes- tens 75 Gew.-%. Der maximale Wassergehalt, bezogen auf bei Zimmertemperatur flüssige Anteile, beträgt 100 Gew.-%, bevorzugt sind 97 Gew.-%, besonders bevorzugt 95 Gew.-%.The inventive method is based on an aqueous liquor. For the purposes of the present invention, aqueous liquors are to be understood as meaning those liquors which, based on portions which are liquid at room temperature, may contain at least 5% by weight of water. Preferably, aqueous liquor contains at least 25 wt .-% water, more preferably at least 50 wt .-% and most preferably at least 75 wt .-%. The maximum water content, based on proportions which are liquid at room temperature, is 100% by weight, preferably 97% by weight, particularly preferably 95% by weight.
Erfindungsgemäß eingesetzte wässrige Flotte kann neben Wasser organische Löse- mittel enthalten, beispielsweise Methanol, Ethanol, Isopropanol, Aceton, Methylethylke- ton, Methylisobutylketon, Ethylenglykol-mono-n-Butylether (Butylglykol), Ethylenglykol- mono-iso-Butylether, Essigsäure, n-Butanol, iso-Butanol, n-Hexanol und Isomere, n- Octanol und Isomere, n-Dodecanol und Isomere. Organische Lösemittel können 0,2 bis 50 Gew.-%, bevorzugt 0,5 bis 35 Gew.-% der erfindungsgemäß eingesetzten wässri- gen Flotte ausmachen. Eine wässrige Flotte mit einem Wassergehalt an 100 Gew.-%, bezogen auf bei Zimmertemperatur flüssige Anteile, enthält dementsprechend keine organischen Lösemittel. Die im erfindungsgemäßen Verfahren eingesetzte wässrige Flotte enthält mindestens einen Feststoff in partikulärer Form, im Rahmen der vorliegenden Erfindung auch Feststoff (A) genannt.In addition to water, aqueous liquors used according to the invention may contain organic solvents, for example methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-isobutyl ether, acetic acid, n Butanol, iso-butanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers. Organic solvents may constitute from 0.2 to 50% by weight, preferably from 0.5 to 35% by weight, of the aqueous liquor used according to the invention. An aqueous liquor with a water content of 100% by weight, based on portions which are liquid at room temperature, accordingly contains no organic solvents. The aqueous liquor used in the process according to the invention comprises at least one solid in particulate form, also called solid (A) in the context of the present invention.
In einer Ausführungsform ist der Anteil von Feststoff (A) mindestens 5,5 g/l wässrige Flotte, bevorzugt mindestens 7 g/l, besonders bevorzugt mindestens 10 g/l.In one embodiment, the proportion of solid (A) is at least 5.5 g / l of aqueous liquor, preferably at least 7 g / l, particularly preferably at least 10 g / l.
Der maximale Anteil kann bei etwa 150 g/l Flotte liegen, bevorzugt maximal 25 g/l. Feststoff (A) kann anorganischer oder organischer Natur sein, bevorzugt ist er anorganisch.The maximum proportion can be about 150 g / l liquor, preferably at most 25 g / l. Solid (A) may be inorganic or organic in nature, preferably inorganic.
Beispiele für geeignete Feststoffe (A) sind Polyethylen, Polypropylen, Polyisobutylen und Polystyrol sowie Copolymere derselben miteinander oder mit einem oder mehre- ren weiteren Olefinen wie beispielsweise Styrol, Methylacrylat, Ethylacrylat, Methyl- methacrylat, n-Butylacrylat, n-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 solids (A) are polyethylene, polypropylene, polyisobutylene and polystyrene, and copolymers thereof with one another or with one or more further olefins, for example styrene, methyl acrylate, ethyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2- Ethylhexyl acrylate, 2-ethylhexyl methacrylate, maleic anhydride or N-methylmaleimide. A preferred polyethylene or polypropylene is described, for example, in EP-A 0 761 696.
Besonders geeignete Feststoffe (A) 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 8000C oder bevorzugt durch physisorbierte oder chemisorbierte organische oder metallorganische Verbindungen hydrophobiert werden. Dazu setzt man Partikel vor dem Beschichtungs- schritt beispielsweise mit metallorganischen Verbindungen um, die wenigstens eine funktionelle Gruppe enthalten, beispielsweise Alkyl-Lithiumverbindungen wie Methyllithium, n-Butyllithium oder n-Hexyllithium; oder Silane wie beispielsweise Hexamethyl- disilazan, Octyltrimethoxysilan und insbesondere halogenierte Silane wie Trimethylch- lorsilan oder Dichlordimethylsilan.Particularly suitable solids (A) 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, aluminum oxide and silicon dioxide being preferred are. 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 hydrophobicized by heating at 400 to 800 0 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-butyllithium or n-hexyllithium; or silanes such as, for example, hexamethyldisilazane, octyltrimethoxysilane and in particular halogenated silanes, such as trimethylchlorosilane or dichlorodimethylsilane.
In einer Ausführungsform der vorliegenden Erfindung setzt man eine Mischung von hydrophobiertem festem anorganischen Oxid mit korrespondierendem nicht- hydrophobiertem anorganischen Oxid ein, beispielsweise in Gewichtsanteilen von 100 : 0 bis 0 :1 00 bevorzugt 99 : 1 bis 60 : 40, besonders bevorzugt 99 : 1 bis 80 : 20.In one embodiment of the present invention, a mixture of hydrophobized solid inorganic oxide with corresponding non-hydrophobicized inorganic oxide is used, for example in proportions by weight of 100: 0 to 0: 100, preferably 99: 1 to 60: 40, particularly preferably 99: 1 to 80:20.
Unter hydrophob wird im Zusammenhang mit dem oder den Feststoffen (A) verstanden, dass seine bzw. ihre Löslichkeit in Wasser unter 1 g/l liegt, bevorzugt unter 0,3 g/l, bestimmt bei Zimmertemperatur. Feststoff (A) kann mit Wasser einen Kontaktwinkel von 90° oder mehr haben, bestimmt bei Zimmertemperatur.Hydrophobic in connection with the solid or solids (A) is understood to mean that its solubility in water is below 1 g / l, preferably below 0.3 g / l, determined at room temperature. Solid (A) may have a contact angle of 90 ° or more with water, determined at room temperature.
Feststoffe (A) können, wenn sie aus anorganischem Material sind, vorzugsweise poröser Natur sein. Die poröse Struktur lässt sich am besten durch die BET-Oberfläche, gemessen nach DIN 66131 , charakterisieren. Eingesetzte Feststoffe (A) 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.Solids (A), when of inorganic material, may preferably be porous in nature. The porous structure is best characterized by the BET surface area, measured according to DIN 66131. Used solids (A) 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.
Feststoff (A) liegt 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 500 nm, bevorzugt bei 350 nm und besonders bevorzugt bei 100 nm. Zur Messung des Partikeldurchmessers kann man sich gängiger Methoden bedienen wie beispielsweise Transmissionselektronenmikroskopie.Solid (A) 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 500 nm, preferably 350 nm and particularly preferably 100 nm Measurement of the particle diameter can be used in common methods such as transmission electron microscopy.
In einer Ausführungsform der vorliegenden Erfindung liegt mindestens ein Feststoff (A) in Form sphärischer Partikel vor, wobei damit solche Feststoffe (A) umfasst sein sollen, von denen mindestens 75 Gew.-%, bevorzugt mindestens 90 Gew.-% in sphärischer Form vorliegen und weitere Partikel in granulärer Form vorliegen können.In one embodiment of the present invention, at least one solid (A) is present in the form of spherical particles, which are intended to encompass those solids (A) of which at least 75% by weight, preferably at least 90% by weight, are present in spherical form and further particles may be in granular form.
In einer Ausführungsform der vorliegenden Erfindung kann mindestens ein Feststoff (A) Aggregate und/oder Agglomerate bilden. Beim Vorliegen eines Feststoffs (A) in Form von Aggregaten und/oder 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 solid (A) may form aggregates and / or agglomerates. In the presence of a solid (A) in the form of aggregates and / or agglomerates, which may consist of 2 to several thousand primary particles and in turn may have spherical shape, the information on the shape and size of the particles refer to the primary particles.
Die im erfindungsgemäßen Verfahren eingesetzte wässrige Flotte enthält mindestens ein hydrophobes Polymer (B).The aqueous liquor used in the process according to the invention contains at least one hydrophobic polymer (B).
Bei einer Ausführungsform der vorliegenden Erfindung handelt es sich bei mindestens einem hydrophoben Polymer um ein Polymer oder Copolymer 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 hydrophobic polymer is a polymer or copolymer 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 derPreferred monomers are selected from the groups of
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, α-Methylstyrol, cis-Stilben, trans-Stilben, Diolefine wie beispielsweise 1 ,3-Butadien, Cyclopentadien, Chloropren oder Isopren, C5-Ci8-Cycloolefine wie beispielsweise Cyclopenten, Cyclohexen, Norbornen, dimeres Cyclopentadien,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; Vinyl aromatics, for example styrene, α-methylstyrene, cis-stilbene, trans-stilbene, Diolefins such as, for example, 1,3-butadiene, cyclopentadiene, chloroprene or isoprene, C 5 -C 18 -cycloolefins such as, for example, cyclopentene, cyclohexene, norbornene, dimeric cyclopentadiene,
Vinylester von linearen oder verzweigten Ci-C2o-Alkancarbonsäuren wie beispielsweise Vinylacetat, Vinylpropionat, Vinyl-n-butyrat, Vinyl-n-hexanoat, Vinyl-n-octanoat, Vinyl- laurat und Vinylstearat,Vinyl esters of linear or branched C 1 -C 20 -alkanoic acids, for example vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl n-hexanoate, vinyl n-octanoate, vinyl laurate and vinyl stearate,
(Meth)acrylsäureester von Ci-C2o-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.(Meth) acrylic esters of C 1 -C 20 -alcohols, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (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.
Hydrophobe Polymere (B), die mindestens ein halogeniertes (Co)monomer einpolyme- risiert enthalten, werden im Rahmen der vorliegenden Erfindung auch als halogenierte (Co)polymere (B) bezeichnet.Hydrophobic polymers (B) which comprise at least one halogenated (co) monomer copolymerized are also referred to in the context of the present invention as halogenated (co) polymers (B).
Zu halogenierten Monomeren gehören chlorierte Olefine wie beispielsweise Vinylchlo- rid und Vinylidenchlorid. Besonders bevorzugt handelt es sich bei hydrophobem Polymer (B) um ein fluoriertes (Co)polymer.Halogenated monomers include chlorinated olefins such as vinyl chloride and vinylidene chloride. Most preferably, hydrophobic polymer (B) is a fluorinated (co) polymer.
Ganz besonders bevorzugte halogenierte Monomere sind fluorhaltige Olefine wie beispielsweise Vinylidenfluorid, Trifluorchlorethylen, Tetrafluorethylen, Hexafluorpropylen, Vinylester von fluorierten oder perfluorierten C3-Cn-Carbonsäuren wie beispielsweise in US 2,592,069 und US 2,732,370 beschrieben,Very particularly preferred halogenated monomers are fluorine-containing olefins such as, for example, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C3-Cn-carboxylic acids as described, for example, in US Pat. Nos. 2,592,069 and 2,732,370,
(Meth)acrylsäureester von fluorierten oder perfluorierten Alkoholen wie beispielsweise fluorierten oder perfluorierten C3-Ci4-Alkylalkoholen, beispielsweise (Meth)acrylatsäureeester von HO-CH2-CH2-CF3, HO-CH2-CH2-C2F5, HO-CH2-CH2-n-C3F7, HO-CH2-CH2HSO-C3F7, HO-CH2-CH2-n-C4F9, HO-CH2-CH2-n- C6Fi3, HO-CH2-CH2-n-C8Fi7, HO-CH2-CH2-n-CioF2i, HO-CH2-CH2-n-Ci2F25, beschrieben beispielsweise in US 2,642,416, US 3,239,557, BR 1 ,1 18,007, US 3,462,296.(Meth) acrylic esters of fluorinated or perfluorinated alcohols, for example fluorinated or perfluorinated C 3 -C 4 -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 F7, HO-CH 2 -CH 2 HSO-C 3 F 7, HO-CH 2 -CH 2 -nC 4 F9, HO-CH 2 -CH 2 -N-C 6 Fi 3 , HO-CH 2 -CH 2 -nC 8 Fi7, HO-CH 2 -CH 2 -n-CioF 2 i, HO-CH 2 -CH 2 -n-Ci 2 F 25 , described for example in US 2,642,416, US 3,239,557, BR 1, 1 18,007, US 3,462,296.
Auch Copolymere von beispielsweise Gycidyl(meth)acrylat mit Estern der Formel IlAlso copolymers of, for example, glycidyl (meth) acrylate with esters of the formula II
in denen die Variablen wie folgt definiert sind: R4 Wasserstoff, CH3, C2H5, R5 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 1 1 , bevorzugt 1 bis 6,where the variables are defined as follows: R 4 is hydrogen, CH 3 , C 2 H 5 , R 5 is CH 3 , C 2 H 5 , x is an integer in the range from 4 to 12, very particularly preferably 6 to 8 y is an integer in the range from 1 to 1 , preferably 1 to 6,
oder Glycidy(meth)acrylat mit Vinylestern von fluorierten Carbonsäuren sind geeignet.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-Ci2-Alkylalkohole wie beispielsweise 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-C5Fn, HO-CH2-CH2-n-C6Fi3, HO-CH2-CH2-n-C7Fi5; mit (Meth)acrylsäureestern nicht-halogenierter Ci-C2o-Alkohole, beispielsweise Me- thyl(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, oder mit ethylenisch ungesättigten Carbonsäuren wie (Meth)acrylsäure.Other suitable copolymers are copolymers of (meth) acrylsäureestern fluoro or perfluoro C 3 -C 2 -alkyl alcohols such as 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 2 -CH 2 -nC 4 F 9, HO-CH 2 -CH 2 -nC 5 Fn, HO- CH 2 -CH 2 -nC 6 Fi 3 , HO-CH 2 -CH 2 -nC 7 Fi 5 ; 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, or with ethylenically unsaturated carboxylic acids such as (meth) acrylic acid.
Eine Übersicht über geeignete halogenierte (Co)polymere (B) findet sich beispielsweise in M. Lewin et al., Chemical Processing of Fibers and Fabrics, Part B, 2. Band, Mar- cel Dekker, New York (1984), Seite S. 172 ff. und S. 178 - 182.An overview of suitable halogenated (co) polymers (B) can be found, for example, in M. Lewin et al., Chemical Processing of Fibers and Fabrics, Part B, Volume 2, Marcel Dekker, New York (1984), p 172 ff., And pp. 178-182.
Weitere geeignete fluorierte Polymere sind beispielsweise in DE 199 120 810 offengelegt.Further suitable fluorinated polymers are disclosed, for example, in DE 199 120 810.
Aus der Gruppe der Olefine mit Siloxangruppen seien Olefine der allgemeinen Formeln III a bis III cFrom the group of olefins with siloxane groups are olefins of the general formulas III a to III c
genannt, in denen die Variablen wie folgt definiert sind: R6 ist gewählt ausin which the variables are defined as follows: R 6 is selected from
Ci-Cis-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 d-Cε-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 Ci-C4-AIkVl wie Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl und tert.-Butyl und ganz besonders Methyl.C 1 -C 6 -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, iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n- Butyl, iso-butyl, sec-butyl and tert-butyl, and especially methyl.
C6-Ci4-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-Ci2-Cycloalkyl, beispielsweise Cyclopropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl, Cycloheptyl, Cyclooctyl, Cyclononyl, Cyclodecyl, Cycloundecyl und Cyclododecyl; bevorzugt sind Cyclopentyl, Cyclohexyl und Cycloheptyl C 6 -C 4 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
R7 ist Methyl oder Wasserstoff.R 7 is methyl or hydrogen.
a ist eine ganze Zahl im Bereich von 2 bis 10.000, insbesondere bis 100,a is an integer in the range of 2 to 10,000, especially up to 100,
b ist eine ganze Zahl im Bereich von 0 bis 6, insbesondere 1 bis 2.b is an integer in the range of 0 to 6, especially 1 to 2.
Wenn es sich bei Feststoff (A) um ein organisches Polymer handelt, so ist hydrophoben Polymer (B) verschieden von Feststoff (A), und bevorzugt ist hydrophobes Polymer (B) ein vorzugsweise halogeniertes Polymer (B) und insbesondere ein fluoriertes Polymer.When solid (A) is an organic polymer, hydrophobic polymer (B) is different from solid (A), and preferably, hydrophobic polymer (B) is a preferably halogenated polymer (B), and particularly a fluorinated polymer.
Im erfindungsgemäßen Verfahren eingesetzte wässrige Flotte enthält weiterhin (C) mindestens ein Kondensationsprodukt von mindestens einer Aminogruppenhalti- gen Verbindung und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol, im Rahmen der vorliegenden Erfindung auch kurz „Kondensationsprodukt (C)" genannt.The aqueous liquor used in the process according to the invention furthermore contains (C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol, also referred to in the context of the present invention as "condensation product (C)".
Bei Aminogruppenhaltigen Verbindungen handelt es sich um organische Verbindungen mit mindestens einer, bevorzugt mindestens zwei und besonders bevorzugt genau zwei oder drei primären Aminogruppen pro Molekül. Beispielsweise kann es sich um 1 ,2-Ethylendiamin oder 1 ,3-Propylendiamin handeln. Bevorzugt wird als Aminogrup- penhaltige Verbindung Harnstoff gewählt. Bei Aldehyden handelt es sich um vorzugsweise aliphatische Aldehyde wie Acetalde- hyd und insbesondere Formaldehyd.Amino-containing compounds are organic compounds having at least one, preferably at least two and more preferably exactly two or three primary amino groups per molecule. For example, it may be 1, 2-ethylenediamine or 1, 3-propylenediamine. Preference is given to choosing urea as amino group-containing compound. Aldehydes are preferably aliphatic aldehydes such as acetaldehyde and especially formaldehyde.
Bei Dialdehyden handelt es sich um vorzugsweise aliphatische Dialdehyde wie Glutar- dialdehyd, Succindialdehyd und insbesondere Glyoxal.Dialdehydes are preferably aliphatic dialdehydes, such as glutaraldehyde, succinic dialdehyde and in particular glyoxal.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Kondensationsprodukt (C) um eine Verbindung der allgemeinen Formel IV.In one embodiment of the present invention, condensation product (C) is a compound of general formula IV.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung handelt es sich In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Kondensations- produkt (C) um eine Verbindung der allgemeinen Formel I,In a preferred embodiment of the present invention, in one embodiment of the present invention, the condensation product (C) is a compound of the general formula I
wobei die Variablen in Formel I und IV jeweils wie folgt definiert sind:wherein the variables in formulas I and IV are each defined as follows:
R1 jeweils verschieden oder vorzugsweise gleich und gewählt ausEach R 1 is different or preferably the same and selected from
Ci-Cβ-Alkyl, verzweigt oder vorzugsweise unverzweigt, ausgewählt aus 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 lineares CrC4-AIkVl wie Methyl, Ethyl, n-Propyl, und n-Butyl,Ci-Cβ-alkyl, branched or preferably unbranched, selected from 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, more preferably linear CrC 4 -AlkVl such as methyl, ethyl, n-propyl, and n-butyl,
(CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3, (CH2-CH2-CH2-CI-l2-O)m-R3, bevorzugt (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist, und vorzugsweise Wasserstoff.(CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH 2 -CH 2 -CH 2- Ci-12-O) mR 3 , preferably (CH 2 CH 2 O) m R 3 , wherein m is an integer in the range of 1 to 50, and preferably hydrogen.
R2 so vorhanden - jeweils verschieden oder vorzugsweise gleich und gewählt aus Ci-Cβ-Alkyl, verzweigt oder vorzugsweise unverzweigt, ausgewählt aus 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 lineares Ci-C4-AIkVl wie Methyl, Ethyl, n-Propyl, und n-Butyl,R 2 is present - in each case different or preferably identical and selected from C 1 -C 6 -alkyl, branched or preferably unbranched, selected from among methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl , tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, particularly preferably linear C 1 -C 4 -alkyl such as methyl, ethyl, n-propyl, and n-butyl,
(CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3, (CH2-CH2-CH2-CI-l2-O)m-R3, bevorzugt (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist,(CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH 2 -CH 2 -CH 2- Ci-12-O) mR 3 , preferably (CH 2 CH 2 O) m R 3 , where m is an integer in the range from 1 to 50,
und vorzugsweise Wasserstoff.and preferably hydrogen.
R3 wird gewählt aus Wasserstoff und Ci-C2o-Alkyl, bevorzugt Ethyl und insbesonde- re Methyl.R 3 is selected from hydrogen and C 1 -C 20 -alkyl, preferably ethyl and in particular methyl.
Besonders bevorzugt sind in Formel I die Variablen R1 und R2 jeweils gleich.Particularly preferred in formula I, the variables R 1 and R 2 are the same.
Ganz besonders bevorzugt handelt es sich bei Kondensationsprodukt (C) um N,N- Dimethylol-4,4-dihydroxyethylenharnstoff (DMDHEU).Very particular preference is given to condensation product (C) with N, N-dimethylol-4,4-dihydroxyethyleneurea (DMDHEU).
Die wässrige Flotte, die im erfindungsgemäßen Verfahren eingesetzt wird, kann eine oder mehrere oberflächenaktive Verbindungen (D) enthalten gewählt beispielsweise aus der Gruppe der ionischen und nichtionischen Emulgatoren.The aqueous liquor used in the process according to the invention may contain one or more surface-active compounds (D) selected, for example, from the group of ionic and nonionic emulsifiers.
Als oberflächenaktive Verbindungen (D) geeignete nichtionische Emulgatoren sind z.B. ethoxylierte Mono-, Di- und Tri-Alkylphenole (Ethoxylierungs-Grad: 3 bis 50, Alkylrest: C4-C12) sowie ethoxylierte Fettalkohole (Ethoxylierungs-Grad: 3 bis 80; Alkylrest: Cs- C36). Beispiele hierfür sind die Lutensol®-Marken der BASF Aktiengesellschaft.Suitable nonionic emulsifiers as surface-active compounds (D) are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C 4 -C 12) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80; Cs-C36). Examples include the Lutensol ® brands of BASF Aktiengesellschaft.
Als oberflächenaktive Verbindungen (D) geeignete anionische Emulgatoren sind z.B. Alkalimetall- und Ammoniumsalze von Alkylsulfaten (Alkylrest: Cs bis C12), von Schwefelsäurehalbestern ethoxylierter Alkanole (Ethoxylierungs-Grad: 4 bis 30, Alkylrest: C12-C18) und ethoxylierter Alkylphenole (Ethoxylierungs-Grad: 3 bis 50, Alkylrest: C4-C12), von Alkylsulfonsäuren (Alkylrest: C12-C18) und von Alkylarylsulfonsäuren (Alkylrest: Cg-ds).Anionic emulsifiers suitable as surface-active compounds (D) are e.g. Alkali metal and ammonium salts of alkyl sulfates (alkyl radical: Cs to C12), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C12-C18) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C4-C12 ), of alkylsulfonic acids (alkyl group: C12-C18) and of alkylarylsulfonic acids (alkyl group: Cg-ds).
Geeignete kationische Emulgatoren sind in der Regel einen Cβ-Cis-Alkyl-, -Aralkyl- oder heterocyclischen Rest aufweisende primäre, sekundäre, tertiäre oder quartäre Ammoniumsalze, Alkanolammoniumsalze, Pyridiniumsalze, Imidazoliniumsalze,Suitable cationic emulsifiers are generally Cβ-Cis-alkyl, aralkyl or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts,
Oxazoliniumsalze, Morpholiniumsalze, Thiazoliniumsalze sowie Salze von Aminoxiden, Chinoliniumsalze, Isochinoliniumsalze, Tropyliumsalze, Sulfoniumsalze und Phosphoniumsalze. Beispielhaft genannt seien Dodecylammoniumacetat oder das entsprechende Hydrochlorid, die Chloride oder Acetate der verschiedenen 2-(N, N, N- Trimethylammonium)ethylparaffinsäureester, N-Cetylpyridiniumchlorid, N-Oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinsäureester, N-cetylpyridinium chloride, N-
Laurylpyridiniumsulfat sowie N-Cetyl-N,N,N-trimethylammoniumbromid, N-Dodecyl- N,N,N-trimethylammoniumbromid, N,N-Distearyl-N,N-dimethylammoniumchlorid sowie das Gemini-Tensid N,N'-(Lauryldimethyl)ethylendiamindibromid. Zahlreiche weitere Beispiele finden sich in H. Stäche, Tensid-Taschenbuch, Carl-Hanser-Verlag, München, Wien, 1981 und in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N-dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and Gemini surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stäche, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981, and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.
Besonders bevorzugte kationische Emulgatoren sind alkoxylierte Fettamine, insbesondere ethoxylierte Cio-C2o-Fettamine mit einem Ethoxylierungsgrad von im Mittel 2 bis 12.Particularly preferred cationic emulsifiers are alkoxylated fatty amines, in particular ethoxylated C 20 -C 20 fatty amines having a degree of ethoxylation of 2 to 12 on average.
Als oberflächenaktive Verbindungen (D) ganz besonders geeignete Emulgatoren polymere Emulgatoren. Zu nennen sind beispielsweise Copolymerisate von Ethylen und mindestens einer α,ß-ungesättigten Mono- oder Dicarbonsäure oder mindestens einem Anhydrid einer α,ß-ungesättigten Mono- oder Dicarbonsäure, beispielsweise Acrylsäure, Methacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure, Methylenmalonsäure, Maleinsäureanyhdrid, Itaconsäureanhydrid. DieAs surface-active compounds (D), particularly suitable emulsifiers are polymeric emulsifiers. Examples include copolymers of ethylene and at least one α, ß-unsaturated mono- or dicarboxylic acid or at least one anhydride of an α, ß-unsaturated mono- or dicarboxylic acid, for example acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, Methylenmalonsäure, Maleinsäureanyhdrid, itaconic anhydride , The
Carboxylgruppen können partiell oder vorzugsweise vollständig neutralisiert sein, beispielsweise mit Alkalimetallionen, Erdalkalimetallionen, Ammonium oder Aminen, beispielsweise Amine wie Triethylamin, Diethylamin, Ethylamin, Trimethylamin, Di- methylamin, Methylamin, Ethyldiisopropylamin, Ethanolamin, Diethanolamin, Trietha- nolamin, N-Methyldiethanolamin, N-(n-Butyl)diethanolamin oder N, N- Dimethylethanolamin.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 oberflächenaktiver Verbindung (D) lässt sich in weiten Grenzen wählen und kann null bis 100 g/l betragen, bevorzugt 0,2 bis 10 g/l.The proportion of surface-active compound (D) can be chosen within wide limits and can be zero to 100 g / l, preferably 0.2 to 10 g / l.
In einer Ausführungsform der vorliegenden Erfindung kann die im erfindungsgemäßen Verfahren eingesetzte wässrige Flotte einen oder mehrere Zusätze (E) enthalten. Geeignet sind beispielsweise Netzmittel, Entschäumer (Schauminhibitoren), Belüftungsmittel, Vernetzer (Härter), Verlaufshilfsmittel und Verdickungsmittel sowie insbesondere Polyvinylacetat, Polyvinylalkohol oder teilverseiftes Polyvinylacetat.In one embodiment of the present invention, the aqueous liquor used in the process according to the invention may contain one or more additives (E). Wetting agents, defoamers (foam inhibitors), aeration agents, crosslinking agents (curing agents), leveling agents and thickeners, and in particular polyvinyl acetate, polyvinyl alcohol or partially saponified polyvinyl acetate are suitable, for example.
Als Zusatz (E) kann man ein oder mehrere Netzmittel einsetzen, beispielhaft sind Al- kylpolyglycoside, Alkylphosphonate, Alkylphenylphosphonate, Alkylphosphate und Al- kylphenylphosphate zu nennen.As additive (E) it is possible to use one or more wetting agents, by way of example alkyl polyglycosides, alkyl phosphonates, alkyl phenyl phosphonates, alkyl phosphates and alkyl phenyl phosphates.
Als Zusatz (E) kann man ein oder mehrere Entschäumer (Schauminhibitoren) einsetzen, beispielhaft sind bei Zimmertemperatur flüssige Silikone, nicht ethoxyliert oder ein- oder mehrfach ethoxyliert, zu nennen.As additive (E) it is possible to use one or more defoamers (foam inhibitors); by way of example, liquid silicones, not ethoxylated or ethoxylated one or more times at room temperature, may be mentioned at room temperature.
Als Zusatz (E) kann man ein oder mehrere Verdickungsmittel zusetzen, das bzw. die beispielsweise natürlichen oder synthetischen Ursprungs sein können. Geeignete synthetische Verdickungsmittel sind Poly(meth)acrylverbindungen, Polycarbonsäuren, Polyether, Polyimine, Polyamide wie beispielsweise Polyacrylamid, und Polyurethane. Insbesondere sind Copolymere mit 85 bis 95 Gew.-% Acrylsäure, 4 bis 15 Gew.-% Acrylamid und etwa 0,01 bis 1 Gew.-% des (Meth)acrylamidderivats der Formel VAs additive (E) it is possible to add one or more thickening agents, which may be of natural or synthetic origin, for example. Suitable synthetic thickeners are poly (meth) acrylic compounds, polycarboxylic acids, Polyethers, polyimines, polyamides such as polyacrylamide, and polyurethanes. In particular, copolymers with 85 to 95% by weight of acrylic acid, 4 to 15% by weight of acrylamide and about 0.01 to 1% by weight of the (meth) acrylamide derivative of the formula V
mit Molekulargewichten Mw im Bereich von 100.000 bis 2.000.000 g/mol zu nennen, in denen R8 für Methyl oder vorzugsweise Wasserstoff steht. Als Beispiele für Verdickungsmittel natürlichen Ursprungs seien genannt: Agar-Agar, Carrageen, modifizierte Stärke und modifizierte Cellulose.with molecular weights M w in the range of 100,000 to 2,000,000 g / mol, where R 8 is methyl or preferably hydrogen. Examples of thickening agents of natural origin include: agar-agar, carrageenan, modified starch and modified cellulose.
Als Zusatz (E) kann man ein oder mehrere Vernetzer (Härter) einsetzen. Beispiele sind Isocyanurate und insbesondere hydrophilierte Isocyanurate sowie gemischte hydrophi- lierte Diisocyanate/Isocyanurate, beispielsweise mit Ci-C4-Alkylpolyethylenglykol um- gesetztes Isocyanurat von Hexamethylendiisocyanat (HDI). Beispiele für derartige Vernetzer sind beispielsweise aus EP-A 0 486 881 bekannt. Weitere Beispiele sind Oxim- verschlossene Isocyanate/Diisocyanate/Isocyanurate, insbesondere Butoxim- verschlossene Diisocyanate und Butoxim-verschlossene Isocyanurate.As additive (E) one can use one or more crosslinkers (hardeners). Examples are isocyanurates and in particular hydrophilicized isocyanurates and also mixed hydrophilicized diisocyanates / isocyanurates, for example isocyanurate of hexamethylene diisocyanate (HDI) reacted with C 1 -C 4 -alkylpolyethyleneglycol. Examples of such crosslinkers are known, for example, from EP-A 0 486 881. Further examples are oxime-blocked isocyanates / diisocyanates / isocyanurates, in particular butoxime-sealed diisocyanates and butoxime-blocked isocyanurates.
Als Zusatz (E) kann man ein oder mehrere Verlaufshilfsmittel einsetzen, beispielsweise Ethylenglykol.As additive (E) one can use one or more leveling agents, for example ethylene glycol.
Als Zusatz (E) kann man ein oder mehrere Belüftungsmittel einsetzen, beispielsweise einen oder mehrere Guerbetalkohole, einfach oder bis zu zehnfach ethoxyliert.As additive (E) one can use one or more aerating agents, for example one or more Guerbet alcohols, simply or up to ten times ethoxylated.
Als bevorzugten Zusatz (E) kann man Polyvinylacetat, Polyvinylalkohol oder teilverseiftes Polyvinylacetat einsetzen, insbesondere zu 0,1 bis 75 mol-% teilverseiftes Polyvinylacetat. Weitere bevorzugte Zusätze (E) sind Mischungen von Polyvinylacetat oder teilverseiftem Polyvinylacetat und Polyvinylalkohol.As preferred additive (E) it is possible to use polyvinyl acetate, polyvinyl alcohol or partially saponified polyvinyl acetate, in particular from 0.1 to 75 mol% partially saponified polyvinyl acetate. Further preferred additives (E) are mixtures of polyvinyl acetate or partially saponified polyvinyl acetate and polyvinyl alcohol.
Als Zusatz (E) kann man schwache Säuren oder schwache Basen als pH-Wert- Regulatoren einsetzen. Geeignet sind beispielsweise Ammoniumsalze wie NH4CI und (NH4^SO4. Weiterhin sind Carbonsäuren geeignet wie beispielsweise Essigsäure oder Zitronensäure.As additive (E) one can use weak acids or weak bases as pH regulators. Suitable examples are ammonium salts such as NH 4 Cl and (NH 4) SO 4 , furthermore suitable are carboxylic acids such as, for example, acetic acid or citric acid.
Als Zusatz (E) kann man ein oder mehrere Biozide einsetzen. Beispiele für Biozide sind beispielsweise 1 ,2-Benzisothiazolin-3-on („BIT") (kommerziell erhältlich als Pro- xel®-Marken der Fa. Avecia Lim.) und dessen Alkalimetallsalze zu nennen, andere geeignete Biozide sind 2-Methyl-2H-isothiazol-3-on („MIT") und 5-Chlor-2-methyl-2H- isothiazol-3-on („CIT"). Im Allgemeinen sind 10 bis 150 ppm Biozid ausreichend, bezogen auf wässrige Flotte.As additive (E) one can use one or more biocides. Examples of biocides are, for example, 1,2-benzisothiazolin-3-one ("BIT") (commercially available as Proxel® brand from Avecia Lim.) And its alkali metal salts, other suitable biocides are 2-methyl 2H-isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H- Isothiazol-3-one ("CIT") Generally, 10 to 150 ppm of biocide is sufficient, based on aqueous liquor.
In einer Ausführungsform der vorliegenden Erfindung enthält die im erfindungsgemä- ßen Verfahren eingesetzte wässrige Flotte: im Bereich von 5,5 bis 150 g/l, bevorzugt 6 bis 25 g/l an Feststoff (A), im Bereich von 10 bis 60 g/l, bevorzugt 15 bis 40 g/l an hydrophobem Polymer (B), im Bereich von 50 bis 150 g/l, bevorzugt 60 bis 120 g/l an Kondensationsprodukt (C), null bis 20 g/l, bevorzugt 3 bis 10 g/l an oberflächenaktiver Verbindung (D), insgesamt null bis insgesamt 150 g/l, bevorzugt 25 bis 100 g/l an Zusätzen (E).In one embodiment of the present invention, the aqueous liquor used in the process according to the invention contains: in the range of 5.5 to 150 g / l, preferably 6 to 25 g / l of solid (A), in the range of 10 to 60 g / 1, preferably 15 to 40 g / l of hydrophobic polymer (B), in the range of 50 to 150 g / l, preferably 60 to 120 g / l of condensation product (C), zero to 20 g / l, preferably 3 to 10 g / l of surface-active compound (D), in total from zero to a total of 150 g / l, preferably from 25 to 100 g / l of additives (E).
Der Rest ist beispielsweise kontinuierliche Phase.The rest is, for example, continuous phase.
Das erfindungsgemäße Verfahren führt man so durch, dass man textiles Material mit der wässrigen Flotte behandelt.The process according to the invention is carried out by treating textile material with the aqueous liquor.
Das erfindungsgemäße Verfahren führt man also so durch, dass man auf das Aufbringen eines Primers verzichtet. Vor der erfindungsgemäßen Behandlung mit der wässrigen Flotte bringt man also keinen Primer auf. Dabei werden unter Primern haftvermit- telnde und/oder hydrophilierende (Co)polymere oder Harze wie N,N-Dimethylol-4,5- diethylenharnstoff (DMDHEU) verstanden.The method according to the invention is thus carried out by omitting the application of a primer. Thus, prior to the treatment according to the invention with the aqueous liquor, no primer is applied. In this context, primers are adhesion-promoting and / or hydrophilicizing (co) polymers or resins, such as N, N-dimethylol-4,5-diethyleneurea (DMDHEU).
Die Temperatur zur Durchführung des erfindungsgemäßen Verfahrens ist an sich unkritisch. Die Flottentemperatur liegt kann im Bereich von 10 bis 800C liegen, bevorzugt 15 bis 600C.The temperature for carrying out the method according to the invention is not critical per se. The liquor temperature can be in the range of 10 to 80 ° C., preferably 15 to 60 ° C.
Die Flottenaufnahme kann man so wählen, dass durch das erfindungsgemäße Verfahren eine Flottenaufnahme von 25 Gew.-% bis 85 Gew.-%, bevorzugt 30 bis 70 Gew.-% resultiert.The liquor pickup can be chosen so that the liquefaction of the process according to the invention results from 25% by weight to 85% by weight, preferably from 30 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.
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 thermisch behandeln, und zwar kontinuierlich oder diskontinuierlich. Die Dauer der thermischen Behandlung 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 thermisch behandeln. Zur Durchführung einer thermischen Behandlung erhitzt man auf Temperaturen von bis zu 1800C, bevorzugt bis zu 1500C. Natürlich ist es erforderlich, die Temperatur der thermischen Behandlung an die Empfindlichkeit des Gewebes anzupassen.Following the treatment according to the invention, it is possible to treat thermally, continuously or discontinuously. The duration of the thermal treatment you can choose within wide limits. Typically, one can thermally treat for a period of about 10 seconds to about 30 minutes, more preferably 30 seconds to 5 minutes. To carry out a thermal treatment, heating is carried out to temperatures of up to 180 ° C., preferably up to 150 ° C. Of course, it is necessary to adapt the temperature of the thermal treatment to the sensitivity of the fabric.
Geeignete Methode zur thermischen Behandlung ist beispielsweise eine Heißlufttrocknung.Suitable method for thermal treatment, for example, a hot air drying.
Ein weiterer Gegenstand der vorliegenden Erfindung sind Textilien, beschichtet nach dem erfindungsgemäßen Verfahren, im Folgenden auch als erfindungsgemäßes Textil bezeichnet. In erfindungsgemäßem Textil ist die Beschichtung in einer Schicht angeordnet. ErfindungsgemäßesTextil zeichnet sich nicht nur durch gute Echtheiten wie beispielsweise Reibechtheiten aus, sondern auch sehr gute Schmutz abweisende Wirkung, geringe Wasserdurchlässigkeit sowie hohe Steifigkeit und geringe Wasserdurchlässigkeit. Erfindungsgemäßes Textil ist besonders gut zur Herstellung von Textilien für den Außenbereich geeignet, beispielsweise für Sonnenschirme und Markisen, aber auch zur Bespannung von Möbeln.Another object of the present invention are textiles coated by the method according to the invention, hereinafter also referred to as textile according to the invention. In textile according to the invention, the coating is arranged in a layer. Textile according to the invention is distinguished not only by good fastnesses, such as, for example, rub fastnesses, but also very good dirt-repelling effect, low water permeability and high rigidity and low water permeability. Textile according to the invention is particularly suitable for the production of textiles for outdoor use, for example for parasols and awnings, but also for covering furniture.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von erfindungsgemäßem Textil als oder zur Herstellung von Markisenstoffen, Verdecken oder Planen. Ein weiterer Gegenstand der vorliegenden Erfindung sind Markisenstoffe, Verdecke oder Planen, hergestellt unter Verwendung von erfindungsgemäßem Textil.Another object of the present invention is the use of textile according to the invention as or for the production of awning fabrics, covering or tarpaulins. Another object of the present invention are awning fabrics, covers or tarpaulin, prepared using textile according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung sind wässrige Flotten, enthaltendAnother object of the present invention are aqueous liquors containing
(A) mindestens einen Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser im Bereich von 1 bis 500 nm, kurz auch Feststoff (A) genannt,(A) at least one solid in particulate form having a mean particle diameter in the range of 1 to 500 nm, also called solid (A) for short,
(B) mindestens ein hydrophobes Polymer, kurz auch Polymer (B) genannt, (C) mindestens einem Kondensationsprodukt von mindestens einer Aminogrup- penhaltigen Verbindung und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol, kurz auch als Kondensationsprodukt (C) bezeichnet,(B) at least one hydrophobic polymer, also called polymer (B) for short, (C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol, also referred to briefly as condensation product (C),
(D) gegebenenfalls mindestens eine oberflächenaktive Verbindung, kurz auch ober- flächenaktive Verbindung (D) genannt,(D) if appropriate at least one surface-active compound, in short also called surface-active compound (D),
(E) gegebenenfalls einen oder mehrere Zusätze.(E) optionally one or more additives.
Feststoff (A), Polymer (B), Kondensationsprodukt (C), oberflächenaktive Verbindung (D) und Zusätze (E) sind vorstehend definiert. In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Kondensationsprodukt (C) um ein Kondensationsprodukt von Harnstoff und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol.Solid (A), polymer (B), condensation product (C), surface active compound (D) and additives (E) are defined above. In one embodiment of the present invention, condensation product (C) is a condensation product of urea and at least one aldehyde or dialdehyde and optionally at least one alcohol.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei hydrophobem Polymer (B) um ein fluoriertes (Co)polymer.In one embodiment of the present invention, hydrophobic polymer (B) is a fluorinated (co) polymer.
In einer Ausführungsform der vorliegenden Erfindung handelt es sich bei Kondensationsprodukt (C) um eine Verbindung der allgemeinen Formel IV.In one embodiment of the present invention, condensation product (C) is a compound of general formula IV.
In einer Ausführungsform der vorliegenden Erfindung handelt es bei Kondensationsprodukt (C) um eine Verbindung der allgemeinen Formel IIn one embodiment of the present invention, condensation product (C) is a compound of general formula I.
wobei in Formel I und IV die Variablen wie folgt definiert sind: R1 jeweils verschieden oder gleich und gewählt aus Wasserstoff, Ci-Cβ-Alkyl, (CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-CVR3,wherein in formulas I and IV the variables are defined as follows: each R 1 is different or the same and selected from hydrogen, C 1 -C 6 -alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -CVR 3 ,
(CH2-CH2-CH2-CH2-O)m-R3 und vorzugsweise (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist,(CH 2 -CH 2 -CH 2 -CH 2 -O) m -R 3 and preferably (CH 2 CH 2 O) m R 3 , where m is an integer in the range of 1 to 50,
R2 jeweils verschieden oder gleich und gewählt aus Wasserstoff, Ci-Cβ-Alkyl, (CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3, (CH2-CH2-CH2-CH2-O)m-R3 und vorzugsweise (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist, R3 gewählt wird aus Wasserstoff und Ci-C2o-Alkyl.Each R 2 is the same or different and selected from hydrogen, C 1 -C 6 -alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -CH 2 -O) m -R 3 and preferably (CH 2 CH 2 O) m R 3 , where m is an integer in the Range is 1 to 50, R 3 is selected from hydrogen and C 1 -C 20 -alkyl.
In einer Ausführungsform der vorliegenden Erfindung enthält erfindungsgemäße wäss- rige Flotte:In one embodiment of the present invention, aqueous liquor of the invention contains:
Im Bereich von 5,5 bis 150 g/l, bevorzugt 6 bis 25 g/l an Feststoff (A), im Bereich von 10 bis 60 g/l, bevorzugt 15 bis 40 g/l an hydrophobem Polymer (B), im Bereich von 50 bis 150 g/l, bevorzugt 60 bis 120 g/l an Kondensationsprodukt (C), null bis 20 g/l, bevorzugt 3 bis 10 g/l an oberflächenaktiver Verbindung (D), insgesamt null bis insgesamt 150 g/l, bevorzugt 25 bis 100 g/l an Zusätzen (E). In einer Ausführungsform der vorliegenden Erfindung weisen erfindungsgemäße Flotten einen pH-Wert im Bereich von 2 bis 9, bevorzugt 3,5 bis 7,5 auf.In the range of 5.5 to 150 g / l, preferably 6 to 25 g / l of solid (A), in the range of 10 to 60 g / l, preferably 15 to 40 g / l of hydrophobic polymer (B), im Range of 50 to 150 g / l, preferably 60 to 120 g / l of condensation product (C), zero to 20 g / l, preferably 3 to 10 g / l of surface-active compound (D), in total from zero to a total of 150 g / 1, preferably 25 to 100 g / l of additives (E). In one embodiment of the present invention, liquors of the invention have a pH in the range from 2 to 9, preferably 3.5 to 7.5.
Die erfindungsgemäße Flotte lässt sich besonders vorteilhaft im erfindungsgemäßen Verfahren einsetzen.The liquor of the invention can be used particularly advantageously in the process according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von erfindungsgemäßen wässrigen Flotten, im Rahmen der vorliegenden Erfindung auch erfindungsgemäßes Herstellverfahren genannt. Zur Durchführung des erfin- dungsgemäßen Herstellverfahrens kann man so vorgehen, dass man die Komponenten Feststoff (A), hydrophobes Polymer (B), Kondensationsprodukt (C) und gegebenenfalls oberflächenaktive Verbindung (D) und gegebenenfalls einen oder mehrere Zusätze (E) miteinander und mit Wasser vermischt, beispielsweise durch Verrühren. Dabei ist die Reihenfolge der Komponenten Feststoff (A), hydrophobes Polymer (B), Kondensationsprodukt (C) und gegebenenfalls oberflächenaktive Verbindung (D) und gegebenenfalls ein oder mehrere Zusätze (E) beliebig. Bevorzugt ist jedoch, dass man eine oder mehrere der Komponenten, insbesondere hydrophobes Polymer (B) und Kondensationsprodukt (C), in mit Wasser oder einem Lösemittel vorvermischter Form einsetzt.Another object of the present invention is a process for the preparation of aqueous liquors according to the invention, in the context of the present invention also called production process according to the invention. To carry out the production process according to the invention, it is possible to use the components solid (A), hydrophobic polymer (B), condensation product (C) and optionally surface-active compound (D) and optionally one or more additives (E) with each other and with Mixed water, for example by stirring. The sequence of the components solid (A), hydrophobic polymer (B), condensation product (C) and optionally surface-active compound (D) and optionally one or more additives (E) is arbitrary. However, preference is given to using one or more of the components, in particular hydrophobic polymer (B) and condensation product (C), in a form premixed with water or a solvent.
Das erfindungsgemäße Herstellverfahren kann man bei beliebigen Temperaturen, insbesondere bei Temperaturen im Bereich von 5 bis 95°C durchführen. Bevorzugt ist Zimmertemperatur.The preparation process according to the invention can be carried out at any temperatures, in particular at temperatures in the range from 5 to 95.degree. Preference is given to room temperature.
Die Erfindung wird durch Arbeitsbeispiele erläutert.The invention will be explained by working examples.
Mengenangaben von wässrigen Mischungen beziehen sich stets auf den Feststoffgehalt, wenn nicht ausdrücklich anders angegebenQuantities of aqueous mixtures always refer to the solids content, unless expressly stated otherwise
I. Herstellung von erfindungsgemäßen wässrigen Formulierungen Es wurden die folgenden Substanzen eingesetzt:I. Preparation of Aqueous Formulations According to the Invention The following substances were used:
Feststoff (A.1 ): mit Dimethylsiloxangruppen modifizierte pyrogene Kieselsäure mit einer BET-Oberfläche von 225 m2/g, bestimmt nach DIN 66131 , Primärpartikeldurchmesser: 10 nm (Medianwert, Zahlenmittel)Solid (A.1): fumed silica modified with dimethylsiloxane groups with a BET surface area of 225 m 2 / g, determined to DIN 66131, primary particle diameter: 10 nm (median value, number average)
Hydrophobes Polymer (B.1 ): wässrige Dispersion (30 Gew.-% Feststoffgehalt) eines statistischen Copolymeren aus 10 Gew.-% Methacrylsäure und 90 Gew.-% mit Mn 2900 g/mol (Gelpermeationschroma- tographie)Hydrophobic polymer (B.1): aqueous dispersion (30% by weight solids content) of a random copolymer of 10% by weight of methacrylic acid and 90% by weight with M n 2900 g / mol (gel permeation chromatography)
Kondensationsprodukt (C.1 ): Verbindung 1.1 (DMDHEU) Condensation product (C.1): Compound 1.1 (DMDHEU)
Kondensationsprodukt (C.2): Verbindung 1.2Condensation product (C.2): compound 1.2
(D.1 ): ^CI2H25-N(CH2CH2-O-CH2CH2-OH)2 (D.1): CI 2 H 25 -N (CH 2 CH 2 -O-CH 2 CH 2 -OH) 2
(D.2): iso-CioH2i(OCH2CH2)5OH(D.2): iso-CioH 2 i (OCH 2 CH 2 ) 5 OH
(E.1): 45 Gew.-% wässrige Dispersion von teilverseiftem Polyvinylacetat, T9: 33°C,(E.1): 45% by weight aqueous dispersion of partially hydrolyzed polyvinyl acetate, T 9 : 33 ° C.,
(E.2) 60 Gew.-% Lösung von trimerem Hexamethylendiisocyanat in Propylenglykol (30(E.2) 60% by weight solution of trimeric hexamethylene diisocyanate in propylene glycol (30
Gew.-%) und n-Ci8H37(0CH2CH2)i50H (10 Gew.-%)% By weight) and n-Ci 8 H 3 7 (OCH 2 CH 2 ) i 5 0H (10% by weight)
(E.3): Polyacrylamid(E.3): polyacrylamide
HOAc: 60 Gew.-% wässrige EssigsäureHOAc: 60% by weight aqueous acetic acid
Butylglyk.: Ethylenglykol-n-butylether (Butylglykol)Butylglycol .: ethylene glycol n-butyl ether (butylglycol)
Allgemeine Vorgehensweise:General procedure:
Man vermischte die Komponenten gemäß Tabelle 1 , füllte mit Wasser auf einen Liter auf und erhielt die erfindungsgemäßen wässrigen Flotten WF.1 bis WF.8, die zur Behandlung von textilen Substraten eingesetzt wurden.The components according to Table 1 were mixed, and the mixture was made up to one liter with water to obtain the aqueous liquors WF.1 to WF.8 according to the invention, which were used for the treatment of textile substrates.
Tabelle 1 : Zusammensetzung von erfindungsgemäßen wässrigen FlottenTable 1: Composition of aqueous liquors according to the invention
Allgemeine Vorgehensweise für die erfindungsgemäße Behandlung von Textil am Beispiel von Polyestergewebe: General procedure for the treatment according to the invention of textile using the example of polyester fabric:
Ein Polyestergewebe mit einem Flächengewicht von 220 g/m2 wurde mit einer erfindungsgemäßen wässrigen Flotte gemäß Tabellen 1 und 2 auf einem Foulard (Hersteller Fa. Mathis, Typ Nr. HVF12085) behandelt. Der Anpressdruck der Walzen betrug 2,1 bar. Es resultierte eine Flottenaufnahme von 40%. Die Auftraggeschwindigkeit betrug 2 m/min. Anschließend wurde das behandelte Polyestergewebe eine Minute lang bei 1200C auf einem Spannrahmen getrocknet. Die abschließende thermische Behandlung erfolgte über einen Zeitraum von einer Minute bei 185°C unter Umluft. Man erhielt erfindungsgemäße behandelte Polyestergewebe PES.1 bis PES.8.A polyester fabric having a weight per unit area of 220 g / m 2 was treated with an aqueous liquor according to the invention according to Tables 1 and 2 on a padder (manufacturer Fa. Mathis, type no. HVF12085). The contact pressure of the rolls was 2.1 bar. This resulted in a fleet intake of 40%. The application speed was 2 m / min. Subsequently, the treated polyester fabric was dried for one minute at 120 0 C on a tenter. The final thermal treatment was carried out over a period of one minute at 185 ° C under circulating air. Treated polyester fabrics PES.1 to PES.8 according to the invention were obtained.
Die anwendungstechnischen Eigenschaften gehen aus Tabelle 2 hervor.The performance properties are shown in Table 2.
Tabelle 2: Anwendungstechnische Eigenschaften von erfindungsgemäß behandeltem TextilTable 2: Performance properties of textile treated according to the invention
Bestimmung des dynamischen Abrollwinkels:Determination of the dynamic roll-off angle:
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 2. Abperleffekt, Aufnahme (Wasseraufnahme) und Durchlass (Wasserdurchlässigkeit) beziehen sich jeweils auf Wasser. Die Wasseraufnahme wurde nach Bundesmann, DIN 53888, geprüft.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 2. Beading effect, absorption (water absorption) and passage (water permeability) refer to water. The water absorption was tested according to Bundesmann, DIN 53888.
Die Wassersäule wurde nach DIN EN 2081 1 bestimmt.The water column was determined according to DIN EN 2081 1.
Zur Durchführung des Honigtests wurde jeweils ein frischer Waldblütenhonig aus einer Höhe von 5 cm mit einer Pipette auf erfindungsgemäßes Textil getropft, das in einem Winkel von 20° eingespannt war. Der Honig verhielt sich, wie aus der Tabelle ersicht- lieh. Dabei bedeuten:To carry out the honey test, a fresh forest honey from a height of 5 cm was dropped with a pipette onto textile according to the invention, which was clamped at an angle of 20 °. The honey behaved as shown in the table. Where:
++ läuft in runden Tropfen ab ohne Rückstand, + läuft ab, bildet kleine Nase beim Laufen 0 läuft ab, bildet sichtbare Nase beim Laufen benetzt ++ runs off in round drops without residue, + runs off, forms small nose while running 0 runs off, makes visible nose wetted when running

Claims

Patentansprüche claims
1. Verfahren zur Herstellung eines beschichteten Textils, dadurch gekennzeichnet, dass man ein textiles Substrat ohne vorheriges Aufbringen eines Primers behan- delt mit einer wässrigen Flotte, enthaltend1. A process for producing a coated textile, which comprises treating a textile substrate without prior application of a primer with an aqueous liquor containing
(A) mindestens einen Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser im Bereich von 1 bis 500 nm,(A) at least one solid in particulate form having a mean particle diameter in the range of 1 to 500 nm,
(B) mindestens ein hydrophobes Polymer,(B) at least one hydrophobic polymer,
(C) mindestens ein Kondensationsprodukt von mindestens einer Aminogruppen- haltigen Verbindung und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol.(C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass es sich bei Kondensationsprodukt (C) um ein Kondensationsprodukt von Harnstoff und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol handelt.2. The method according to claim 1, characterized in that it is condensation product (C) is a condensation product of urea and at least one aldehyde or dialdehyde and optionally at least one alcohol.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei hydrophoben Polymer (B) um ein fluoriertes (Co)olymer handelt.3. The method according to claim 1 or 2, characterized in that it is hydrophobic polymer (B) is a fluorinated (co) polymer.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass man nach der Behandlung mit wässriger Flotte thermisch behandelt.4. The method according to any one of claims 1 to 3, characterized in that it is treated thermally after treatment with aqueous liquor.
5. Verfahren nach einem der Ansprühe 1 bis 4, dadurch gekennzeichnet, dass es sich bei Kondensationsprodukt (C) um eine Verbindung der allgemeinen Formel5. The method according to any one of claims 1 to 4, characterized in that it is condensation product (C) to a compound of the general formula
handelt, wobei die Variablen wie folgt definiert sind: R1 jeweils verschieden oder gleich und gewählt aus Wasserstoff, Ci-Cβ-Alkyl,wherein the variables are defined as follows: R 1 in each case different or the same and selected from hydrogen, C 1 -C 6 -alkyl,
(CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3, (CH2-CH2-CH2-CH2-CVR3 und (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist, R2 jeweils verschieden oder gleich und gewählt aus Wasserstoff, Ci-Cβ-Alkyl, (CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3,(CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -CH 2 -CVR 3 and (CH 2 CH 2 O) m R 3 , where m is an integer ranging from 1 to 50, each R 2 is different or the same and selected from hydrogen, C 1 -C 8 Alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 ,
(CH2-CH2-CH2-CH2-CVR3 und (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist, R3 gewählt wird aus Wasserstoff und Ci-C2o-Alkyl. (CH 2 -CH 2 -CH 2 -CH 2 -CVR 3 and (CH 2 CH 2 O) m R 3 , wherein m is an integer in the range of 1 to 50, R 3 is selected from hydrogen and Ci-C 2- O-alkyl.
6. Textil, behandelt nach einem Verfahren nach einem der Ansprüche 1 bis 5.6. textile, treated by a method according to any one of claims 1 to 5.
7. Verwendung von Textil nach Anspruch 6 als oder zur Herstellung von Markisen- Stoffen, Verdecken oder Planen.7. Use of textile according to claim 6 as or for the production of awning fabrics, covering or tarpaulins.
8. Markisenstoffe, Verdecke oder Planen, hergestellt unter Verwendung von Textil nach Anspruch 6.8. Awning fabrics, coverings or tarpaulins made using textile according to claim 6.
9. Wässrige Flotte, enthaltend9. Aqueous liquor containing
(A) mindestens einen Feststoff in partikulärer Form mit einem mittleren Partikeldurchmesser im Bereich von 1 bis 500 nm,(A) at least one solid in particulate form having a mean particle diameter in the range of 1 to 500 nm,
(B) mindestens ein hydrophobes Polymer,(B) at least one hydrophobic polymer,
(C) mindestens einem Kondensationsprodukt von mindestens einer Aminogrup- penhaltigen Verbindung und mindestens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem Alkohol.(C) at least one condensation product of at least one amino-containing compound and at least one aldehyde or dialdehyde and optionally at least one alcohol.
10. Wässrige Flotte nach Anspruch 9, dadurch gekennzeichnet, dass es sich bei Kondensationsprodukt (C) um ein Kondensationsprodukt von Harnstoff und min- destens einem Aldehyd oder Dialdehyd und gegebenenfalls mindestens einem10. Aqueous liquor according to claim 9, characterized in that the condensation product (C) is a condensation product of urea and at least one aldehyde or dialdehyde and optionally at least one
Alkohol handelt.Alcohol acts.
1 1. Wässrige Flotte nach Anspruch 9 oder 10, dadurch gekennzeichnet, dass es sich bei hydrophobem Polymer (B) um ein fluoriertes (Co)polymer handelt.1 1. Aqueous liquor according to claim 9 or 10, characterized in that it is hydrophobic polymer (B) is a fluorinated (co) polymer.
12. Wässrige Flotte nach einem der Ansprüche 9 bis 11 , dadurch gekennzeichnet, dass es sich bei Kondensationsprodukt (C) um einer Verbindung der allgemeinen Formel I12. Aqueous liquor according to one of claims 9 to 11, characterized in that it is condensation product (C) to a compound of general formula I.
handelt, wobei die Variablen wie folgt definiert sind:where the variables are defined as follows:
R1 jeweils verschieden oder gleich und gewählt aus Wasserstoff, Ci-Cβ-Alkyl, (CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3, (CH2-CH2-CH2-CH2-CVR3 und (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist,Each R 1 is the same or different and selected from hydrogen, C 1 -C 6 -alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -CH 2 -CVR 3 and (CH 2 CH 2 O) m R 3 , where m is an integer in the range of 1 to 50 is
R2 jeweils verschieden oder gleich und gewählt aus Wasserstoff, Ci-Cβ-Alkyl, (CHCH3-CH2-O)m-R3, (CH2-CHCH3-O)m-R3, (CH2-CH2-CH2-O)m-R3, (CH2-CH2-CH2-CI-l2-O)m-R3, und (CH2CH2O)mR3, wobei m eine ganze Zahl im Bereich von 1 bis 50 ist, (A) R3 gewählt wird aus Wasserstoff und Ci-C2o-Alkyl. Each R 2 is the same or different and selected from hydrogen, C 1 -C 6 -alkyl, (CHCH 3 -CH 2 -O) m -R 3 , (CH 2 -CHCH 3 -O) m -R 3 , (CH 2 -CH 2 -CH 2 -O) m -R 3 , (CH2-CH2-CH2-CI-l2-O) m R 3, and (CH 2 CH 2 O) m R 3, wherein m is an integer ranging from 1 to 50, (A) R 3 is selected from hydrogen and Ci-C2o-alkyl.
EP08707879A 2007-01-19 2008-01-14 Method for the production of a coated textile Withdrawn EP2122042A1 (en)

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EP07100838A EP1947233A1 (en) 2007-01-19 2007-01-19 Method for producing a coated textile
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US2732370A (en) * 1956-01-24 Polymers
US2642416A (en) * 1950-05-26 1953-06-16 Minnesota Mining & Mfg Fluorinated acrylates and polymers
US2592069A (en) * 1951-03-05 1952-04-08 Minnesota Mining & Mfg Fluorocarbon vinyl esters and polymers
US3239557A (en) * 1962-01-18 1966-03-08 Du Pont Process for converting halides to esters
US3462296A (en) * 1966-07-22 1969-08-19 Du Pont Fluorinated oil- and water-repellent copolymer and process for treating fibrous materials with said copolymer
DE102004025368A1 (en) * 2004-05-19 2005-12-08 Basf Ag Process for producing structured surfaces
US20070197111A1 (en) * 2004-05-19 2007-08-23 Basf Aktiengesellschaft Method for finishing absorbent materials
DE102004038218A1 (en) * 2004-08-05 2006-03-16 Basf Ag Process for finishing absorbent materials

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