EP1929084A2 - Procede de traitement de surfaces - Google Patents

Procede de traitement de surfaces

Info

Publication number
EP1929084A2
EP1929084A2 EP06793413A EP06793413A EP1929084A2 EP 1929084 A2 EP1929084 A2 EP 1929084A2 EP 06793413 A EP06793413 A EP 06793413A EP 06793413 A EP06793413 A EP 06793413A EP 1929084 A2 EP1929084 A2 EP 1929084A2
Authority
EP
European Patent Office
Prior art keywords
groups
copolymer
mixture
particulate form
water
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Withdrawn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
EP06793413A
Other languages
German (de)
English (en)
Inventor
Oihana Elizalde
Michael Schmitt
Marc Bothe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1929084A2 publication Critical patent/EP1929084A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/55—Epoxy 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/347—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated ethers, acetals, hemiacetals, ketones or aldehydes
    • 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
    • D06M15/70—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D06M15/71—Cooling; Steaming or heating, e.g. in fluidised beds; with molten metals
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/02—Moisture-responsive characteristics
    • D10B2401/021—Moisture-responsive characteristics hydrophobic

Definitions

  • the present invention relates to a method for the treatment of surfaces, characterized in that the surface is treated with
  • the present invention relates to treated surfaces. Furthermore, the present invention preferably relates to aqueous formulations and to a process for the preparation of preferably aqueous formulations according to the invention.
  • WO 04/74568 discloses a process for finishing textile materials by treatment with at least one aqueous liquor which contains at least one organic polymer and at least one organic or inorganic solid in particulate form, the organic or inorganic solid (s) in the liquor is present in a proportion of at least 5.5 g / l.
  • silica gel in particular pyrogenic silica gel is preferably recommended.
  • potato starch as recommended in EP 1 283 296, is soluble in aqueous liquors depending on the temperature to a certain extent, so that the diameter of the potato starch particles can not be optimally adjusted during a coating.
  • inorganic solids such as, for example, silica
  • the tendency for agglomeration is determined to a certain extent, which on the one hand is disadvantageous during use, on the other hand makes it difficult to control the structural parameters.
  • the inventive method is based on surfaces.
  • Surfaces in the sense of the present invention may consist of any materials and belong to arbitrary objects.
  • surfaces of fibrous materials such as paper, paperboard, leather, imitation leather, Alcantara, and in particular surfaces are surfaces of textiles.
  • textiles are to be understood as meaning textile fibers, textile semi-finished and finished products and finished goods produced therefrom which, in addition to textiles for the clothing industry, also include, for example, carpets and other home textiles as well as textile structures serving technical purposes.
  • This also includes unshaped structures such as flakes, linear structures such as twines, threads, yarns, lines, cords, ropes, threads and body structures such as felts, fabrics, nonwovens and wadding.
  • Textiles in the context of the present invention can be of natural origin, for example cotton, wool or flax, or synthetic, for example polyamide, polyester, modified polyester, polyester blends, polyamide blends, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester microfibers and fiberglass fabrics , Particularly preferred are textiles made of cotton.
  • one surface (side) may be treated by the process according to the invention and the other not, or both surfaces (sides) may be treated by the process according to the invention.
  • Workwear be useful to treat the outer surface by the method according to the invention and the inside (body side) not; and on the other hand it may be useful to treat both sides (top and bottom) of some technical textiles such as awnings by the method according to the invention.
  • water repellents selected from (a1) halogen-containing organic (co) polymers, (a2) paraffins and (a3) compounds having at least one Cio-C ⁇ o-alkyl group per molecule.
  • Suitable halogen-containing organic (co) polymers (a1) are, for example, chlorinated and in particular fluorinated (co) polymers which are prepared by free-radical (co) polymerization of one or more mono- or polyhalogenated, preferably chlorinated and particularly preferably fluorinated (co) monomers can be.
  • halogenated (co) monomers are fluorine-containing olefins such as, for example, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, hexafluoropropylene, vinyl esters of fluorinated or perfluorinated C 3 -C 20 -carboxylic acids, as described, for example, in US Pat. Nos.
  • (meth) acrylic esters of fluorinated or perfluorinated alcohols such as fluorinated or perfluorinated C3-Ci4-alkyl alcohols, such as (meth) acrylatklaeester of HO-CH 2 -CH 2 -CF 3, HO-CH 2 -CH 2 -C 2 F 5, HO-CH 2 -CH 2 -NC 3 F 7 , HO-CH 2 -CH 2 -iso-C 3 F 7 , HO-CH 2 -CH 2 -nC 4 F 9 , HO-CH 2 -CH 2 -n-C 6 Fi 3 , HO -CH 2 -CH 2 -nC 8 Fi7, HO-CH 2 -CH 2 -OnC 6 Fi 3 , HO-CH 2 -CH 2 -OnC 8 Fi 7 , HO-CH 2 -CH 2 -nC 10 F 21 , HO-CH 2 -CH 2 -CH 2 -CF 3
  • copolymers of, for example, copolymers of, for example, (meth) acrylic acid and / or dC 2 o-alkyl esters of (meth) acrylic acid or glycidyl (meth) acrylate with esters of the formula I are also copolymers of, for example, copolymers of, for example, (meth) acrylic acid and / or dC 2 o-alkyl esters of (meth) acrylic acid or glycidyl (meth) acrylate with esters of the formula I.
  • R 1 is hydrogen, CH 3 , C 2 H 5 , R 2 CH 3 , C 2 H 5 , x is an integer in the range of 4 to 12, preferably 6 to 8, y is an integer Number in the range of 1 to 11, preferably 1 to 6,
  • halo-containing organic (co) polymers (a).
  • More than halogen-containing organic (co) polymers (a) include copolymers of (meth) acrylklaestern fluorinated, in particular perfluorinated 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 -n-C 6 F 13 , HO-CH 2 -CH 2 -nC 8 F 17 , HO-CH 2 -CH 2 -OnC 6 F 13 , HO-CH 2 -CH 2 -OnC 8 F 17 , HO-CH 2 -CH 2 -nC 10 F 21 , HO-CH 2 -CH 2 -nC 12 F 25 , with
  • fluorinated polymers and copolymers useful as halogen-containing organic (co) polymers (a1) 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.
  • fluorinated (co) polymers which are suitable as halogen-containing organic (co) polymers (a1) are described, for example, in DE 199 120 810.
  • a halogen-containing (co) polymer (a1) or several different halogen-containing (co) polymers (a1) can be used to carry out the process according to the invention.
  • Halogen-containing (co) polymer (a1) is used to carry out the process according to the invention in preferably uncrosslinked form, but it can crosslink during drying.
  • paraffins (a2) may, for example, be liquid or solid at room temperature and be of natural or preferably synthetic origin.
  • Preferred paraffins (a2) are synthetic paraffins such as, for example, Fischer-Tropsch waxes, low-pressure polyethylene waxes, for example produced with the aid of Ziegler-Natta catalysts or metallocene catalysts, furthermore partially oxidized low-pressure polyethylene waxes having an acid number in the range from 1 to 150 mg KOH / g paraffin, determined according to DIN 53402, whereby low-pressure polyethylene waxes not only homopolymer waxes of ethylene, but also copolymers of polyethylene with a total of up to 20 wt .-% comonomer such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-dodecene and in particular so-called paraffin waxes and isoparaffin
  • paraffin waxes in the context of the present invention solid, in particular at room temperature, in the range of 40 to 80 0 C, preferably 50 to 75 ° C melting paraffins understood, ie saturated hydrocarbons, branched or unbranched, cyclic or preferably acyc- lisch, individually or preferably as a mixture of several saturated hydrocarbons.
  • Paraffin waxes in the context of the present invention are preferably composed of saturated hydrocarbons having 18 to 45 carbon atoms
  • isoparaffins in the context of the present invention are preferably composed of saturated hydrocarbons having 20 to 60 carbon atoms per molecule.
  • hydrophobizing agents (a) are linear or heterocyclic, preferably heteroaromatic, compounds having at least one C 10 -C 30 -alkyl group, preferably having one C 12 -C 40 -alkyl group per molecule (a3), hereinafter also referred to briefly as compound (a3), where Cio-C6o-alkyl group (s) may be different or preferably the same and branched or preferably unbranched. Trains t forthcoming such compounds (a3), which when heated to temperatures in the range of 120 to 200 0 C, at least one fatty amine or a fatty alcohol may cleave at least, so an amine or an alcohol having a Cio-C ⁇ o-alkyl group. Very particular preference is given to compounds of the general formula II
  • R 3 is selected from C 1 -C 6 -alkyl, branched or preferably unbranched, for example n-CioH 2i, n-C 12 H 25, n-C 16 H 29, n-C 16 H 33, n-CisH 3 7, n-C 20 H 4i, n-CaoH ⁇ i, n-C 40 H 8i, n-C ⁇ oHioi, n-C6oHi2i, and R 9 -OCH2, wherein R 9 is selected Cio-C ⁇ o-alkyl, branched or preferably unbranched, for example n-CioH 2 i, n-Ci2H 2 5, n-Ci4H 2 9, n -Ci6H 3 3, n-3 Ci8H 7, n-C2oH4i, n-C3oH6i, n-C4oHsi, nC 5 oHioi, ,
  • carbon numbers and corresponding hydrogen numbers are to
  • R 4 to R 8 are different or preferably identical and selected from hydrogen, R 3 , CH 2 -OH, CH 2 -O-Ci-Ci 0 -AlkVl, in particular CH 2 -OCH 3 , CH 2 -OC 2 H 5 , CH 2 -OnC 4 H 9 , CH 2 -OCH 2 CH 2 OH, CH 2 -OCH 2 CH 2 0-Ci-Cio-alkyl, in particular CH 2 -OCH 2 CH 2 OCH 3 , CH 2 -OCH 2 CH 2 OC 2 H 5 , CH 2 -OCH 2 CH 2 OnC 4 H 9 , CH 2 - (OCH 2 CH 2 ) 2 OH, CH 2 - (OCH 2 CH 2 ) 2 0-Ci-Cio-Alkyl, in particular CH 2 - (OCH 2 CH 2 ) 2 OCH 3 , CH 2 - (OCH 2 CH 2 ) 2 OC 2 H 5 , and CH 2 - (OCH 2 CH
  • the hydrophobizing agent (a) used is a combination of at least one paraffin (a2) and at least one compound (a3).
  • Suitable crosslinked organic copolymers in particulate form (b) are halogen-containing and preferably halogen-free copolymers which are prepared by free-radical copolymerization. tion of at least one monoethylenically unsaturated comonomer and at least one at least twice ethylenically unsaturated comonomer (crosslinker) can be obtained and which are present in particulate form.
  • suitable monoethylenically unsaturated comonomers are, for example, mono-vinylaromatics, for example ⁇ -methylstyrene and in particular styrene, and C 1 -C 10 -alkyl esters of ethylenically unsaturated carboxylic acids, for example acrylic acid or methacrylic acid, in particular are methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, ethylhexyl acrylate, n-butyl methacrylate, t-butyl methacrylate and methyl methacrylate called.
  • acrylonitrile is suitable.
  • Suitable crosslinkers are, for example, di- and trivinylaromatics, for example ortho-divinylbenzene, meta-divinylbenzene and para-divinylbenzene, furthermore ethylenically unsaturated carboxylic acids esterified with ethylenically unsaturated alcohol, for example allyl (meth) acrylate, (meth) acrylates of two or trihydric alcohols, for example ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, diethylene glycol di (meth) acrylate), 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 1,1,1-trimethylolpropane di (meth) acrylate, 1,1,1-trimethylolpropane tri (meth) acrylate.
  • di- and trivinylaromatics for
  • crosslinked organic copolymers in particulate form (b) for example, up to 20 mol%, preferably 1 to 10 mol% and particularly preferably at least 3 mol% of crosslinker with at least 80 mol%, preferably at least least 90 mol% and particularly preferably up to 97 mol% of one or more of the abovementioned monoethylenically unsaturated comonomers.
  • the copolymer can be reduced by suitable methods of particle formation after the actual synthesis, for example by grinding. It is also possible to carry out the synthesis in such a way that copolymer of monoethylenically unsaturated comonomer or monounsaturated comonomer and crosslinker is obtained in particulate form, for example by carrying out the synthesis in the form of emulsion polymerization, also as polymerization in miniemulsion, or as suspension polymerization.
  • particulate form is understood to mean that crosslinked copolymer (b) is in the form of particles which are not dissolved in water or aqueous medium.
  • the particles may have an irregular shape or preferably have a regular shape, for example ellipsoidal or spherical shape, whereby it is intended to include those particles of which at least
  • crosslinked organic copolymer in particulate form (b) is present neither in the form of aggregates nor in the form of agglomerates.
  • cross-linked organic copolymer in particulate form (b) has a weight average molecular weight in the range of 10 to 450 nm, preferably in the range of 20 to 250 nm, more preferably 50 to 100 nm Particle diameter can be used common methods such as transmission electron microscopy.
  • crosslinked organic copolymer in particulate form (b) has a homogeneous particle size distribution, i. at least 80% by weight of the particles have a diameter in the range of ⁇ 20% of the mean diameter.
  • crosslinked organic copolymer in particulate form (b) has a bimodal or multimodal particle size distribution.
  • crosslinked organic copolymer in particulate form (b) a certain temperature dimensional stability, that is, at 30 to 200 0 C, preferably 120 to 180 0 C, particularly preferably 150 to 170 ° C mounted crosslinked organic copolymer in Particulate form (b) changes its shape not measurable over a period of 1 second to 30 minutes, preferably up to 3 minutes.
  • Copolymers of one or more monoethylenically unsaturated comonomers such as, for example, monovinylaromatics, monoethylenically unsaturated carboxylic acids, C 1 -C 10 -alkyl esters of monoethylenically unsaturated carboxylic acids are simple as film-forming copolymer with epoxide groups, NH-ChbOH groups or acetoacetyl groups (c) ethylenically unsaturated carboxylic acid amides, polyfunctional derivatives of ethylenically unsaturated carboxylic acids, with one or more comonomers having epoxide groups, NH-ChbOH groups or acetoacetyl groups.
  • monoethylenically unsaturated comonomers such as, for example, monovinylaromatics, monoethylenically unsaturated carboxylic acids, C 1 -C 10 -alkyl esters of monoethyl
  • Particularly suitable monovinyl aromatics are, for example, ⁇ -methylstyrene, para-methylstyrene, 2,4-dimethylstyrene and in particular styrene.
  • Particularly suitable monoethylenically unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, E- and ZC-tonic acid, itaconic acid and in particular acrylic acid and methacrylic acid.
  • Particularly suitable C 1 -C 10 -alkyl esters of monoethylenically unsaturated carboxylic acids are esters of branched or unbranched C 1 -C 10 -alkanol with one of the above-mentioned monoethylenically unsaturated carboxylic acids.
  • Examples include: methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, 2-Ethylehexyl methacrylate.
  • Particularly suitable monoethylenically unsaturated carboxylic acid amides are N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide and in particular acrylamide and methacrylamide.
  • Particularly suitable polyfunctional derivatives of ethylenically unsaturated carboxylic acids are compounds of the general formula IV
  • X 1 , X 2 are identical or different and selected from oxygen, NH and NR 11 ,
  • A is a spacer, for example branched or unbranched C 2 -C 2 o-alkylene or phenylene.
  • Examples of C 2 -C 2 o-alkyls are - (CH 2 ) 2 -, -CH 2 -CH (CH 3 ) -, - (CH 2 ) 3 -, -CH 2 -CH (C 2 H 5 ) - , - (CHz) 4 -, - (CH 2) S-, - (CHz) 6 -, - (CHz) 7 -, - (CHz) 8 -, - (CHZ) 9 -, - (CHz) io- ; preferably C 2 -C 4 -alkylene; in particular - (CH 2 ) 2 -, -CH 2 -CH (CH 3 ) -, - (CH 2 ) 3
  • R 10 , R 11 are identical or different and selected from C 1 -C 10 -alkyl, for example 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, n-heptyl, n-octyl, 2- Ethylhexyl, n-nonyl, n-decyl, more preferably unbranched C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl and n-butyl.
  • C 1 -C 10 -alkyl for example methyl, e
  • Particularly suitable comonomers with epoxide groups are, for example, glycidyl esters of maleic acid, fumaric acid, E- and Z-crotonic acid and in particular of acrylic acid and of methacrylic acid.
  • Particularly suitable comonomers with NH-CH 2 OH groups are, for example, reaction products of formaldehyde with monoethylenically unsaturated carboxylic acid amides, in particular acrylic acid N-methylolamide and methacrylic acid-N-methylolamide.
  • Particularly suitable comonomers with acetoacetyl groups are, for example, (meth) acrylates of alcohols of the general formula V
  • R 12 is selected from straight-chain or branched C 1 -C 10 -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, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl , n-decyl, particularly preferably unbranched C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl and n-butyl.
  • C 1 -C 10 -alkyl such as methyl,
  • Film-forming copolymers having epoxide groups, NH-ChbOH groups or acetoacetyl groups (c) can be prepared by methods known per se, for example by emulsion polymerization with one or more free-radical initiators in the presence of one or more emulsifiers.
  • film-forming copolymers having epoxide groups, NH-ChbOH groups or acetoacetyl groups (c) by emulsion polymerization in seed-driving mode, that is to say initially adding one or more water-insoluble polymers, for example polystyrene, in very small particles, for example, with an average diameter of 15 to 30 nm, which then promote the formation of droplets during the copolymerization.
  • the polymers added at the beginning of the copolymerization in very small particles are not to be confused with crosslinked organic copolymer in particulate form (b).
  • film-forming copolymer having epoxy groups, NH-ChbOH groups or acetoacetyl groups (c) at room temperature has a viscosity in the range of 10 to 200 mPa ⁇ s as determined, for example, by Brookfield.
  • a glass transition temperature T 9 in the range of -50 to +30 0 C, preferably from -20 to +30 0 C.
  • film-forming copolymer having epoxide groups, NH-ChbOH groups or acetoacetyl groups has 0.1 to
  • emulsifiers (d) are anionic, cationic and nonionic surface-active compounds.
  • Suitable nonionic surface-active compounds are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C4 to C12) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80, alkyl radical: Cs to C36).
  • ethoxylated mono-, di- and tri-alkylphenols degree of ethoxylation: from 3 to 50, alkyl radical: C4 to C12
  • ethoxylated fatty alcohols degree of ethoxylation: from 3 to 80, alkyl radical: Cs to C36
  • Lutensol ® brands from BASF Aktiengesellschaft
  • Triton ® - grades from Union Carbide.
  • Further suitable nonionic surface-active compounds are those of the general formula VI
  • R 13 selected for example, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, iso-decyl, n-undecyl, n-dodecyl, iso-
  • C3-C4o alkenyl having one to five CC double bonds wherein the CC double bonds may be, for example, isolated or conjugated.
  • R 14 is the same or different and selected from hydrogen and methyl, preferably
  • n are the same or different and selected from integers in the range of 0 to 20, preferably 2 to 12.
  • Suitable anionic surface-active compounds are, for example alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C to C 2), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl: C 2 to C) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl: C4 to C 2), of alkylsulfonic acids (alkyl: C 2 -Cis) and of alkylarylsulfonic acids (alkyl radical: Cg to Ci ⁇ ).
  • alkyl sulfates alkyl radical: C to C 2 2
  • sulfuric monoesters of ethoxylated alkanols degree of ethoxylation: from 4 to 30, alkyl: C 2 to C
  • ethoxylated alkylphenols degree of ethoxylation: 3 to 50, alkyl: C4 to C 2
  • Suitable anionic surfactants are alkali metal and ammonium salts of sulfited succinic C5-C4o-alkyl half esters.
  • Suitable cationic surface-active compounds are generally primary, secondary, tertiary or quaternary ammonium salts containing C ⁇ -C 1-6 alkyl, aralkyl or heterocyclic, alkanolammonium salts, pyridinium salts, imidazoline salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of Amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
  • Examples which may be mentioned are dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffins, N-cetylpyridinium chloride, N-laurylpyridinium sulfate, N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini-surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide.
  • the process according to the invention can be carried out, for example, by treating the surface to be treated with at least one preferably aqueous formulation which
  • Aqueous formulations may be any aqueous suspensions, preference being given to aqueous liquors.
  • Aqueous formulations and in particular aqueous liquors may have a solids content in the range of 10 to 70 wt .-%, preferably 30 to 50 wt .-%.
  • the process according to the invention is carried out by first treating the surface to be treated with a preferably aqueous formulation containing at least one hydrophobizing agent (a) and furthermore a crosslinked organic copolymer in particulate form (b) and subsequently followed by a further treatment with a new liquor containing at least one film-forming copolymer with epoxide groups, NH-ChbOH groups or acetoacetyl groups (c), but no crosslinked organic copolymer in particulate form (b).
  • the process according to the invention is carried out by first treating the surface to be treated with a preferably aqueous formulation containing at least one hydrophobizing agent (a) and furthermore at least one crosslinked organic copolymer in particulate form (b) , followed by further treatment with a novel, preferably aqueous formulation containing another hydrophobizing agent (a) and a film-forming copolymer having epoxy groups, NH-CH 2 HH groups or acetoacetyl groups (c), but no crosslinked organic copolymer in particulate form (b).
  • the process according to the invention is carried out by first treating the surface to be treated with a preferably aqueous formulation which comprises at least one film-forming copolymer having epoxide groups, NH-CH 2 ⁇ H groups or acetoacetyl groups (c) and furthermore at least one crosslinked organic copolymer in particulate form (b), and then followed by a further treatment with a new, preferably aqueous formulation containing a hydrophobizing agent (a).
  • the process according to the invention is carried out by first treating the surface to be treated with a preferably aqueous liquor containing at least one hydrophobizing agent (a), at least one cross-linked organic copolymer in particulate form (b) and a film-forming copolymer having epoxide groups, NH-CH 2 ⁇ H groups or acetoacetyl groups (c), and then followed by a further treatment with a new liquor which contains neither hydrophobizing agent (a) nor film-forming copolymer having epoxide groups, NH-CH 2 ⁇ H groups or acetoacetyl groups ( c), but contains the already used in the first step crosslinked organic copolymer in particulate form (b).
  • the temperature for carrying out the treatment according to the invention is not critical per se.
  • the temperature may be in the range of 10 to 60 ° C., preferably 15 to 30 ° C.
  • aqueous formulation and especially preferably aqueous liquor may have a pH in the range of 2 to 9, preferably 3.5 to 7.5.
  • the liquor pickup can be selected such that a liquor pickup of 25% by weight to 95% by weight is preferred by the process according to the invention 60 to 90 wt .-% results.
  • the method according to the invention is carried out in conventional machines used for finishing textiles, for example foulards.
  • foulards with vertical textile teineinyak, containing as an essential element two superimposed rollers through which the textile is guided.
  • aqueous formulation is preferably filled in and wets the textile. The pressure squeezes the textile and ensures a constant application.
  • foulards textile is first passed through a dip and then up through two pressed rollers. In the latter case one speaks also of foulards with vertical Textileinzug from below. Foulards are described, for example, in Hans-Karl Rouette, "Handbuch der Textilveredlung", Deutscher fraverlag 2003, p. 618-620.
  • the surface to be treated is contacted with an aqueous formulation containing (a) at least one hydrophobizing agent, (b) at least one crosslinked organic copolymer in particulate form,
  • Contacting according to the invention can be effected, for example, by single or multiple spraying, sprinkling, pouring over or printing.
  • Aqueous formulations according to the present invention may contain one or more organic solvents, for example alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, acetic acid, n-butanol, iso-butanol, n-hexanol and isomers, n-octanol and isomers, n-dodecanol and isomers.
  • alcohols such as methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso
  • Organic solvents may constitute from 1 to 40% by weight, preferably from 2 to 25% by weight, of the continuous phase of aqueous formulation used according to the invention.
  • aqueous formulations are meant those formulations in which the continuous phase consists predominantly or in extreme cases exclusively of water.
  • an optionally heated gas stream in particular with an optionally heated inert gas stream, for example nitrogen. If it is desired to use a heated gas stream, for example, temperatures in the range from 30 to 200 ° C., preferably from 120 to 180 ° C., particularly preferably from 150 to 170 ° C., are suitable.
  • tempering in the context of the present invention, continuously or discontinuously.
  • the duration of tempering can be chosen within wide limits. Usually, you can over the duration of about 1 second to 30 minutes, in particular tempered to 3 minutes.
  • a heat treatment by heating to temperatures up to 180 0 C, preferably 150 to 170 0 C. It is of course necessary to adjust the temperature of annealing to the sensitivity of the material from which the inventively treated surface.
  • a special suitable method for tempering for example, a hot air drying.
  • surfaces are treated with a preferably aqueous formulation comprising (a) from 0.1 to 20% by weight, preferably from 1 to 15% by weight of hydrophobing agent, (b) from 1 to 25% by weight , preferably 5 to 15% by weight of crosslinked organic copolymer in particulate form,
  • statements in wt .-% are each based on total preferably aqueous formulation.
  • an aqueous formulation used to carry out the process according to the invention contains one or more auxiliary substances (e), for example up to 50% by weight, based on total amounts of preferably aqueous formulation.
  • auxiliary substances e
  • adjuvants (e) are selected from biocides, thickeners, foam inhibitors, wetting agents Plasticizers, handle modifiers, fillers, crosslinkers (hardeners), and film-forming aids.
  • a biocide suitable as excipient (s) is, for example, 1,2-benzisothiazolin-3-one ("BIT”) (commercially available as Proxel® grades from Avecia Lim.) And its alkali metal salts, other suitable biocides being 2-Methyl-2H-isothiazol-3 (“MIT”) and 5-chloro-2-methyl-2H-isothiazol-3-one (“CIT”) Generally, 10 to 150 ppm of biocide is sufficient, based on preferably aqueous Formulation.
  • BIT 1,2-benzisothiazolin-3-one
  • MIT 2-Methyl-2H-isothiazol-3
  • CIT 5-chloro-2-methyl-2H-isothiazol-3-one
  • one or more thickeners may be added, which may be of natural or synthetic origin, for example.
  • Suitable synthetic thickeners are poly (meth) acrylic compounds, polycarboxylic acids, polyethers, polyimines, polyamides 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.
  • M w molecular weights in the range of 100,000 to 200,000 g / mol, in which R 15 is methyl or preferably hydrogen.
  • thickeners of natural origin include: agar-agar, carrageenan, modified starch and modified cellulose.
  • thickener from 0 to 10% by weight, based on the aqueous formulation used in the process according to the invention, of thickener can be used, preferably from 0.05 to 5% by weight and more preferably from 0.1 to 3% by weight.
  • Exemplary of foam inhibitors suitable as auxiliaries (e) are, at room temperature, liquid silicones, not ethoxylated or mono- or polyoxyethylenated.
  • auxiliaries examples include alkyl polyglycosides, alkyl phosphonates, alkylphenyl phosphonates, alkyl phosphates and alkylphenyl phosphates.
  • suitable as auxiliaries (e) plasticizers are ester compounds selected from the groups of alkanols completely esterified aliphatic or aromatic di- or polycarboxylic acids and at least monoesterified with alkanol phosphoric acid.
  • alkanols are d-Cio-alkanols.
  • alkanol completely esterified aromatic di- or polycarboxylic acids are completely esterified with alkanol phthalic acid, isophthalic acid and mellitic acid; Examples thereof include: di-n-octyl phthalate, di-n-nonyl phthalate, di-n-decyl phthalate, di-n-octyl isophthalate, di-n-nonyl isophthalate, di-n-decyl isophthalate.
  • Preferred examples of aliphatic di- or polycarboxylic acids completely esterified with alkanol are, for example, dimethyl adipate, diethyl adipate, diisobutyl adipate, glutaric acid dimethyl ester, diethyl glutarate, di-n-glutarate, diisobutyl glutarate, succinic acid, diethyl succinate, succinic acid.
  • Preferred examples of phosphoric acid which is at least monoesterified with alkanol are C 1 -C 10 -alkyl-di-C 6 -C 14 -aryl phosphates, such as isodecyldiphenyl phosphate.
  • plasticizers are at least one aliphatic or aromatic di- or polyols esterified with C 1 -C 10 -alkylcarboxylic acid.
  • a preferred example of at least one aliphatic or aromatic di- or polyols esterified with C 1 -C 10 -alkylcarboxylic acid is 2,2,4-trimethylpentane-1,3-diol monoisobutyrate.
  • polyesters obtainable by polycondensation of aliphatic dicarboxylic acid and aliphatic diol, for example adipic acid or succinic acid and 1,2-propanediol, preferably with an M w of 200 g / mol, and polypropylene glycol alkylphenyl ether, preferably with an M w of 450 g / mol.
  • plasticizers are polypropylene glycols having a molecular weight M w in the range from 400 to 800 g / mol, etherified with two different alcohols, wherein preferably one of the alcohols may be an alkanol, in particular a C 1 -C 10 -alkanol and the other alcohol is preferably an aromatic alcohol may be, for example, o-cresol, m-cresol, p-cresol and in particular phenol.
  • Fillers suitable as excipient (s) include, for example, melamine and pigments in particulate form.
  • suitable handle improvers are, for example, silicone emulsions to call, i. aqueous emulsions of silicones, which may preferably carry hydrophilic groups such as OH groups or alkoxylate groups.
  • Crosslinking agents (hardeners) suitable as auxiliary (s) are, for example, optionally etherified condensation products of urea, glyoxal and formaldehyde, preferably two to four times etherified with methanol or ethanol with preferably linear ⁇ -C4-alkanol
  • crosslinkers which are suitable as auxiliary (s) 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 -alkylpolyethylene glycol.
  • suitable crosslinkers are known, for example, from EP-A 0 486 881.
  • Suitable as an excipient (e) film former (film-forming agent) is diethylene glycol call.
  • the surface to be coated is provided with at least one primer (f) before the treatment with (a) to (c), optionally emulsifier (d) and optionally excipient (s).
  • primer (f) provides the surface to be treated according to the invention with charge which is opposite to the charge of crosslinked organic copolymer in particulate form (b).
  • a primer (f) which is anionic.
  • Suitable primers (f) may be, for example, polymeric or non-polymeric in nature.
  • suitable polymeric primers may have a number average molecular weight in the range of 5,000 to 500,000 g / mole.
  • cationic primer (f) are, for example, polyethyleneimine and particularly aminosiloxanes such as siloxanes at least one (CH2) W is NH-R have 16 group, in which an integer w is in the range of 1 to 10, in particular 2 to 7 and R 16 is selected from hydrogen, preferably linear C 1 -C 4 alkyl and (CH 2) w NH-R 17 , wherein R 17 is selected from hydrogen and preferably linear C 1 -C 4 alkyl, further polyvinylimidazole.
  • Further suitable cationic primers (f) are polymers of diallyldi-C 1 -C 4 -alkylammonium halide, in which C 1 -C 4 -alkyl is preferably linear.
  • Suitable cationic primers (f) are reaction products of equimolar amounts of preferably cyclic diamines with epichlorohydrin and an alkylating agent such as, for example, dimethyl sulfate, C 1 -C 10 -alkyl halide, in particular methyl iodide, or benzyl halide, in particular benzyl chloride.
  • Such reaction products may have molecular weights M w in the range of 1,000 to 1,000,000 g / mol and are constructed as follows, illustrated by the example of the reaction of equimolar amounts of piperazine with epichlorohydrin and benzyl chloride:
  • Suitable anionic primers (f) are, for example, homo- or copolymers of anionic monomers, in particular of ethylenically unsaturated sulfonic acids, ethylenically unsaturated amine oxides or (meth) acrylic acid, optionally with one or more C 1 -C 10 -alkyl esters of (meth) acrylic acid.
  • Further suitable anionic primers are, for example, anionic polyurethanes, which in connection with the present invention are those polyurethanes which contain at least one sulfonic acid group or carboxylic acid group per molecule, preparable, for example, using 1,1-dimethylolpropionic acid.
  • primers (f) it is preferable to use it in an aqueous formulation and to prepare it before treatment with crosslinked organics.
  • schsch copolymer in particulate form (b) apply.
  • suitable working techniques include spraying, sprinkling and, in particular, padding.
  • a cationic primer (f) is applied to cotton surface, optionally treated thermally and then treated with crosslinked organic copolymer in particulate form (b), emulsifier (c) and hydrophobizing agent (a) and film-forming copolymer Epoxy groups, NH-ChbOH groups or acetoacetyl groups (c). Thereafter, it is treated thermally.
  • an anionic primer (f) is applied to polyester surface, optionally treated thermally and with crosslinked organic copolymer in particulate form (b), emulsifier (c) and water repellent (a) and film-forming copolymer with epoxide groups,
  • a further subject of the present invention are surfaces coated with (f) optionally at least one primer, (a) at least one hydrophobizing agent,
  • Surfaces according to the invention can advantageously be prepared by the process according to the invention described above.
  • Surfaces according to the invention are structured and have a water-repellent effect and show little tendency to become soiled.
  • optionally used emulsifier (d) or emulsifiers (d) are deposited on surfaces according to the invention not or only in traces and thus substantially lack the coated surfaces according to the invention.
  • optionally used adjuvant (s) or auxiliary substances (e) on surfaces according to the invention are not or deposited only in traces and thus substantially lacking the coated surfaces according to the invention.
  • surface according to the invention is characterized in that the treatment effects a coating which may be uneven or, preferably, uniform. It is understood uniformly that the structuring is regular, uneven, that the structuring is irregular, i. One observes structured areas and non-structured areas of the surface.
  • surfaces according to the invention have a coating with an average coverage in the range of 1 to 10 g / m 2 , preferably 1, 5 to 5 g / m 2 .
  • surfaces according to the invention are surfaces of textiles.
  • Another object of the present invention are aqueous formulations containing
  • aqueous formulations according to the invention contain
  • formulations according to the invention contain one or more excipients, preferably up to 10% by weight.
  • aqueous formulations according to the invention have a pH in the range from 2 to 9, preferably 3.5 to 7.5.
  • aqueous formulations according to the invention have a solids content in the range from 10 to 70% by weight, preferably from 30 to 50% by weight.
  • aqueous formulations according to the invention have a dynamic viscosity in the range from 50 to 5000 mPa.s, preferably 100 to 4000 mPa.s and particularly preferably 200 to 2000 mPa.s, measured for example with a Brookfield reagent. Viscometer according to DIN 51562-1 to 4.
  • aqueous formulations according to the invention contain crosslinked organic (co) polymer (b) having a weight average weight in the range of 10 to 450 nm.
  • aqueous formulations according to the invention With aqueous formulations according to the invention, the process according to the invention described above can be carried out particularly well, and they can easily be processed into liquors, for example by dilution with water, with which the process according to the invention can likewise be carried out well.
  • a further subject of the present invention is a process for the preparation of aqueous formulations according to the invention, also referred to below as preparation process according to the invention.
  • preparation process a process for the preparation of aqueous formulations according to the invention.
  • the procedure is preferably such that one
  • the particle diameter distribution of dispersed or emulsified copolymers was determined by Coulter Counter from Malvern according to ISO 13321.
  • Mixture 1.1.1.2 0.6 g of Na 2 S 2 Os in 100 ml of demineralized water
  • a suspension containing 160 ml of demineralized water and 9.1 g of polystyrene seed (average diameter 30 nm, 33% by weight suspension in water) was placed in a 5 l vessel with stirrer, nitrogen inlet and three metering devices. Nitrogen was passed through the suspension over a period of one hour. Subsequently, the mixture was heated to 75 ° C. Thereafter, simultaneous addition of mixture 1.1.1.1, mixture 1.1.1.2 and mixture 1.1.1.3 was started. Mixture 1.1.1.1 was added over 3 hours, mixture 1.1.1.2 and mixture 1.1.1.3 within 3 hours 15 minutes. During the addition, the temperature was maintained at 75 ° C.
  • the dispersion thus obtainable was filtered through a 125 ⁇ m mesh.
  • the filtration time was 4 minutes. This removed about 2 grams of coagulum.
  • aqueous dispersion Disp.1 containing a film-forming copolymer with NH-ChbOH groups (c.1) was obtained.
  • the solids content was 38.7 wt .-%, the dynamic viscosity was 50 mPa-s.
  • the dispersion thus obtainable was filtered through a 125 ⁇ m mesh.
  • the filtration time was 4 minutes. This removed about 2 grams of coagulum.
  • DMAPMAM N, N-dimethylaminopropylmethacrylamide
  • the mixture was stirred for a further 30 minutes at 75 ° C and then for deodorizing simultaneously a solution of 1, 2 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 1, 2 g of acetone disulfite (13 wt .-% in water), diluted with 30 ml of distilled water, dosed over a period of 90 minutes.
  • 1, 2 g of tert-butyl hydroperoxide 70 wt .-% in water
  • a solution of 1, 2 g of acetone disulfite 13 wt .-% in water
  • Blend 1.2.1.1 was added within 2 hours, the remainder of mixture 1.2.1.2 within 2 hours 15 minutes. During the addition, the temperature was maintained at 75 ° C.
  • the mixture was stirred for a further 30 minutes at 75 ° C and then for deodorizing simultaneously a solution of 1, 2 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 1, 2 g of acetone disulfite (13 wt .-% in water), diluted with 30 ml of distilled water, dosed over a period of 90 minutes.
  • 1, 2 g of tert-butyl hydroperoxide 70 wt .-% in water
  • a solution of 1, 2 g of acetone disulfite 13 wt .-% in water
  • the mixture was stirred for a further 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 1.7 g tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 1, 5 g of acetone disulfite (13 wt .-% in water), diluted with 30 ml of distilled water, dosed over a period of 90 minutes.
  • the mixture was stirred for a further 30 minutes at 85 ° C and then for deodorizing simultaneously a solution of 2.1 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 11.5 g of acetone disulfite (13% by weight in water), diluted with 30 ml of distilled water, added over a period of 90 minutes.
  • aqueous dispersion WD.4 containing crosslinked organic copolymer in particulate form (b.4) was obtained.
  • the solids content was 37.7 wt .-%, the dynamic viscosity was 30 mPa-s.
  • Particle diameter distribution maximum at 122 nm.
  • a suspension containing 300 ml of deionized water and 45.5 g of a 33% by weight polystyrene seed (average diameter 30 nm, in water) was placed in a 5 l kettle with anchor stirrer, nitrogen inlet and three metering devices. Nitrogen was then passed through the suspension for a quarter of an hour. Subsequently, the suspension was heated to 85 ° C.
  • mixture 1.2.5.1 and mixture 1.2.5.2 were started simultaneously.
  • Mixture 1.2.5.1 was added within 3 hours, mixture 1.2.5.2 within 3 hours 15 minutes.
  • the temperature was maintained at 85 ° C.
  • the mixture was stirred for 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 1, 4 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 1, 5 g of acetone disulfite (13 wt .-% in water), diluted with 25 ml of distilled water, metered in over a period of 90 minutes. Then it was cooled to room temperature. A pH of 7 was adjusted with 25% by weight aqueous ammonia. Subsequently, the dispersion thus obtainable was filtered through a 125 ⁇ m mesh. The filtration time was 4 minutes. This removed about 2 grams of coagulum.
  • aqueous dispersion WD.5 containing crosslinked organic copolymer in particulate form (b.5) was obtained.
  • the solids content was 37.9 wt .-%, the dynamic viscosity was 32 mPa-s.
  • Particle diameter distribution maximum at 117 nm.
  • a suspension containing 300 ml of deionized water and 60.6 g of a 33% by weight polystyrene seed (mean diameter 30 nm, in water) was placed in a 5 l kettle with anchor stirrer, nitrogen inlet and three metering devices. Nitrogen was then passed through the suspension for a quarter of an hour. Subsequently, the suspension was heated to 85 ° C.
  • the mixture was stirred at 85 ° C. for a further 30 minutes and then, for deodorization, simultaneously a solution of 1.4 g of tert-butyl hydroperoxide (70% by weight in water), diluted with 30 ml of distilled water, and a solution of 1, 5 g of acetone disulfite (13 wt .-% in water), diluted with 25 ml of distilled water, dosed over a period of 90 minutes.
  • aqueous dispersion WD.6 containing crosslinked organic copolymer in particulate form (b.6) was obtained.
  • the solids content was 38 wt .-%, the dynamic viscosity was 30 mPa-s.
  • a suspension containing 300 ml of deionized water and 48.5 g of a 33% by weight polystyrene seed (average diameter 30 nm, in water) was placed in a 5 l kettle with anchor stirrer, nitrogen inlet and three metering devices. Nitrogen was then passed through the suspension for a quarter of an hour. Subsequently, the suspension was heated to 85 ° C.
  • mixture 1.2.7.1 and mixture 1.2.7.2 were started simultaneously.
  • Mixture 1.2.7.1 was added within 3 hours, mixture 1.2.7.2 within 3 hours 15 minutes.
  • the temperature was maintained at 85 ° C.
  • the mixture was stirred for 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 1, 4 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 1, 5 g of acetone disulfite (13 wt .-% in water), diluted with 25 ml of distilled water, metered in over a period of 90 minutes.
  • a suspension containing 300 ml of demineralized water and 15.2 g of a 33% by weight polystyrene seed (mean diameter 30 nm, in water) was placed in a 5 l kettle with anchor stirrer, nitrogen inlet and three metering devices. Thereafter, nitrogen was passed through the resulting suspension over a period of a quarter of an hour. Subsequently, the suspension was heated to 85 ° C.
  • mixture 1.2.10.1 was added within 3 hours, mixture 1.2.10.2 within 3 hours 15 minutes. During the addition, the temperature was maintained at 85 ° C.
  • the mixture was stirred at 85 ° C. for a further 30 minutes and then, for deodorization, simultaneously a solution of 1.4 g of tert-butyl hydroperoxide (70% by weight in water), diluted with 30 ml of distilled water, and a solution of 1, 5 g of acetone disulfite (13 wt .-% in water), diluted with 25 ml of distilled water, dosed over a period of 90 minutes.
  • aqueous dispersion WD.10 containing crosslinked organic copolymer in particulate form (b.10) was obtained.
  • the solids content was 37.6 wt .-%, the dynamic viscosity was 32 mPa-s.
  • Particle diameter distribution maximum at 157 nm.
  • aqueous dispersion WD.11 having a pH of 7.0 containing crosslinked organic copolymer in particulate form (b.11) was obtained.
  • the solids content contributed 37.2 wt .-%, the dynamic viscosity was 32 mPa-s.
  • Particle diameter distribution maximum at 117 nm.
  • Mixture 1.2.13.1 200 g of demineralized water 150 g of styrene, 256.6 g of n-butyl acrylate, 3.5 g of acrylic acid 45 g of 1,4-butanediol diacrylate
  • a suspension containing 300 ml of deionized water and 60.6 g of a 33% by weight polystyrene seed (mean diameter 30 nm, in water) was placed in a 5 l kettle with anchor stirrer, nitrogen inlet and three metering devices. Thereafter, nitrogen was passed through the resulting suspension over a period of a quarter of an hour. Subsequently, the suspension was heated to 85 ° C. Thereafter, simultaneous addition of mixture 1.2.13.1 and mixture 1.2.13.3 was started. Mixture 1.2.13.1 was added within 2 hours 30 minutes, mixture 1.2.13.3 within 3 hours 15 minutes. During the addition, the temperature was maintained at 85 ° C. Immediately after completion of the addition of mixture 1.2.13.1, the addition of mixture 1.2.13.2 was begun, which was added within 30 minutes.
  • the mixture was stirred for 30 minutes at 85 ° C and then for deodorization simultaneously a solution of 1, 4 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 30 ml of distilled water, and a solution of 1, 5 g of acetone disulfite (13 wt .-% in water), diluted with 25 ml of distilled water, metered in over a period of 90 minutes.
  • An aqueous dispersion WD.13 containing crosslinked organic copolymer in particulate form (b.13) was obtained.
  • the solids content was 37.7 wt .-%
  • the dynamic viscosity was 32 mPa-s.
  • Particle diameter distribution maximum at 101 nm.
  • aqueous dispersion WD.14 having a pH of 9.2 containing crosslinked organic copolymer in particulate form (b.14) was obtained.
  • the solids content was 34 wt .-%, the dynamic viscosity was 30 mPa-s. Particle diameter distribution: maximum at 252 nm.
  • Random copolymer with M n of 30,000 g / mol (GPC) of 10 wt .-% methacrylic acid and 90 wt .-% CH2 CHCOO-CH2-CH2-OnC 6 Fi3 in aqueous dispersion (20 wt .-% solids) (a1. 1),
  • Paraffin wax (unbranched, melting range 65 - 70 0 C, average C number per molecule: 40) (a2.1)
  • the particles of (b) in the aqueous formulations F.1 to F.3 according to the invention did not tend to agglomerate.
  • Table 1 Compositions of aqueous formulations according to the invention
  • Mixture 1.4.1 146 g of deionized water 130.8 g of styrene, 245.2 g of n-butyl acrylate, 12 g of acrylic acid,
  • the mixture was stirred for 30 minutes at 75 ° C and then for deodorization simultaneously a solution of 1, 2 g of tert-butyl hydroperoxide (70 wt .-% in water), diluted with 22 ml of distilled water, and a solution of 0.8 g of HO-ChbSCbNa, diluted with 25 ml of distilled water, added over a period of 90 minutes.
  • primer (fA.1) in aqueous dispersion with a pH of 7.5.
  • the solids content was 39.6 wt .-%, the dynamic viscosity was 310 mPa-s.
  • a cationic primer (f «.1), a reaction product of equimolar amounts of piperazine with epichlorohydrin and benzyl chloride was used, molecular weight M w 15,000 g / mol.
  • Cotton 1 m ⁇ 30 cm, 100% cotton fabric, bleached, not mercerized, twill weave, basis weight 196 g / m 2 ("BW")
  • Polyester 1 m ⁇ 30 cm, polyester staple fiber fabric, basis weight 220 g / m 2 ("PES")
  • Foulard Manufacturer: Mathis, type no. HVF12085, contact pressure 1 - 3 bar.
  • the contact pressure was always adjusted so that the liquor pickup (based on the Weight of goods) was 60% for polyester and 90% for cotton, unless otherwise stated.
  • the fleet had room temperature, unless stated otherwise.
  • Dryer continuous dryer of the company Mathis THN 12589 test method: spray test: AATCC 22-2001, oil grade: AATCC 118-2002,
  • Water repellency AATCC 193-2004, smoothness: AATCC 124-2001 Washing conditions: Delicate wash at 30 0 C, 15 g / l of a mild detergent (FEWA), Washing machine: Miele Novotronic T440C, Adjustment: Tumbler dry, iron damp.
  • FEWA mild detergent
  • the aqueous liquors were prepared by mixing (diluting) the components listed in Table 2 with water to one liter.
  • the auxiliary (e.4) used was a hydrophilized isocyanurate / diisocyanate from EP 0 486 881, Example 4.
  • PES was first padded with an aqueous liquor containing 8.3 g / l cationic primer (f ⁇ .1). The liquor pickup was 60%, the run 0.5 g (f ⁇ .1) / m 2 PES. Subsequently, it was treated thermally at 120 0 C in a dryer for 2 minutes.
  • the aqueous liquors were prepared by mixing (diluting) the formulations according to the invention indicated in Table 2 with water to one liter.
  • the auxiliary (e.4) used was a hydrophilized isocyanurate / diisocyanate from EP 0 486 881, Example 4.
  • BW was padded with an aqueous liquor according to Table 2. It was then dried for 2 minutes on a tenter at 110 0 C to a residual moisture content of 7% and then treated thermally over a period of 2 minutes at 160 0 C in a dryer. Inventive textile BW.2 or BW.7 according to Table 2 was obtained.
  • BW.3 and BW.7 For the preparation of BW.3 and BW.7 according to the invention, the procedure was analogous to that in Table 2, but the starting material used was 1 m 30 cm, 100% cotton fabric, bleached, not mercerized, twill weave, basis weight 120 g / m 2 , and the mixture was treated thermally at 150 0 C (instead of 160 0 C). Inventive textile BW.3 or BW.7 was obtained. The spray test gave 90, the smoothness DP 3.25 (for BW.3) and 3.5 (for BW.7).
  • PES was first padded with an aqueous liquor containing 8.3 g / l anionic primer (f A .1). The liquor pickup was 60%, the run 0.5 g (f A .1) / m 2 PES. Subsequently, it was treated thermally at 120 0 C in a dryer for 2 minutes.
  • aqueous liquors were prepared by mixing (diluting) the formulations according to the invention indicated in Table 2 with water to one liter.
  • BW was padded with an aqueous liquor according to Table 2 (1st step). It was dried on a tenter for two minutes at 110 0 C and then padded with a liquor according to Table 2 (2nd step). Thereafter, the thus treated textile was treated for 2 minutes at 160 0 C in a dryer.
  • Inventive textile BW.4 according to Table 2 was obtained.
  • the aqueous liquors were prepared by mixing (diluting) the components listed in Table 2 with water to one liter.
  • BW was first padded with an aqueous liquor containing 5 g / l of cationic primer (f ⁇ .1). The liquor pickup was 90%, the run 0.5 g (f ⁇ .1) / m 2 PES. Subsequently, it was treated thermally at 140 0 C in a dryer for 2 minutes. Subsequently, an aqueous liquor was padded according to Table 2 (1st step). It was dried on a tenter for two minutes at 110 0 C and then padded with a liquor according to Table 2 (2nd step). Thereafter, the thus treated textile was treated for 2 minutes at 160 0 C in a dryer. Inventive textile BW.5 or BW.6 according to Table 2 was obtained.
  • the aqueous liquors were prepared by mixing (diluting) the components listed in Table 2 with water to one liter.
  • the auxiliary (e.4) used was a hydrophilized isocyanurate / diisocyanate from EP 0 486 881, Example 4.
  • Oil note / 10 Oil note after 10 household washes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

Procédé de traitement de surfaces, qui consiste à traiter lesdites surfaces avec (a) au moins un produit imperméabilisant, (b) au moins un copolymère organique réticulé sous forme particulaire, (c) au moins un copolymère filmogène contenant des groupes époxyde, des groupes NH-CH2OH ou des groupes acétoacétyle, (d) et éventuellement un ou plusieurs émulsifiants, puis à sécher lesdites surfaces après le traitement.
EP06793413A 2005-09-16 2006-09-11 Procede de traitement de surfaces Withdrawn EP1929084A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005044520A DE102005044520A1 (de) 2005-09-16 2005-09-16 Verfahren zur Behandlung von Oberflächen
PCT/EP2006/066232 WO2007031491A2 (fr) 2005-09-16 2006-09-11 Procede de traitement de surfaces

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EP1929084A2 true EP1929084A2 (fr) 2008-06-11

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US (1) US20080250571A1 (fr)
EP (1) EP1929084A2 (fr)
KR (1) KR20080046713A (fr)
CN (1) CN101263258A (fr)
BR (1) BRPI0615936A2 (fr)
DE (1) DE102005044520A1 (fr)
WO (1) WO2007031491A2 (fr)

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CN101535560A (zh) * 2006-11-17 2009-09-16 巴斯夫欧洲公司 含水配制剂及其用途
BRPI0811545A2 (pt) * 2007-05-22 2014-11-18 Basf Se Processo para o tratamento de uma superfície de um têxtil, superfície de têxtil, formulação aquosa, e, processo para a produção de uma formulação aquosa
WO2018026724A1 (fr) * 2016-08-01 2018-02-08 Daikin America, Inc. Composition de cire destinée à être utilisée sur des planches
CN109957968A (zh) * 2017-12-26 2019-07-02 北京绿伞化学股份有限公司 一种常温下使用的消防服整理剂及其制备方法和应用

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US4044197A (en) * 1975-03-21 1977-08-23 Wacker-Chemie Gmbh Thermally self-cross-linkable ethylene/vinyl acetate copolymers
EP0886176A1 (fr) * 1997-06-19 1998-12-23 Eastman Kodak Company Elément formant image contenant des particules polymériques et lubrifiant
US6939922B2 (en) * 2001-03-30 2005-09-06 Rohm And Haas Company Coating and coating composition
DE10128894A1 (de) * 2001-06-15 2002-12-19 Basf Ag Verfahren zur schmutzablösungsfördernden Behandlung von Oberflächen textiler und nicht-textiler Materialien
WO2003014202A1 (fr) * 2001-08-07 2003-02-20 Teijin Dupont Films Japan Limited Film polyester en couches etire bi-axialement et film a couche de revetement dure
EP1371693A3 (fr) * 2002-06-14 2004-01-07 Rohm And Haas Company Revêtements, couches et articles résistants aux dommages et comprenant des nanoparticules réticulées
CN1225515C (zh) * 2002-09-30 2005-11-02 罗姆和哈斯公司 含有交联的纳米颗粒的耐破损涂层、薄膜和制品
DE10306893A1 (de) * 2003-02-18 2004-08-26 Basf Ag Verfahren zur Hydrophobierung von textilen Materialien
US7213309B2 (en) * 2004-02-24 2007-05-08 Yunzhang Wang Treated textile substrate and method for making a textile substrate
JP2007523272A (ja) * 2004-02-24 2007-08-16 ミリケン・アンド・カンパニー 処理した繊維製品基材および該繊維製品基材の製造方法

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DE102005044520A1 (de) 2007-03-22
WO2007031491A2 (fr) 2007-03-22
CN101263258A (zh) 2008-09-10
US20080250571A1 (en) 2008-10-16
BRPI0615936A2 (pt) 2012-12-18
KR20080046713A (ko) 2008-05-27
WO2007031491A3 (fr) 2007-11-01

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