WO2008090191A2 - Particules, procédé de fabrication et utilisation - Google Patents

Particules, procédé de fabrication et utilisation Download PDF

Info

Publication number
WO2008090191A2
WO2008090191A2 PCT/EP2008/050788 EP2008050788W WO2008090191A2 WO 2008090191 A2 WO2008090191 A2 WO 2008090191A2 EP 2008050788 W EP2008050788 W EP 2008050788W WO 2008090191 A2 WO2008090191 A2 WO 2008090191A2
Authority
WO
WIPO (PCT)
Prior art keywords
water
particles
particles according
polymer
acid
Prior art date
Application number
PCT/EP2008/050788
Other languages
German (de)
English (en)
Other versions
WO2008090191A3 (fr
Inventor
Guido Vandermeulen
Harald Keller
Heike Becker
Michael Schmitt
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 WO2008090191A2 publication Critical patent/WO2008090191A2/fr
Publication of WO2008090191A3 publication Critical patent/WO2008090191A3/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • C03C23/0075—Cleaning of glass
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/75—Hydrophilic and oleophilic coatings

Definitions

  • the present invention relates to particles having a mean diameter in the range of 3 nm to 100 nm, comprising (A) an inorganic solid,
  • the present invention relates to dispersions, in particular aqueous dispersions containing particles of the invention, and to a process for the preparation of the dispersions of the invention. Furthermore, the present invention relates to the use of particles according to the invention, for example by using the dispersions of the invention.
  • cleaning agents for hard surfaces are proposed, which are able to cover 33 to 86% of a surface with hydrophilizing substance and comprising a mixture of colloidal silica sol and a polymeric material such as acrylic polymers.
  • aqueous dispersions of composite particles of polymer and finely divided inorganic solid are known, wherein the polymer is preferably prepared by emulsion polymerization in the presence of the inorganic solid, such dispersions are particularly suitable for priming mineral substrates, especially of glassy substrates.
  • WO 02/060998 discloses non-thixotropic rinsing agents, for example, for dishes which are a mixture of generally hydrophilic non-photoactive nanoparticles and a carrier medium, in particular water, and may also contain further constituents, for example a surfactant or a dispersing polymer , Such rinsing agents are prepared by mixing the above ingredients and are capable of coating the surface of dishes. The cleaning effect can be improved, however.
  • the object therefore was to provide means for cleaning and hydrophilizing surfaces, in particular solid surfaces, which have an improved cleaning action and an improved slowing down of re-soiling. Another object was to provide suitable ingredients for agents for cleaning and hydrophilizing surfaces. Another object was to provide a process for the preparation of agents for cleaning and hydrophilizing surfaces and the ingredients suitable therefor.
  • Particulates according to the invention have an average diameter in the range of 3 nm to 100 nm, preferably up to 50 nm, particularly preferably 5 to 40 nm, and comprise (A) an inorganic solid,
  • the mean particle diameters are preferably determined with the aid of the analytical ultracentifuge (cf., for this purpose, SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of polymer Dispersions with an Eight-Cell AUC Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Gurchtle, pages 147 to 175).
  • the values given for the particle diameter preferably correspond to the so-called d ⁇ o values.
  • Solid (A) is a solid which is preferably in particulate form, for example having a mean particle diameter of not more than 100 nm, preferably not more than 50 nm, in particular from 1 to not more than 40 nm.
  • Stable aqueous dispersion means those which have an initial solids concentration of not more than 1% by weight, based on the aqueous dispersion of the respective inorganic solid (A), of more than 90 without stirring or shaking for one hour after their preparation % By weight of the originally dispersed inorganic solid (A) in dispersed form and whose dispersed solid particles have a maximum diameter of 100 nm.
  • inorganic solids (A) are, for example, metals in the form of metal powders, metal compounds such as metal oxides and metal salts, but also metalloids and
  • Non-metal compounds and further colloidal graphite and diamond suitable are suitable.
  • metal powder noble metal colloids such as palladium, silver, ruthenium, platinum, gold and rhodium and alloys containing them can be used.
  • metal oxides which may be mentioned are titanium dioxide (for example commercially available as Hombitec® grades from Sachtleben Chemie GmbH),
  • metal salts are in principle applicable: sulfides, such as iron (II) sulfide, iron (III) sulfide, iron (II) disulfide (pyrite), tin (II) sulfide, tin (IV) sulfide, mercury (II) sulfide, cadmium (II) sulfide, zinc sulfide , Copper (II) sulfide, silver sulfide, nickel (II) sulfide, cobalt (II) sulfide, cobalt (III) sulfide, manganese (II) sulfide, chromium (III) sulfide , Titanium (II) sulfide, titanium (III) sulfide, titanium (IV) sulfide, zirconium (IV) sulfide, antimony (III
  • Silicon dioxide suitable according to the invention is commercially available and can be used, for example, as Aerosil® (trademark of Degussa AG), Levasil® (trademark of Bayer AG), Ludox® (trademark of DuPont), Nyacol® and Bindzil® (trademarks of Akzo-Nobel) and Snowtex® (trademark of Nissan Chemical Industries, Ltd.).
  • Aerosil® trademark of Degussa AG
  • Levasil® trademark of Bayer AG
  • Ludox® trademark of DuPont
  • Nyacol® and Bindzil® trademarks of Akzo-Nobel
  • Snowtex® trademark of Nissan Chemical Industries, Ltd.
  • inorganic solids (A) those are particularly suitable whose solubility in water at 20 ° C.
  • 1 bar (absolute) is at most 1 g / l, preferably at most 0.1 g / l and in particular at most 0.01 g / l.
  • silica sols which have an electrophoretic mobility with a negative sign.
  • Inorganic solid (A) may in one embodiment of the present invention be a mixture of two or more inorganic solids (A), both of which are selected from the aforementioned materials.
  • Particles according to the invention furthermore comprise a (co) polymer (B) which is composed of at least 70% by weight, preferably at least 85% by weight, of (co) monomers which have a solubility of at least 10 in water at 25 ° C. g / l. If (co) polymer (B) is a copolymer, up to 30% by weight, preferably up to 15% by weight, of one or more comonomers which in water at 25 ° C. may also be copolymerized Have solubility of less than 10 g / l.
  • (Co) polymer (B) is prepared in the presence of inorganic solid (A). To some extent, (co) polymer (B) is associated with inorganic solid (A), for example, (co) polymer (B) may coat inorganic solid (A).
  • (co) polymer (B) is composed of at least 70% by weight, preferably at least 85% by weight, of at least one of the following (co) monomers, which are also considered to be good in the context of the present invention water-soluble comonomers are referred to:
  • Styrenesulfonic acid 2-methacryloxyethylsulfonic acid, vinylsulfonic acid and vinylphosphonic acid
  • Phosphoric acid monoesters of n-hydroxyalkyl (meth) acrylates preferably of ⁇ -hydroxy-C 2 -C 4 -alkyl (meth) acrylates, more preferably of 2-hydroxyethyl (meth) acrylate, furthermore n-hydroxyalkyl (meth) acrylates, in particular ⁇ Hydroxy-C 2 -C 4 -alkyl (meth) acrylates such as, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate, acrylonitrile, Methyl esters of ethylenically unsaturated carboxylic acids and monoethyl esters of ethylenically unsaturated dicarboxylic acids, such as methyl acrylate, methyl methacrylate, dimethylmaleic acid, monomethyl maleate,
  • Esters of acrylic acid or methacrylic acid with monoethyl ether of oligomeric ethylene glycol having 1 to 20 -CH 2 CH 2 O units esters of acrylic acid or methacrylic acid with monomethyl ether of oligomeric ethylene glycol with 1 to 20 -CH 2 CH 2 O units, esters of acrylic acid or methacrylic acid with mono-n- propyl ether or monoisopropyl ether of oligomeric ethylene glycol having 1 to 20 -CH 2 CH 2 O units, esters of acrylic acid or methacrylic acid with mono-n-butyl ether of oligomeric ethylene glycol having 1 to 20 -CH 2 CH 2 O units.
  • Preferred (co) monomers are acrylic acid, methacrylic acid, maleic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methyl acrylate and methyl methacrylate.
  • (co) polymer (B) is constructed exclusively of one or more of the abovementioned (co) monomers.
  • polymer (B) in another embodiment of the present invention (co) polymer (B) to at least 70 wt .-%, preferably at least 85 wt .-% of one or more of the aforementioned comonomers and further one or more comonomers constructed, which 25 ° C have a solubility of less than 10 g / l and which are also referred to as poorly water-soluble comonomers.
  • Examples of poorly water-soluble comonomers are ethylene, 2-vinylpyridine, 4-vinylpyridine, vinylaromatic monomers such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 C atoms, such as vinyl acetate, vinyl propionate , Vinyl n-butyrate, vinyl laurate and vinyl stearate, esters of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids preferably having 3 to 6 carbon atoms, in particular acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, with in general 2 alkanols containing up to 12, preferably up to 8 and in particular up to 4, carbon atoms, such as, in particular, ethyl acrylate and methacrylate, n-butyl, isobutyl and
  • (co) polymer (B) is at least 70% by weight, preferably at least 85% by weight, of one or more of the abovementioned readily water-soluble comonomers and furthermore one or more built comonomers containing a tertiary amino group or a quaternary ammonium group.
  • Examples are 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 4-amino-n-butyl acrylate, 4-amino-n-butyl methacrylate, 2- (N-methylamino) ethyl acrylate, 2- (N-methylamino) ethyl methacrylate, 2- (N-ethylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (Nn-propylamino) ethyl acrylate, 2- (Nn-propylamino) ethyl methacrylate, 2- (N-iso-propylamino) ethyl acrylate, 2 - (N-iso-propylamino) ethyl acrylate, 2 - (N-isopropy
  • (co) polymer (B) is at least 70% by weight, preferably at least 85% by weight, of one or more of the abovementioned comonomers and furthermore up to a maximum of 20% by weight, preferably at least 5% by weight of one or more comonomers, which carry one or more siloxane groups per molecule.
  • Examples of comonomers which carry one or more siloxane groups per molecule are trialkoxysilanes having vinyl groups, acryloxy groups or methacryloxy groups as the ethylenically unsaturated group, for example 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane or vinyltriethoxysilane. Preference is given to 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane.
  • the missing to 100 wt .-% fraction can be selected from one or more of the above readily water-soluble or poorly water-soluble comonomers.
  • the weight ratio of inorganic solid (A) to (co) polymer (B) is in the range of 100 to 1 to 1.1 to 1, preferably in the range of 50 to 1 to 2.5 to 1.
  • Another object of the present invention is a process for the preparation of particles according to the invention.
  • inorganic solid (A) preference is given to mixing at least one inorganic solid (A) with water and / or one or more water-miscible organic solvents and then organic (co) polymer (B) by (co) polymerization of (Co) produces monomers, of which at least 70 wt .-% in water at 25 ° C have a solubility of at least 10 g / l, and then optionally water and / or water-miscible organic solvents removed.
  • the preparation of (co) polymer (B) is carried out by free-radical (co) polymerization.
  • free-radical initiators preference is given to using one or more free-radical initiators. In principle, these may be peroxides or azo compounds. Of course, redox initiator systems come into consideration.
  • peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, especially their mono- and di-sodium, potassium or ammonium salts, or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or diarylperoxides, such as di-tert-butyl or di-cumyl peroxide are used.
  • inorganic peroxides such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, especially their mono- and di-sodium, potassium or ammonium salts
  • organic peroxides such as alkyl hydroperoxides, for example tert-but
  • the azo compounds are essentially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (AIBA, corresponding to V-50 from Wako Chemicals). Use.
  • Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides.
  • Suitable reducing agents may be sulfur compounds having a low oxidation state, such as alkali metal sulfites, for example potassium and / or sodium sulfite, alkali hydrogen sulfites, for example potassium and / or sodium hydrogen sulfite, alkali metal metabisulfites, for example potassium and / or sodium metabisulfite, formaldehyde sulfoxylates, for example potassium and / or Sodium formaldehyde sulfoxylate, alkali salts, especially potassium and / or sodium salts of aliphatic sulfinic acids and alkali metal hydrogen sulfides, such as, for example, potassium and / or sodium hydrosulfide, salts of polyvalent metals, such as iron (II) sulfate, iron (II) Ammonium sulfate, iron (II) phosphate, endiols such as dihydroxymaleic acid, benzoin and / or ascorbic acid and reducing
  • polymerization temperature to conduct the (co) zero to 150 0 C are suitable, preferably 20 to 1 10 0 C, and particularly preferably 70 to 110 0 C.
  • the pressure conditions in the representation of particles according to the invention are generally not critical. For example, normal pressure is possible. You can also choose pressures in the range of 1, 01 to 10 bar. If you want to work at temperatures above 100 0 C or above the temperature corresponding to the boiling point of the continuous phase used at atmospheric pressure, so it is preferable to work at a higher pressure, ie up to 10 bar.
  • the preparation of particles according to the invention takes place in the absence of surface-active substances, in particular non-polymerizable surface-active substances such as, for example, surfactants, protective colloids, emulsifiers or wetting agents.
  • surface-active substances such as, for example, surfactants, protective colloids, emulsifiers or wetting agents.
  • (co) polymer (B) preference is given to using a dispersion medium, in particular water and / or water-miscible organic solvents such as, for example, methanol, ethanol, n-propanol, 2-propanol, acetone, tetrahydrofuran and Polyols such as ethylene glycol, diethylene glycol, triethylene glycol and glycerol. Preference is given to water and mixtures of water with one or more water-miscible solvents and mixtures of several water-miscible solvents.
  • a dispersion medium in particular water and / or water-miscible organic solvents such as, for example, methanol, ethanol, n-propanol, 2-propanol, acetone, tetrahydrofuran and Polyols such as ethylene glycol, diethylene glycol, triethylene glycol and glycerol.
  • water and mixtures of water with one or more water-miscible organic solvents having a boiling point of not more than 120 ° C., for example ethanol, n-propanol, 2-propanol, acetone and tetrahydrofuran.
  • (Co) polymer (B) desires to add, and then add during the free radical (co) polymerization, the remaining amount of free radical initiator continuously or discontinuously in accordance with the consumption. Finally, one can submit inorganic solid (A) in the reaction medium, then add the (co) monomers from which one wishes to prepare (co) polymer (B), and then for the purpose of triggering the free radical (co) polymerization of the radical initiator - optionally after Consistent with the consumption - to add continuously or discontinuously.
  • Particulates of the invention are generally obtained in the form of a preferably aqueous dispersion, which is also the subject of the present invention.
  • a process for the preparation of dispersions of the invention is an object of the present invention.
  • Particles according to the invention can be isolated from the aqueous dispersion according to the invention by processes known per se, for example filtration, centrifuging or spray drying. By isolating particles according to the invention, the water used or other solvents are also removed.
  • aqueous dispersions according to the invention contain from 0.1 to 80% by weight of particles according to the invention.
  • dispersions of the invention contain no surfactants, that is, for example, no alkoxylated fatty or oxoalcohols or sulfated alkoxylated fatty acids.
  • one or more surfactants in particular one or more nonionic surfactants, are added after the actual preparation of particles according to the invention or dispersions of the invention.
  • nonionic surfactants such as polyethyleneglyoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C 4 to C 12) and ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: Cs to C36), in particular C 12 -C 14 -fatty alcohol ethoxylates, degree of ethoxylation: 3 to 8, C 13 -C 15 -oxoalcohol ethoxylates, degree of ethoxylation: 3 to 30, C 16 -C 16 -fatty alcohol ethoxylates, degree of ethoxylation: 11 to 80, Cio-oxoalcohol ethoxylates, degree of ethoxylation: 3 to 11 and C 13 -oxoalcohol ethoxylates, degree of ethoxylation: 3 to 20 ,
  • nonionic surfactants such as polyethyleneglyoxylated mono
  • from 0.1 to 5% by weight of surfactant, based on the total dispersion according to the invention, is preferably from 0.3 to 2% by weight.
  • Cleaning agents according to the invention may contain one or more further components ( ⁇ ) to ( ⁇ ): at least one surfactant selected from the group consisting of anionic, nonionic and amphoteric surfactants, as component ( ⁇ ),
  • component (y) optionally ammonia and / or at least one alkanolamine, as component (y),
  • component ( ⁇ ) optionally one or more other auxiliaries and additives, as component ( ⁇ ).
  • Detergents according to the invention may contain 0.01 to 80% by weight, preferably 0.01 to 30% by weight, particularly preferably 0.01 to 20% by weight, very particularly preferably 0.01 to 5% by weight of at least one Surfactants selected from anionic, nonionic and amphoteric surfactants, as component ( ⁇ ) included.
  • Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols containing 8 to 22, preferably 8 to 18 carbon atoms, e.g. C 9 -C 10 alcohol sulfates, C 12 -C 13 alcohol sulfates, C 14 -C 18 -alcohol sulfates such as lauryl sulfate, cetyl sulfate, myristyl sulfate, p-mityl sulfate, stearyl sulfate or tallow fatty alcohol sulfate.
  • Suitable anionic surfactants are sulfated ethoxylated C 8 -C 22 -alcohols (alkyl ether sulfates) or their water-soluble salts.
  • Compounds of this type are prepared, for example, by first alkoxylating a C 8 -C 22 -alcohol, preferably cio-cis-alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product.
  • Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 2 to 30, moles of ethylene oxide being used per mole of fatty alcohol.
  • the alkoxylation of the alcohols can also be carried out with propylene oxide alone and optionally butylene oxide.
  • alkoxylated Cs-C22 alcohols containing ethylene oxide and propylene oxide or ethylene oxide and butylene oxide.
  • the alkoxylated C 8 -C 22 -alcohols may be the ethylene oxide, contain pylene oxide and butylene oxide units in the form of blocks or in random distribution.
  • alkanesulfonates such as C8-C24-, preferably C10-C18-alkanesulfonates and soaps such as the Na and K salts of C8-C24-carboxylic acids.
  • anionic surfactants are C8-C20-linear alkylbenzenesulfonates (LAS), preferably linear Cg-ds-alkylbenzenesulfonates and -alkyltoluenesulfonates.
  • LAS C8-C20-linear alkylbenzenesulfonates
  • anionic surfactants are C8-C24-olefinsulfonates and -disulfonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates having from 20 to 50 C atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl taurates, acylmethyl taurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or halobamides, alkylsulfosuccinic acids or their amides, mono- and diesters of s, al
  • Suitable anionic surfactants are also mono- or dialkyl phosphates.
  • Anionic surfactants are preferably added to dispersions according to the invention in the form of salts.
  • Suitable salts are alkali metal salts such as sodium, potassium, lithium salts and ammonium salts such as hydroxyethylammonium, N, N-di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.
  • Anionic surfactants can be used individually or in combination of different anionic surfactants and in admixture with the other surfactants mentioned. It is possible to use anionic surfactants of only one class, e.g. only fatty alcohol sulfates or only alkylbenzenesulfonates, but also mixtures of different classes, e.g. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates.
  • Preferred anionic surfactants are alkyl ether sulfates, alkyl sulfates and alkyl phosphates.
  • nonionic surfactants are alkoxylated Cs-C22 alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates.
  • the alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide.
  • Usable as surfactants in this case are all alkoxylated alcohols which contain at least two molecules of an abovementioned alkylene oxide added.
  • the alkylene oxide used is preferably ethylene oxide.
  • the alcohols preferably have 10 to 18 carbon atoms.
  • Suitable nonionic surfactants are alkylphenol ethoxylates having C 6 -C 14 -alkyl chains and from 5 to 30 mol of ethylene oxide units.
  • nonionic surfactants are alkyl polyglucosides having 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1, 1 to 5 glucoside units.
  • Another class of nonionic surfactants are N-alkylglucamides.
  • nonionic surfactants are alkylamine alkoxylates or alkylamide ethoxylates.
  • Detergents according to the invention preferably contain 3 to 12 moles of ethylene oxide ethoxylated Cio-Ci6 alcohols, more preferably ethoxylated fatty alcohols. Further preferred are alkyl polyglucosides, alkylamine alkoxylates and amide ethoxylates.
  • nonionic surfactants or a combination of different nonionic surfactants or a mixture with further abovementioned surfactants. Preference is given to alkoxylated C8-C22 alcohols alone.
  • amphoteric surfactants are alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates or amphoteric imidazolium compounds.
  • Preferred examples are cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, coco amphocarboxyglycinate and cocoamphoacetate.
  • component ( ⁇ ) anionic surfactants, nonionic surfactants or combinations of anionic and nonionic surfactants.
  • component ( ⁇ ) is selected from fatty alcohol sulfates, alkyl ether sulfates, fatty alcohol alkoxylates and mixtures thereof.
  • water-soluble organic solvent used as component ( ⁇ ) is in an amount of 0 to 50 wt .-%, preferably 0.1 to 30 wt .-%, particularly preferably 0.5 to 15 wt .-%, most preferably 1 to 10 wt .-% used in the compositions of the invention.
  • Suitable water-soluble organic solvents are C 1 -C 6 alcohols and / or ether alcohols, mixtures of different alcohols and / or ether alcohols being preferred.
  • Suitable alcohols are glycerol, propylene glycol, ethylene glycol, ethanol, isopropanol and n-propanol.
  • Suitable ether alcohols are ether alcohols having up to 10 carbon atoms in the molecule, for example ethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monobutyl ether, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether. Particularly preferred are ethylene glycol monobutyl ether and propylene glycol monobutyl ether.
  • component C is selected from ethanol, isopropanol, n-propanol, ethylene glycol monobutylene, propylene glycol monobutyl ethers and mixtures of two or more of said water-soluble organic solvents.
  • the weight ratio of alcohol and ether alcohol is preferably 1: 2 to 4: 1.
  • the weight ratio is preferably 1: 6 to 6: 1, more preferably 1 to 5 to 5 to 1, very particularly preferably 4 to 1, with the proportion of the ether alcohol having fewer carbon atoms in particular being preferably the higher of the two.
  • Ammonia and / or at least one alkanolamine as component (y) or at least one inorganic acid, carboxylic acid and / or sulfonic acid as component ( ⁇ ) can each be used in a proportion of generally 0 to 5 wt .-%, preferably 0.01 to 3 wt .-%, more preferably 0.02 to 1 wt .-%, most preferably 0.05 to 0.5 wt .-% in inventive detergents use.
  • component (y) it is preferred to use ammonia and / or those alkanolamines which contain 1 to 9 carbon atoms in the molecule.
  • the alkanolamines used are preferably ethanolamines, particularly preferably monoethanolamine.
  • the cleaning agent according to the invention may additionally contain at least one inorganic acid, carboxylic acid or sulfonic acid, wherein the molar ratio of ammonia and / or alkanolamine to carboxylic acid is preferably from 1 to 0.9 to 1 to 0.1 .
  • Suitable carboxylic acids are carboxylic acids containing from 1 to 6 carbon atoms, which may be mono-, di- or polycarboxylic acids. Examples of suitable
  • Carboxylic acids are formic acid, acetic acid, glycolic acid, lactic acid, citric acid. R, succinic and adipic acid, preferably formic acid, acetic acid, citric acid and lactic acid, most preferably acetic acid.
  • suitable sulfonic acids are amidosulfonic acid and methanesulfonic acid, preferably amidosulfonic acid.
  • suitable inorganic acids are HCl and H3PO4.
  • component ( ⁇ ) used builder detergent according to the invention to a proportion of generally 0 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.1 to 3 wt .-% is added.
  • Builders include inorganic builders and organic (co) builders.
  • Suitable inorganic builders are all customary inorganic builders such as aluminosilicates, silicates, carbonates, phosphates and phosphonates.
  • Suitable inorganic builders are known per se and e.g. in DE-A 101 60 993.
  • low molecular weight polycarboxylates can be used.
  • salts of phosphonic acids and oligomeric or polymeric polycarboxylates are suitable.
  • copolymers and terpolymers of unsaturated C 4 -C 8 -dicarboxylic acids with monoethylenically unsaturated monomers which may additionally be modified, and also polyglyoxylic acids, polyamidocarboxylic acids and modified polyamicocarboxylic acids, polyaspartic acid or cocondensates of aspartic acid with further amino acids, C 4 -C 25 -mono- or -Dicarboxylic acids and / or C4-C25 mono- or diamines, condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds having molecular weights M n of generally up to 10,000 g / mol, preferably up to 5,000 suitable.
  • Suitable organic (co) builders are e.g. mentioned in DE-A 101 60 993.
  • cleaning agents according to the invention may comprise, in addition to particles and water according to the invention and one or more components ( ⁇ ) to ( ⁇ ), one or more auxiliaries and additives as component ( ⁇ ).
  • auxiliaries and additives may be present in an amount of from 0 to 5% by weight, preferably from 0.01 to 3% by weight, in cleaning compositions according to the invention.
  • Suitable auxiliaries and additives include all auxiliaries and additives conventionally used in hard surface treatment and cleaning agents, preferably dyes, perfume oils, pH regulators, for example NaOH, preservatives, complexing agents for alkaline earth metal ions, enzymes, bleaching systems, soil release polymers, Foam boosters, foam suppressants or foam inhibitors, biocides, tarnish and / or corrosion inhibitors, suspending agents, fillers, inorganic adjusters, disinfectants, hydrotropes, antioxidants, solubilizers, dispersants, processing aids, solubilizers, plasticizers and antistatic agents.
  • auxiliaries and additives are e.g. mentioned in DE-A 101 60 993.
  • Detergents according to the invention are generally prepared by mixing particles of the invention or dispersions of the invention and, if desired, one or more of components ( ⁇ ) to ( ⁇ ) and water.
  • Another object of the present invention is the use of particles of the invention or aqueous dispersions of the invention, in particular using one or more cleaning agents according to the invention, for the hydrophilization of solid surfaces.
  • Another object of the present invention is a process for the hydrophilization of solid surfaces using particles of the invention or aqueous dispersions of the invention or in particular using one or more cleaning agents according to the invention.
  • Another object of the present invention are solid surfaces coated with particles of the invention or using preferably aqueous dispersions of the invention or in particular using one or more cleaning agents according to the invention.
  • Solid surfaces in the context of the present invention are surfaces of solids.
  • Preferred solids are plastics such as plastic films, for example polyester films or polyamide films, in particular films of polyolefins such as polyethylene or polypropylene or of thermoplastic polyurethane, furthermore surfaces of polymethyl methacrylate or of polystyrene.
  • Other well-suited solid surfaces are surfaces of ceramic, glass, porcelain, stone, in particular natural stone, and also of concrete, washed concrete or solid metal.
  • Solid surfaces may be indoor or outdoor floor coverings made of one of the abovementioned materials or of plastic, in particular of polyvinyl chloride (PVC), or of wood.
  • PVC polyvinyl chloride
  • the process according to the invention for hydrophilization can be carried out in such a way that particles according to the invention, in particular in the form of a preferably aqueous dispersion according to the invention, are applied to the relevant solid surface and then dried, for example at room temperature.
  • the application can be carried out, for example, by application or rubbing with a cloth or sponge soaked with the dispersion according to the invention, furthermore by spraying, dipping, roller application, roller application or application with the aid of a printing press.
  • the coating need not be continuous, in many cases it is sufficient if parts of the respective solid surface are covered with particles of the invention and other parts are not.
  • Solid surfaces according to the invention usually look well-cleaned, in particular after carrying out the process according to the invention for the hydrophilization of solid surfaces, in addition they show a lower tendency to re-soiling. Drops of water or aqueous solutions will not adhere to the surfaces, but will deliquesce and form a thin film of liquid that drains easily from the surface. This avoids the formation of stains, especially limescale, and dirt edges. In addition, inventive solid surfaces show a reduced tendency to fog.
  • a special subject matter of the present invention are films coated with particles according to the invention or using preferably aqueous dispersions according to the invention.
  • Such coated films are also referred to as films according to the invention in the context of the present invention.
  • particles according to the invention are suitable as such, but in particular in the form of preferably aqueous dispersions according to the invention for coating films.
  • coated films according to the invention are thermoplastic polyurethane
  • such coated films according to the invention are particularly suitable for producing layered materials, for example those which further comprise at least one textile layer.
  • thermophysiological comfort for example, characterized by breathability, thermal insulation, moisture transport, drying time, as well as good sensory comfort, such as clamping force textile / skin, surface roughness / hair, contact surface textile / Skin, stiffness.
  • a further object was to provide a process by which textile substrates can be produced which exhibit both permanently good thermophysiological wearing comfort, for example characterized by breathability, thermal insulation, perspiration transport, drying time, and good sensory wearing comfort, for example textile / skin staple force, surface roughness hairiness, contact area textile / skin, stiffness.
  • films of the invention are particularly well suited to produce the desired textile substrates, in the form of layered substrates.
  • the present invention thus relates to the use of films according to the invention for the production of layered materials, and the subject of the present invention is furthermore a process for the production of layered materials using films according to the invention.
  • Another object of the present invention are layered materials comprising at least one textile material and a film according to the invention.
  • a film according to the invention for carrying out the process according to the invention, it is possible, for example, to proceed by combining a film according to the invention with at least one textile material.
  • textile material is combined with the side of the film according to the invention which is not coated with particles according to the invention.
  • Textile materials in the context of the present invention are textile semifinished and finished products and finished products made therefrom, which include, in addition to textiles for the clothing industry, for example, carpets and other home textiles as well as technical purposes serving textile structures. These include unshaped structures such as flakes and preferably area or body structures such as felts, fabrics, knitwear, nonwovens and wadding. Textile materials 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 fabric.
  • Textile materials in the context of the present invention may be colored such as dyed or printed, and they may be finished, for example, equipped without ironing.
  • non-colored textile material is used.
  • non-finished textile material is based on non-finished textile material.
  • the initially defined layered material further comprises a thermoplastic polyurethane film.
  • Thermoplastic polyurethanes also referred to for short as TPU
  • films produced therefrom are known as such.
  • Thermoplastic polyurethanes preferably TPU elastomers
  • TPU elastomers are well known, are commercially available and generally consist of a soft phase of higher molecular weight polyhydroxyl compounds, e.g. from polyester or Polyetherseg- elements, and a urethane hard phase formed from low molecular weight chain extenders and di- or polyisocyanates.
  • thermoplastic polyurethanes by reacting (a) isocyanates, preferably diisocyanates with
  • (b) isocyanate-reactive compounds usually having a molecular weight (Mw) of 500 to 10,000 g / mol, preferably 500 to 5,000 g / mol, more preferably 800 to 3,000 g / mol, and
  • (C) chain extenders having a molecular weight of 50 to 499, optionally in the presence of
  • isocyanates (a) it is possible to use generally known aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, for example tri-, tetra-, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methylpentamethylene diisocyanate 1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl-5-isocyanato methylcyclohexane (isophorone diisocyanate, IPDI), 1,4- and / or 1,3-bis (isocyanatomethyl) cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4- and / or 2, 6-cyclohexane diiso
  • 4,4'-MDI is used.
  • aliphatic diisocyanates in particular hexamethylene diisocyanate (HDI)
  • aromatic diisocyanates such as 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) and mixtures of the above-mentioned isomers.
  • isocyanate-reactive compounds (b) it is possible to use the generally known isocyanate-reactive compounds, for example polyesterols, polyetherols and / or polycarbonatediols, which are usually also grouped under the term "polyols", with molecular weights (M w ) in the region of 500 and 8,000 g / mol, preferably 600 to 6,000 g / mol, in particular 800 to 3,000 g / mol, and preferably an average functionality to isocyanates of 1, 8 to 2.3, preferably 1, 9 to 2.2, in particular 2.
  • polyesterols polyetherols and / or polycarbonatediols
  • M w molecular weights
  • Polyether polyols are preferably used, for example those based on generally known starter substances and customary alkylene oxides, for example ethylene oxide, 1,2-propylene oxide and / or 1,2-butylene oxide, preferably polyetherols based on polyoxytetramethylene (polyTHF), 1 , 2-propylene oxide and ethylene oxide.
  • Polyetherols have the advantage that they have a higher hydrolytic stability than polyesterols, and are preferably as component (b).
  • Polyetherols are preferably by addition of alkylene oxides, in particular ethylene oxide, propylene oxide and mixtures thereof, of diols such as ethylene glycol, 1, 2-propylene glycol, 1, 2-butylene glycol, 1, 4-butanediol, 1, 3-propanediol, or at Triols such as glycerol, prepared in the presence of highly active catalysts.
  • highly active catalysts include cesium hydroxide and dimetal cyanide catalysts, also referred to as DMC catalysts.
  • a frequently used DMC catalyst is zinc hexacyanocobaltate.
  • the DMC catalyst can be left in the polyetherol after the reaction, preferably it is removed, for example by sedimentation or filtration.
  • Chain extenders (c) used are aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 50 to 499 g / mol and at least two functional groups, preferably compounds having exactly two functional groups per molecule, known per se -
  • diamines and / or alkanediols having 2 to 10 carbon atoms in the alkylene radical in particular 1, 3-propanediol, butanediol-1, 4, hexanediol-1, 6 and / or di-, tri-, tetra-, penta-, Hexa, hepta, octa, nona and / or Dekaalkylenglykole having 3 to 8 carbon atoms per molecule, preferably corresponding oligo- and / or polypropylene glycols, whereby mixtures of chain extenders (c) can be used.
  • components (a) to (c) are difunctional compounds, i. Diisocyanates (a), difunctional polyols, preferably polyetherols (b) and difunctional chain extenders, preferably diols.
  • Suitable catalysts (d), which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the constituent components (b) and (c), are per se known tertiary amines, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo- (2,2,2) -octane ("DABCO”) and similar tertiary amines, and especially organic metal compounds such as titanic acid ferric compounds, such as, for example, iron (III) acetylacetonate, tin compounds, eg tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilau
  • auxiliaries and / or additives (e) can also be added to components (a) to (c).
  • components (a) to (c) are blowing agents, anti-blocking agents, surface-active substances, fillers, for example nanoparticle-based fillers, in particular fillers based on CaCC 3, nucleating agents, lubricants, dyes and pigments, antioxidants, for example against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers, metal deactivators
  • the component (e) also includes hydrolysis stabilizers such as, for example, polymeric and low molecular weight carbodiimides,
  • the thermoplastic polyurethane contains triazole and / or triazole derivative and antioxidants In an amount of from 0.1 to 5% by weight, based on the total weight of the thermoplastic polyurethane in question, antioxidants are generally suitable substances which inhibit or prevent undesired oxidative processes in the plastic to be protected Indioxidants commercial
  • antioxidants are hindered phenols, aromatic amines, thiosynergists, trivalent phosphorus organophosphorus compounds, and hindered amine light stabilizers.
  • sterically hindered phenols can be found in Plastics Additive Handbook, 5th edition, H. Zweifel, ed, Hanser Publishers, Kunststoff, 2001 ([1]), pp. 98-107 and p.116- p121
  • Aromatic amines can be found in [1] pp. 107-108.
  • thiosynergists are given in [1], p.104-105 and p.1 12-113.
  • phosphites can be found in [1], p.109-112.
  • Hindered Amine Light Stabilizer examples are given in [1], p.123-136.
  • the antioxidant mixture are preferably phenolic antioxidants.
  • the antioxidants in particular the phenolic antioxidants, have a molecular weight of greater than 350 g / mol, more preferably greater than 700 g / mol and a maximum molecular weight (M w ) of at most 10,000 g / mol, preferably up to a maximum of 3,000 g / mol on.
  • thermoplastic polyurethane films preferably calcium carbonate.
  • chain regulators chain terminators
  • chain regulators usually having a molecular weight of 31 to 3000 g / mol.
  • Such chain regulators are compounds which have only one isocyanate-reactive functional group, e.g. monofunctional alcohols, monofunctional amines and / or monofunctional polyols.
  • chain regulators can generally be used in an amount of from 0 to 5, preferably 0.1 to 1, parts by weight, based on 100 parts by weight of component (b), and fall by definition under component (c).
  • the components (b) and (c) can be selected in relatively broad molar ratios.
  • the reaction for the preparation of the thermoplastic polyurethanes may be at a ratio of 0.8 to 1, 4: 1, preferably at a ratio of 0.9 to 1, 2: 1, more preferably at a ratio of 1, 05 to 1, 2 : 1.
  • the index is defined by the ratio of the total isocyanate groups used in the reaction of component (a) to the isocyanate-reactive groups, i. the active hydrogens, components (b) and optionally (c) and, optionally, monofunctional isocyanate-reactive components as chain terminators such as e.g. Monoalcohols.
  • thermoplastic polyurethanes can be carried out continuously by processes known per se, for example with reaction extruders or the belt process according to one-shot or the prepolymer process, or batchwise by the prepolymer process known per se.
  • the action coming components (a), (b), (c) and optionally (d) and / or (e) are mixed successively or simultaneously with each other, wherein the reaction starts immediately.
  • the components (a), (b), (c) and optionally (d) and / or (e) are introduced individually or as a mixture in the extruder, for example at temperatures of 100 to 280 0 C, preferably 140 to 250 0 C, and reacted.
  • the resulting thermoplastic polyurethane is usually extruded, cooled and granulated.
  • the thermoplastic polyurethane can optionally be modified by formulation on an extruder.
  • thermoplastic polyurethane is extruded according to methods known per se into a film, which is also referred to in the context of the present invention as a thermoplastic polyurethane film.
  • thermoplastic polyurethane films may have an average thickness in the range of 5 to 100 ⁇ m, preferably 10 to 50 ⁇ m, particularly preferably 15 to 40 ⁇ m.
  • Layered materials according to the invention have a good breathability.
  • breathability one can use various methods known per se. For example, ASTM D-6701 is suitable.
  • the contact angle in particular the static contact angle
  • the static contact angle with water of the present invention layer-shaped materials can be, for example, according to methods known per se determined and is, for example up to 50 °, preferably in the range of 10 to 35 °, measured at 20 0 C.
  • the contact angle of numerous uncoated thermo- plastic polyurethane films with water is in many cases at 75 to 80 °, measured at 20 0 C.
  • layered materials according to the invention are strongly hydrophilized on the side of the thermoplastic polyurethane film coated with particles according to the invention. Moisture, especially water, no longer separates in the form of separate drops, but as a thin film.
  • thermophysiological comfort It is also observed that the moisture transport of layered materials according to the invention is greatly improved compared to materials comprising a textile material and a thermoplastic polyurethane film, but no inventive Particulate particles.
  • the drying time is usually significantly shorter, which leads to a significantly improved thermophysiological comfort.
  • Inventive layered materials furthermore have very good fastness properties, for example rub fastnesses, wash fastnesses and wet rub fastnesses. For this purpose, no plasma activation of the film in question is usually required.
  • the coated film in particular the coated thermoplastic polyurethane film, be on the inside of the garment in question.
  • the coated with particles of the invention side of the film in question directed to the body side of the wearer of such garment according to the invention.
  • the production method according to the invention can be carried out without plasma activation of the surface of the thermoplastic polyurethane film.
  • the procedure is to combine a textile material with a film, in particular with a thermoplastic polyurethane film, which is coated on the side facing away from the textile material with particles according to the invention.
  • the procedure is to coat a film, in particular a thermoplastic polyurethane film which is bonded to a textile material, with particles according to the invention.
  • the coating of film, in particular of thermoplastic polyurethane film with particles according to the invention is carried out by treating the relevant film with a preferably aqueous dispersion according to the invention.
  • thermoplastic polyurethane film when coating the film, in particular the thermoplastic polyurethane film, optionally in combination with textile, no shear forces are exerted which lead to an expansion of the relevant film, in particular no shear forces which are so significant irreversible stretching of the film in question.
  • Such a treatment can be carried out, for example, by spraying with preferably aqueous formulation or by immersion in a preferably aqueous dispersion according to the invention.
  • spraying or immersion is on it To ensure that only one side of the film in question brings with inventive preferably aqueous dispersion in contact.
  • the coating is carried out at temperatures in the range from 5 to 95 ° C., preferred are 10 to 50 ° C., particularly preferably 10 to 30 ° C.
  • the preferably aqueous formulation used for coating films contains in the range from 0.1 to 80% by weight, preferably 0.5 to 50% by weight, of particles according to the invention.
  • the preferably aqueous formulation used for coating contains no further components other than water and particles according to the invention.
  • the aqueous formulation used for coating may contain one or more further constituents, for example one or more wetting agents or one or more surface-active substances, for example one or more surfactants, which are selected from anionic or anionic surfactants nonionic surfactants, nonionic surfactants being preferred.
  • one or more surfactants which are selected from anionic or anionic surfactants nonionic surfactants, nonionic surfactants being preferred.
  • nonionic surfactants are, in particular, polyalkoxylated fatty acids, polyalkoxylated fatty acid amides, polyalkoxylated non-quaternized fatty acid amines, polyalkoxylated mono- and diglycerides, optionally polyalkoxylated alkyl polyglycosides, preferably selected from alkyl polyglucosides and sugar ester alkoxylates, and polyethylenated fatty amines, especially up to 20-fold alkoxylated C8-C30 fatty amines, saturated or mono- or polyunsaturated.
  • nonionic surfactants are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C4-C12) and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80, alkyl radical: C8-C36).
  • examples are the Lutensol ® brands of BASF Aktiengesellschaft.
  • suitable wetting agents are, in particular, polyvinyl alcohol and partially saponified polyvinyl acetates, which are commercially available, for example, as Mowiol® grades.
  • saponified polyvinyl acetates for example with up to 40 mol% residual acetyl content, in particular with up to 15 mol%, are preferred.
  • % Residual acetyl content in each case based on the respective non-hydrolyzed polyvinyl acetate.
  • Suitable amounts of wetting agents mentioned above are, for example, a total of 0.01 to 5 wt .-%, preferably 0.05 to 3 wt .-%, based on aqueous dispersion according to the invention.
  • n-butyl glycol which can be used in amounts of up to 30 wt .-%, based on inventive aqueous dispersion.
  • the preferably aqueous dispersion according to the invention is allowed to act on the film, for example over a period of time ranging from 5 minutes to 2 hours, preferably 10 to 45 minutes, before further processing the coated film, for example by thermal treatment or by bonding with textile material.
  • a preferably aqueous dispersion according to the invention is allowed to act on the thermoplastic polyurethane film, for example over a period of time in the range from 5 minutes to 2 hours, preferably 10 to 45 minutes, before being coated
  • Further processed polyurethane film for example by thermal treatment or by bonding with textile material.
  • the coating of the film is fixed, in particular the coating of the thermoplastic polyurethane film after treatment with preferably aqueous dispersion according to the invention, for example by thermal treatment.
  • the thermal treatment can be, for example, at temperatures ranging from 20 to 140 0 C, preferably 50 to 120 0 C, particularly preferably by lead 70 to 100 ° C.
  • Suitable devices for the thermal treatment are, for example, drying cabinets and tenter frames.
  • the thermal treatment can be carried out in one or more steps, for example two or three steps, wherein the temperature in the respective subsequent steps is preferably increased in each case.
  • the average layer thickness of particles according to the invention on thermoplastic polyurethane film in the range of 5 nm to 5 .mu.m, preferably in the range of 10 nm to 2 .mu.m and more preferably in the range of 20 nm to 1 micron.
  • the layer thickness is in each case at one over a Period of 10 minutes at 100 0 C and another 10 minutes at 125 ° C dried polyurethane film determined, for example by microscopic determination or by weighing. It is also possible to determine a theoretical layer thickness by determining the wet layer thickness and, taking into account the concentration of particles according to the invention, calculating the layer thickness of particles according to the invention on thermoplastic polyurethane film.
  • the film optionally coated with particles according to the invention is combined, in particular with thermoplastic particles coated with particles according to the invention, with textile material, for example by gluing or by lamination.
  • the treatment of film with preferably aqueous dispersion according to the invention is carried out by coating a composite body comprising a film and a carrier material to which the relevant film has been applied with particles according to the invention in such a way that the coating is applied to the film. After that you can treat thermally. Thereafter, the film coated with particles according to the invention is separated from the support material and bonded to the textile material.
  • the composite can also be referred to as a layered material in the context of the present invention.
  • thermoplastic polyurethane film with preferably aqueous dispersion according to the invention is carried out in such a way that a composite body comprising a thermoplastic polyurethane film and a carrier material onto which the relevant thermoplastic polyurethane film is applied coated with particles of the invention, in such a way that the coating is applied to the thermoplastic polyurethane film.
  • a composite body comprising a thermoplastic polyurethane film and a carrier material onto which the relevant thermoplastic polyurethane film is applied coated with particles of the invention, in such a way that the coating is applied to the thermoplastic polyurethane film.
  • the thermoplastic polyurethane film coated with particles according to the invention is separated from the carrier material and bonded to the textile material.
  • the composite can also be referred to as a layered material in the context of the present invention.
  • carrier materials are preferably sheet-like materials, in particular film-like materials, for example polymer films such as, for example, polyolefin films or polyester films.
  • the thickness of the carrier material may be greater or smaller than the thickness of the film to be coated, in particular the be thermoplastic polyurethane film, preferably, the thickness of the support material in the range of 1, 1 to 10 times as large as the relevant film or thermoplastic polyurethane film.
  • the thickness of the film to be coated preferably of the thermoplastic polyurethane film to be coated and the carrier material, is the same.
  • a composite body is used for carrying out the production method according to the invention, which comprises, inter alia, a carrier material, in many cases an even more uniform coating with particles according to the invention succeeds.
  • a textile material is applied to the film according to the invention, preferably to the thermoplastic polyurethane film coated with particles according to the invention, preferably on the side which is coated with particles according to the invention.
  • Another object of the present invention are layered materials comprising a film according to the invention, and a support material.
  • Another object of the present invention is the use of layered materials according to the invention, in particular one which comprises a thermoplastic polyurethane film coated with particles of the invention, and at least one textile material, as or for the production of clothing.
  • Another object of the present invention is a process for the production of garments using at least one layered material according to the invention, in particular at least one that a film of the invention, preferably a thermoplastic polyurethane film coated with particles of the invention, and at least comprises a textile material.
  • Another object of the present invention are garments, produced using at least one layered material according to the invention, in particular at least one which comprises a thermoplastic polyurethane film coated with particles of the invention, and at least one textile material.
  • suitable clothing items include: shoes, in particular those with textile parts such as hiking and sports shoes, furthermore jackets, coats, trousers, pullovers, stockings, belts, work clothing, protective clothing, smocks and coveralls, in particular sportswear.
  • Other suitable clothing items suits are protective suits for high-temperature workplaces, for example for the fire brigade or for steel cookers.
  • Garments according to the invention are distinguished by great thermophysiological and sensory wearing comfort, in particular good breathability, good moisture transport and short drying times of perspiration and condensate, with at the same time good fastnesses, in particular washing and rubbing fastnesses.
  • the LD value is the light transmission, measured with:
  • the K value was determined using a LAUDA processor viscosity measurement system
  • PVS1 with Ubbelohde capillary No. I: 1% by weight of particles in demineralized water at
  • 125 g of silica sol with an average particle diameter of 15 nm and a solids content of 40% are diluted with 781, 40 g of demineralized water and placed in a 2 l polymerization vessel. It was heated with stirring to an internal temperature of 99 ° C. 49 g of methacrylic acid, 1 g of methacrylic acid 3-trimethoxysilylpropyl ester (MEMO) and 0.710 g of sodium peroxodisulfate dissolved in 50 g of demineralized water were then metered in over the course of 2 hours. The mixture was then stirred at the same temperature for a further 2 hours.
  • MEMO methacrylic acid 3-trimethoxysilylpropyl ester
  • a homogeneous-looking dispersion D.3 containing particles P.3 according to the invention was obtained with the following analytical data.
  • silica SoI with an average particle diameter of 15 nm and a solids content of 40% was diluted with 803.38 g of deionized water and placed in a 2-liter polymerization vessel. It was heated with stirring to an internal temperature of 99 ° C. 1 l, 70 g of hydroxyethyl methacrylate, 1, 30 g of methyl methacrylate, 1, 30 g of dimethyl aminoethyl methacrylate (DMAEMA) and 0.203 g of sodium peroxodisulfate, dissolved in 195 g of demineralized water, added. The mixture was then stirred at the same temperature for a further 2 hours.
  • DMAEMA dimethyl aminoethyl methacrylate
  • a homogeneous-looking dispersion D.4 containing particles P.4 according to the invention was obtained with the following analytical data.
  • a homogeneous-looking dispersion D.5 containing particles P.5 according to the invention was obtained with the following analytical data.
  • Example I Inventive dispersions of Example I were diluted to a concentration of 1 to 2% (see Table 1) and applied with a nonwoven cloth on the surface to be hydrophilized.
  • the diluent was either a mixture of 70 parts by weight of water and 30 parts by weight of n-butyl glycol (VM 1) or a 1% aqueous solution of a Cio-Guerbet alcohol alkoxylated with 7 mol of ethylene oxide (VM 2).
  • VM 1 n-butyl glycol
  • VM 2 1% aqueous solution of a Cio-Guerbet alcohol alkoxylated with 7 mol of ethylene oxide
  • Detergents RM1.1 to RM5.1 and RM1.2 to RM5.2 were obtained according to the invention. This designates the first digit in the detergents according to the invention in each case the particles P.1 to P.5 according to the invention and the second digit the diluent.
  • Example I For the treatment of ceramic tiles, dispersions of Example I according to the invention were diluted with water (VM 3).
  • the plate was mounted vertically and sprayed with water.
  • the spraying is done with 10 strokes from a spray bottle.
  • the water was allowed to drain and waited 15 minutes for the plate to dry completely. Then you determined again the contact angle.
  • the spraying, drying and measuring of the contact angle was performed a further four times analogously to determine the stability of the hydrophilization.
  • Dispersion D.2 according to the invention was diluted with VM 1 (see Example II.), So that the concentration of particles according to the invention was 0.5%, and the cleaning agent RM2.1 (0.5%) according to the invention was obtained.
  • the specimens were then tilted slightly and rinsed with 150 ml of drinking water (10.4 ° dH).
  • Dispersion D.1 was coated with a spiral doctor blade from Erichsen (30 ⁇ m wet layer thickness) onto a composite of a thermoplastic polyurethane film, thickness 20 ⁇ m, prepared from MDI, 1,4-butanediol and polyethylene glycol, and a polypropylene film, thickness 50 ⁇ m , geräkelt, on the polyurethane side.
  • the composite thus coated was oven-dried for a period of 10 minutes at 100 ° C. and for a further 10 minutes at 125 ° C.
  • Inventive layered material SFM.1 was obtained from a coated thermoplastic polyurethane film which had a very thin ( ⁇ 1 ⁇ m), homogeneous-looking particle coating under the microscope, and a polypropylene film.
  • the contact angle with water was 25 °, determined at 20 0 C.
  • the inventive stratiform material SFM.1 was subjected to a 20-minumble shower test, ie, there was measured on the polyurethane side at an angle of 45 ° for 20 minutes a powerful water jet exposed from a shower head. After the shower test, it was dried for 15 minutes at 100 0 C and measured the contact angle at 20 0 C again. The contact angle was 27 °.
  • the water vapor permeability of the thermoplastic polyurethane film coated according to the invention was measured (ASTM D-6701). The water vapor permeability was 8,000 g / m 2 ⁇ day.
  • Dispersion D.1 was applied to a layered material comprising a thermoplastic polyurethane film which had been laminated to a polyester fabric (basis weight 210 g / m 2 ) using a spiral doctor from Erichsen (20 ⁇ m wet layer thickness), below Laminate called, on the polyurethane side of the laminate geräkelt.
  • the thus-coated laminate was dried over a period of 10 minutes at 100 0 C and another 10 minutes at 125 ° C in the oven.
  • Inventive layered material SFM.2 was obtained which had a very thin ( ⁇ 1 ⁇ m), homogeneous-looking coating under the microscope.
  • the contact angle with water was 22 °, measured at 20 0 C.
  • the layered material SFM.2 according to the invention was washed ten times in the washing machine with a mild detergent at 40 0 C, then the contact angle with water was measured again.
  • the contact angle with water was 23 °, measured at 20 0 C.
  • the Wasserdampf was good.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Nanotechnology (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des particules ayant un diamètre moyen de 3 nm à 100 nm, contenant (A) un matériau solide anorganique, et (B) un (co)polymère organique composé d'au moins 70 % en poids de (co)monomères présentant une solubilité d'au moins 10 g/l dans de l'eau à 25 °C, le rapport massique du matériau solide anorganique (A) sur le (co)polymère (B) étant de 100:1 à 1,1:1.
PCT/EP2008/050788 2007-01-26 2008-01-24 Particules, procédé de fabrication et utilisation WO2008090191A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP07101265 2007-01-26
EP07101265.2 2007-01-26

Publications (2)

Publication Number Publication Date
WO2008090191A2 true WO2008090191A2 (fr) 2008-07-31
WO2008090191A3 WO2008090191A3 (fr) 2010-01-07

Family

ID=39322711

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2008/050788 WO2008090191A2 (fr) 2007-01-26 2008-01-24 Particules, procédé de fabrication et utilisation

Country Status (1)

Country Link
WO (1) WO2008090191A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009013426A1 (de) * 2009-03-18 2010-09-23 THÖNE, Gerd Dämmmaterial

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661311A2 (fr) * 1993-11-09 1995-07-05 Nippon Shokubai Co., Ltd. Particules fines de composé et compositions filmogènes
WO1997000995A1 (fr) * 1995-06-23 1997-01-09 Minnesota Mining And Manufacturing Company Composition et procede permettant de conferer des proprietes repulsives durables a des substrats
DE19821665A1 (de) * 1997-05-28 1998-12-03 Basf Ag Compositpigmente auf Basis von polyalkylenpolyaminmodifizierten nanopartikulären Metalloxiden und anionischen Farbstoffen
WO2000069976A1 (fr) * 1999-05-12 2000-11-23 Universite De Franche-Comte Sol de silice, composition le comprenant, procede de traitement et ses utilisations
DE19952383A1 (de) * 1999-10-30 2001-05-17 Henkel Kgaa Wasch- und Reinigungsmittel
EP1302514A2 (fr) * 2001-10-09 2003-04-16 Mitsubishi Chemical Corporation Composition de revêtement durcissable par rayonnement

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0661311A2 (fr) * 1993-11-09 1995-07-05 Nippon Shokubai Co., Ltd. Particules fines de composé et compositions filmogènes
WO1997000995A1 (fr) * 1995-06-23 1997-01-09 Minnesota Mining And Manufacturing Company Composition et procede permettant de conferer des proprietes repulsives durables a des substrats
DE19821665A1 (de) * 1997-05-28 1998-12-03 Basf Ag Compositpigmente auf Basis von polyalkylenpolyaminmodifizierten nanopartikulären Metalloxiden und anionischen Farbstoffen
WO2000069976A1 (fr) * 1999-05-12 2000-11-23 Universite De Franche-Comte Sol de silice, composition le comprenant, procede de traitement et ses utilisations
DE19952383A1 (de) * 1999-10-30 2001-05-17 Henkel Kgaa Wasch- und Reinigungsmittel
EP1302514A2 (fr) * 2001-10-09 2003-04-16 Mitsubishi Chemical Corporation Composition de revêtement durcissable par rayonnement

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009013426A1 (de) * 2009-03-18 2010-09-23 THÖNE, Gerd Dämmmaterial

Also Published As

Publication number Publication date
WO2008090191A3 (fr) 2010-01-07

Similar Documents

Publication Publication Date Title
EP1984555B1 (fr) Procede de traitement de substrats textiles
DE60220689T2 (de) Befeuchtetes wischtuch enthaltend polymere biguanidverbindungen für die behandelung von oberflächen
EP2071072B1 (fr) Composition de traitement pour produits textiles
DE112006000649B4 (de) Verfahren zur Herstellung einer Nanomembran auf einem Substrat
EP2084321B1 (fr) Procédé de traitement de substrats
EP1984556A1 (fr) Procede de traitement de substrats
DE10215522A1 (de) Kationisch modifizierte anionische Polyurethandispersionen
CN109715772B (zh) 片材形式的洗涤剂组合物
DE102006016638A1 (de) Mikroporöse Beschichtung auf Basis von Polyurethan-Polyharnstoff
EP3481887B1 (fr) Préparations en tant qu'agents d'hydrofugation
DE102007055725A1 (de) Mehrlagiges Material, umfassend mindestens zwei metallisierte Schichten auf mindestens einem Textil, und Verfahren zu seiner Herstellung
WO2002038852A1 (fr) Polyisocyanates a pouvoir hydrophile modifie et polyurethanes permettant l'appret anti-plis de textiles contenant de la cellulose
DE102007013141A1 (de) Amphotere Polymere als Soil Release Additive in Wasch- und Reinigungsmitteln
EP2997091A1 (fr) Effets hydrofuges sur des surfaces textiles
WO2018146016A1 (fr) Polymères pour le traitement hydrophobe et oléophobe de textiles
WO2008090191A2 (fr) Particules, procédé de fabrication et utilisation
EP3555155B1 (fr) Feuilles multicouches à action lavante et détergente, leur procédé de fabrication et d'utilisation
EP1776501B1 (fr) Procede pour appreter des materiaux absorbants
WO2008083908A1 (fr) Matériaux stratiformes à fort pouvoir respirant et procédé pour les produire
EP2931769B1 (fr) Principes actifs polymères améliorant le pouvoir détergent primaire
EP2992075B1 (fr) Polymères en peigne comme renforçateurs de détergence pour des lessives
DE102005004299A1 (de) Verfahren zur Behandlung von flexiblen Substraten
JP7239158B2 (ja) 撥水剤、撥水処理された繊維基材の製造方法、撥水性繊維物品、コーティング膜付き撥水性繊維物品、及びコーティング膜付き撥水性繊維物品の製造方法
EP2176308B1 (fr) Dispersions aqueuses, leur fabrication et leur utilisation
JP3851290B2 (ja) アニオン性ジオールからなるポリウレタン形成用ポリオール成分および組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 08708131

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 08708131

Country of ref document: EP

Kind code of ref document: A2