EP1287102B1 - Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rin age, agents d'entretien, detergents et nettoyants - Google Patents

Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rin age, agents d'entretien, detergents et nettoyants Download PDF

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EP1287102B1
EP1287102B1 EP01938247A EP01938247A EP1287102B1 EP 1287102 B1 EP1287102 B1 EP 1287102B1 EP 01938247 A EP01938247 A EP 01938247A EP 01938247 A EP01938247 A EP 01938247A EP 1287102 B1 EP1287102 B1 EP 1287102B1
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weight
water
hydrophobic polymers
particulate
anionic
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EP1287102A1 (fr
Inventor
Dieter Boeckh
Ralf NÖRENBERG
Jürgen Detering
Werner Bertleff
Holger SCHÖPKE
Reinhold J. Leyrer
Jürgen HUFF
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BASF SE
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BASF SE
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    • 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
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0031—Carpet, upholstery, fur or leather cleansers
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the invention relates to the use of cationically modified, particulate, hydrophobic polymers as an additive to rinsing, care, washing and cleaning agents and rinsing, care, washing and cleaning agents containing the cationically modified, particulate, hydrophobic polymers.
  • Dispersions of particles of hydrophobic polymers are used in the art to modify the properties of surfaces.
  • aqueous dispersions of finely divided hydrophobic polymers as binders in paper coating slips for the coating of paper or as a paint.
  • the in each case on a substrate according to common methods, e.g. by means of doctoring, brushing, impregnating or impregnating applied dispersions are dried. In the process, the dispersed particles on the respective surface form a coherent film.
  • Aqueous washing, rinsing, cleaning and care processes are usually carried out in a highly diluted liquor, the ingredients of each applied formulation does not remain on the substrate, but rather be disposed of with the wastewater.
  • the modification of surfaces with dispersed hydrophobic particles succeeds in the abovementioned processes only to a completely unsatisfactory extent.
  • a detergent formulation which contains a water-insoluble finely divided substance such as biocides and certain cationic polymers which increase the deposition and retention of the biocides on the surfaces of the laundry.
  • US-A-5 476 660 also discloses the principle of using polymeric retention aids for cationic or zwitterionic dispersions of polystyrene or wax containing an active substance embedded in the dispersed particles. These dispersed particles are referred to as “carrier particles", because they adhere to the treated surface and there release the active substance, for example when used in surfactant-containing formulations.
  • the present invention has for its object to provide a further method for modifying surfaces available.
  • the object is achieved according to the invention with the use of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by coating with polyvalent metal ions and / or cationic surfactants and whose particle size is 10 nm to 100 ⁇ m, as an additive to rinsing, care, , Detergents and cleaners.
  • the cationically modified particulate hydrophobic polymers are obtainable, for example, by treating aqueous dispersions of particulate hydrophobic polymers having a particle size of 10 nm to 100 ⁇ m with an aqueous solution of polyvalent metal salts, an aqueous solution of a cationic surfactant or mixtures thereof. This is most easily accomplished by combining an aqueous dispersion of particulate hydrophobic polymers having a particle size of 10 nm to 100 ⁇ m with an aqueous solution of a water-soluble metal salt or a surfactant.
  • the two components are mixed at room temperature, but can be mixed at temperatures of, for example, 0 ° to 100 ° C, provided that the dispersions do not coagulate on heating.
  • the dispersions of the particulate hydrophobic polymers can be stabilized with the aid of an anionic emulsifier or protective colloid.
  • Other dispersions which can be used with equal success are free of protective colloids and emulsifiers and contain as hydrophobic polymers copolymers which contain at least one anionic monomer in copolymerized form.
  • Such dispersions of anionic group-containing copolymers may optionally additionally contain an emulsifier and / or a protective colloid.
  • anionic emulsifiers and / or protective colloids are used.
  • cationically modified dispersions of particulate hydrophobic polymers in 0.1% by weight aqueous dispersion have an interfacial potential of -5 to +50 mV, preferably from -2 to +25 mV, in particular from 0 to +15 mV.
  • the interfacial potential is determined by measuring the electrophoretic mobility in dilute aqueous dispersion and the pH of the intended application liquor.
  • the pH of the aqueous dispersions of the cationically modified, particulate, hydrophobic polymers is for example 1 to 12 and is preferably in the range of 2 to 10, in particular in the range of 2.5 to 8.
  • the pH of the aqueous dispersions is from 1 to 7.5, preferably from 2 to 5.5, in particular from 2.5 to 5.
  • the hydrophobic polymers to be used according to the invention are insoluble in water at the pH of the application. They are present therein in the form of particles having an average particle size of 10 nm to 100 .mu.m, preferably 25 nm to 20 .mu.m, more preferably 40 nm to 2 microns and especially 60 to 800 nm and can be obtained from the aqueous dispersions as a powder.
  • the mean particle size of the hydrophobic polymers may be e.g. be determined under the electron microscope or by means of light scattering experiments.
  • a preferred embodiment of particles of the hydrophobic polymers to be used according to the invention exhibits a pH-dependent solubility and swelling behavior.
  • the particles are water-insoluble and retain their particulate character when dispersed in concentrated as well as in dilute aqueous media.
  • carboxyl-containing hydrophobic polymer particles swell in water under neutral and alkaline conditions.
  • This behavior of hydrophobic polymers having anionic groups is known from the literature, cf. M. Siddiq et al., In Colloid. Polym. Sci. 277, 1172-1178 (1999) report the behavior of particles of methacrylic acid / ethyl acrylate copolymers in an aqueous medium.
  • Hydrophobic polymers for example, are obtainable by polymerization of monomers from the group of alkyl esters of monoethylenically unsaturated C 3 -C 5 -carboxylic acids and monohydric C 1 -C 22 alcohols, hydroxyalkyl esters of monoethylenically unsaturated C 3 -C 5 carboxylic acids and divalent C 2 - C 4 -alcohols, vinyl esters of saturated C 1 -C 18 -carboxylic acids, ethylene, propylene, isobutylene, C 4 -C 24 - ⁇ -olefins, butadiene, styrene, ⁇ -methylstyrene, acrylonitrile, methacrylonitrile, tetrafluoroethylene, vinylidene fluoride, fluoroethylene, Chlorotrifluoroethylene, hexafluoropropene, esters and amides of C 3 -C 5 monoethylenically uns
  • hydrophobic copolymers are copolymers of ethyl acrylate and vinyl acetate, copolymers of butyl acrylate and styrene, copolymers of (meth) acrylic acid esters of perfluoroalkyl-substituted alcohols of the formula CF 3 - (C 2 F 4 ) n - (CH 2 ) m -OH or C 2 F.
  • the anionic character of the polymers mentioned can be achieved, for example, by reacting the monomers on which the copolymers are present in the presence of small amounts of anionic monomers such as acrylic acid, methacrylic acid, styrenesulfonic acid, acrylamido-2-methylpropanesulfonic acid, vinylsulfonate and / or maleic acid and optionally Presence of emulsifiers and / or protective colloids copolymerized.
  • anionic monomers such as acrylic acid, methacrylic acid, styrenesulfonic acid, acrylamido-2-methylpropanesulfonic acid, vinylsulfonate and / or maleic acid and optionally Presence of emulsifiers and / or protective colloids copolymerized.
  • anionic character of the polymers mentioned can also be achieved by carrying out the copolymerization in the presence of anionic protective colloids and / or anionic emulsifiers.
  • anionic character of the mentioned polymers can also be achieved by emulsifying or dispersing the finished polymers in the presence of anionic protective colloids and / or anionic emulsifiers.
  • Polymers containing at least one anionic monomer (b) or (c) can be used without additional anionic emulsifiers or protective colloids. Polymers containing less than 0.5% by weight of anionic monomers are most commonly used together with at least one anionic emulsifier and / or protective colloid.
  • Preferably used hydrophobic polymers contain less than 75 wt .-% of a nonionic water-insoluble monomer (a) in copolymerized form, whose homopolymers have a glass transition temperature Tg (in the index) of more than 60 ° C.
  • Preferably used monomers (b) are acrylic acid, methacrylic acid, maleic acid or maleic monoesters of C 1 -C 8 -alcohols.
  • Examples of monomers of group (c) are acrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, methallylsulfonic acid, vinylsulfonic acid and the alkali metal and ammonium salts of these monomers.
  • Suitable monomers (d) are acrylamide, methacrylamide, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, N-vinyl oxazolidone, methylpolyglycol acrylates, methylpolyglycol methacrylates and methylpolyglycol acrylamides.
  • Preferably used monomers (d) are vinylpyrrolidone, acrylamide and N-vinylformamide.
  • Suitable multiply ethylenically unsaturated monomers are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols.
  • the OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups. Examples are butanediol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate and tripropylene glycol diacrylate.
  • Suitable multiply ethylenically unsaturated monomers are e.g. Allyl esters of unsaturated carboxylic acids, divinylbenzene, methylenebisacrylamide and divinylurea.
  • Such copolymers can be prepared by the known methods of solution, precipitation, suspension or emulsion polymerization of the monomers using free-radical polymerization initiators.
  • the particulate hydrophobic polymers are obtained by the process of emulsion polymerization in water.
  • the polymers have, for example, molecular weights of from 1 000 to 2 million, preferably from 5 000 to 500 000, in most cases the molecular weights of the polymers are in the range from 10 000 to 150 000.
  • regulators can be added during the polymerization.
  • typical regulators are mercapto compounds such as mercaptoethanol or thioglycolic acid.
  • polymers can be precipitated by lowering the solubility of the polymers in the solvent.
  • Such a method consists, for example, in dissolving a copolymer containing acidic groups in a suitable water-miscible solvent and metering it in an excess of water such that the pH of the original is at least 1 lower than the equivalent pH of the template copolymers.
  • equivalence pH is meant the pH at which 50% of the acidic groups of the copolymer are neutralized.
  • polymers which partially or completely react or associate with them and precipitate out can additionally be added during the dispersion.
  • polymers are, for example, polysaccharides, polyvinyl alcohols and polyacrylamides.
  • Particulate, hydrophobic polymers may also be prepared by the controlled emulsification of a melt of the hydrophobic polymers.
  • strong shear forces e.g. in an Ultra-Turrax
  • emulsifying aids, pH regulators and / or salts in order to obtain stable finely divided dispersions.
  • additional polymers such as polysaccharides, polyvinyl alcohols or polyacrylamides, in particular if the hydrophobic polymer contains anionic groups.
  • Another method for preparing finely divided hydrophobic polymers containing anionic groups is that one adds aqueous, alkaline solutions of the polymers preferably under the action of strong shear forces with an acid.
  • anionic emulsifiers examples include anionic surfactants and soaps.
  • anionic surfactants alkyl and alkenyl sulfates, sulfonates, phosphates and phosphonates, alkyl and alkenyl benzene sulfonates, alkyl ether sulfates and phosphates, saturated and unsaturated C 10 -C 25 carboxylic acids and their salts can be used.
  • nonionic and / or betaine emulsifiers can be used.
  • suitable emulsifiers can be found e.g. in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.
  • anionic protective colloids are water-soluble anionic polymers.
  • very different types of polymers can be used.
  • Suitable anionically substituted polysaccharides are, for example, carboxymethylcellulose, carboxymethyl starch, oxidized starch, oxidized cellulose and other oxidized polysaccharides and the corresponding derivatives of the partially degraded polysaccharides.
  • Suitable water-soluble anionic copolymers are, for example, copolymers of acrylic acid with vinyl acetate, acrylic acid with ethylene, acrylic acid with acrylamide, acrylamidopropanesulfonic acid with acrylamide or acrylic acid with styrene.
  • nonionic and / or betaine protective colloids may be used.
  • An overview of commonly used protective colloids can be found in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 411-420.
  • hydrophobic polymers are preferably used anionic polymeric protective colloids, which lead to primary particles with anionic groups on the particle surface.
  • the cationically modified, particulate, hydrophobic polymers to be used according to the invention are obtainable by coating the surface of the anionically dispersed, particulate, hydrophobic polymers with polyvalent metal ions and / or cationic surfactants.
  • An occupancy of the particles with polyvalent metal ions is achieved by, for example, adding to an aqueous dispersion of anionically dispersed hydrophobic polymers an aqueous solution of at least one water-soluble, polyvalent metal salt or dissolving a water-soluble polyvalent metal salt therein.
  • Suitable metal salts are, for example, the water-soluble salts of Ca, Mg, Ba, Al, Zn, Fe, Cr or mixtures thereof.
  • Other water-soluble heavy metal salts derived for example from Cu, Ni, Co and Mn, are in principle usable, but not desired in all applications.
  • water-soluble metal salts are calcium chloride, calcium acetate, magnesium chloride, aluminum sulfate, aluminum chloride, barium chloride, zinc chloride, zinc sulfate, zinc acetate, ferrous sulfate, ferric chloride, chromium (III) sulfate, copper sulfate, nickel sulfate , Cobalt sulfate and Manganese sulfate.
  • the water-soluble salts of Ca, Mg, Al and Zn are used for cationization.
  • cationic surfactants of very different structure.
  • An overview of a selection of suitable cationic surfactants can be found in Ullmann's Enzyklischen der Industrielle Chemie, Sixth Edition, 1999, Electronic Release, chapter “Surfactants”, Chapter 8, Cationic Surfactants.
  • Particularly suitable cationic surfactants are e.g.
  • modifying the properties of smooth or textured surfaces with dispersions is important. It is not always possible to modify the surfaces by impregnating, spraying and brushing with concentrated dispersions. Often it is desirable to modify by means of rinsing the material to be treated with a highly diluted, active substance-containing liquor or by spraying a highly diluted one to carry out aqueous formulation. It is often desirable to combine the modification of the surface of materials in the context of a laundry, cleaning and / or care or impregnation of the surface.
  • surfaces of different materials are considered, eg hard macroscopic surfaces such as floor and wall coverings, exposed concrete, stone facades, plastered facades, glass surfaces, ceramic surfaces, metal surfaces, enamelled surfaces, plastic surfaces, wood surfaces, surfaces of coated wood or painted surfaces, microscopic Surfaces such as porous bodies (eg foams, woods, leather, porous building materials, porous minerals), fiber structures such as fiber surfaces in textiles and textile tiles, floor and wall coverings, floor and wall coatings or coatings, furniture coverings and cellulose fleeces.
  • treated surfaces are floor and wall coverings made of plastics or ceramics, furniture surfaces and objects made of glass and metal.
  • textiles in particular cotton fabric and cotton blended fabrics, carpets and upholstery covers are preferably required for treatment.
  • the modification of the surfaces can consist, for example, in a hydrophobing, soil release finish, dirt-repellent finish, reinforcement of the fiber composite and protection against chemical or mechanical influences or damage.
  • the cationically modified, particulate, hydrophobic polymers are used to modify surfaces of the above-exemplified materials as an additive to rinse, conditioner, impregnating, washing and cleaning products. They can be used, for example, as the sole active component in aqueous rinsing and care compositions and, depending on the composition of the polymer, for example, facilitate soil removal in a subsequent wash, lower soil adhesion during use, an improvement in the structural integrity of fibers, an improvement in the molding process. and structure preservation of fabrics, a hydrophobing of the surface of the laundry and a handle improvement.
  • the concentration of the cationically modified, particulate, hydrophobic polymers when used in the rinsing or care bath, in the detergent liquor or in the cleaning bath is, for example, 0.0002 to 1.0% by weight, preferably 0.0005 to 0.25% by weight. %, more preferably 0.002 to 0.05 wt .-%.
  • the treatment of laundry, textile surfaces, leather, wood and hard surfaces is preferably carried out with aqueous liquors containing at least 0.5 mmol / l of water-soluble Ca, Mg or Zn salts and / or at least 0.05 mmol of water-soluble Al Salts and / or contain at least 50 ppm of at least one cationic surfactant.
  • Laundry aftertreatment and laundry care products may be liquid, gel or solid.
  • the agents of this preferred embodiment are particularly suitable for achieving soil release promoting properties. From so aftertreated laundry soiling that occur in the use phase, easily removed in the subsequent wash.
  • the agents of this preferred embodiment are particularly suitable for achieving hydrophobicizing or impregnating properties. From so aftertreated laundry water is absorbed or transmitted to a much lesser extent.
  • the agents of this preferred embodiment are particularly suitable for achieving dirt-repellent properties, in particular oil and grease-soiling. So aftertreated tissue absorbs oil and grease dirt to a lesser extent.
  • Suitable acids are both mineral acids such as sulfuric acid or phosphoric acid or organic acids such as carboxylic acids or sulfonic acids. Strong acids such as sulfuric acid, phosphoric acid or sulfonic acids are generally used in partially neutralized form.
  • the cationic modification of the particulate, hydrophobic polymers is preferably carried out before use in the aqueous treatment agents, but it can also in the preparation of aqueous treatment agents or the application of anionically emulsified, particulate, hydrophobic polymers with a particle size of 10 nm to 100 microns, for example, by mixing aqueous dispersions of eligible particulate polymers with the other constituents of the respective treatment agent in the presence of water-soluble salts of polyvalent metals and / or cationic surfactants.
  • anionic particles or formulations containing these particles directly to the rinsing, washing or cleaning liquor, if it is ensured that sufficient amounts of polyvalent metal ions and / or cationic surfactants are present in dissolved form in the liquor.
  • Cationic surfactants are used for example in concentrations of 50 to 100 ppm, preferably 75 to 500 ppm and in particular from 100 to 300 ppm in the aqueous liquor.
  • anionic particles or formulations containing these particles can also be added before, after or at the same time as a formulation containing cationic surfactants.
  • composition of typical anionic dispersions which can be processed by mixing with water-soluble salts of polyvalent metals and / or cationic surfactants and other components to rinse, care, impregnating, washing and cleaning agents, are the dispersions I to V described below whose dispersed particles are each to be observed in the electron microscopic examination as discrete particles with the indicated average particle diameter:
  • the dispersion contained 1.25 wt .-% of a Anionic surfactant as an emulsifier and 20 wt .-% of a low molecular weight starch as a protective colloid. It had a pH of 4.
  • the average diameter of the dispersed particles of the dispersion was 176 nm.
  • the dispersion contained 0.8% by weight of an anionic surfactant as an emulsifier and had a pH of 4.
  • the dispersion contained 0.8 wt .-% of an anionic surfactant as emulsifier and had a pH of 4.
  • aqueous dispersion of a polymer of 64% by weight of n-butyl acrylate, 32% by weight of methyl methacrylate and 4% by weight of acrylic acid was 35% by weight.
  • the mean diameter of the dispersed particles of the dispersion was 80 nm.
  • the dispersion contained 1.5% by weight of an anionic surfactant as an emulsifier and had a pH of 6.
  • typical formulations according to the invention with soil release action can be prepared, which are used, for example, in household washing in the final rinse of the washing machine in a dosage of 2 to 5 g / l, preferably 3 g / l:
  • the formulation may optionally contain other ingredients such as common soil release polymers for polyesters, grayness inhibitors, perfume, dyes, enzymes, hydrotropes, solvents, nonionic surfactants, silicone oil, a fabric softener and / or a thickener.
  • common soil release polymers for polyesters, grayness inhibitors, perfume, dyes, enzymes, hydrotropes, solvents, nonionic surfactants, silicone oil, a fabric softener and / or a thickener.
  • the formulation may optionally contain further ingredients such as conventional soil release polymers for polyesters, grayness inhibitors, perfume, dyes, enzymes, hydrotropes, solvents, nonionic surfactants, silicone oil, a fabric softener and / or a thickener.
  • further ingredients such as conventional soil release polymers for polyesters, grayness inhibitors, perfume, dyes, enzymes, hydrotropes, solvents, nonionic surfactants, silicone oil, a fabric softener and / or a thickener.
  • the anionic character of the abovementioned dispersions can optionally additionally be adjusted by polymerizing the polymers in the presence of small amounts (up to 10% by weight) of anionic monomers such as acrylic acid, styrenesulfonic acid, vinylphosphonic acid or acrylamido-2-methylpropanesulfonic acid ,
  • anionic monomers such as acrylic acid, styrenesulfonic acid, vinylphosphonic acid or acrylamido-2-methylpropanesulfonic acid
  • These dispersions are preferably first cationically modified by treatment with water-soluble polyvalent metal salts or with cationic surfactants, or the cationic modification of the dispersions is carried out during the preparation of the rinse or conditioner as described above under Formulations I to IV.
  • the cationically modified, particulate, hydrophobic polymers to be used according to the invention which are thus obtainable have a hydrophobing, fiber-reinforcing and dirt-repellent action on the textiles treated with them in the rinse cycle of the household washing machine.
  • the formulation can be used, for example, in a dilution with water in a weight ratio of 1:50 to 1: 1000 for rinsing or aftertreatment of the abovementioned materials.
  • the formulation can be used, for example, in a dilution with water in a weight ratio of 1:20 to 1: 5000 for rinsing or aftertreatment of the abovementioned materials.
  • the dispersions I to V can also be used, for example, directly or as a formulation with further constituents in water containing at least 0.5 mol / l of Ca 2+ , Mg 2+ or Zn 2+ or at least 0.05 mol / l of Al 3 + contains.
  • formulations of this preferred embodiment are particularly suitable for imparting improved soil release to the surfaces so treated in the subsequent cleaning.
  • the better soil removal is achieved in particular if the subsequent cleaning is carried out with a neutral or alkaline cleaning liquor.
  • the formulations of this preferred embodiment are particularly suitable for imparting water-repellent or impregnating properties to the cleaned surfaces. Water is absorbed to a lesser extent from surfaces treated in this way, and water is less able to penetrate the surface.
  • the formulations of this preferred embodiment are particularly suitable for imparting dirt-repellent, in particular oil and greasy soil-repelling properties to the surface thus cleaned.
  • the laundry aftertreatment and conditioning agents and detergents described above may also be formulated as solid compositions based on the same ingredients.
  • solid forms are powders, granules and tablets.
  • the surfaces of fabrics, fibers, glass, plastics, metals, wood and ceramics treated with the cationically modified dispersions of hydrophobic polymers to be used according to the invention are easier to remove from soiling after a soiling in a subsequent aqueous washing or cleaning process than the untreated surfaces , With the cationically modified dispersions to be used according to the invention, a much higher soil release effect is achieved, in particular on cotton and cellulose fibers, than with known water-soluble soil release polymers.
  • the surfactants, builders, co-builders, complexing agents, solvents, color transfer inhibitors, soil release polyesters, bleaches, bleach activators, grayness inhibitors, enzymes, perfumes, solvents, thickeners, oils, waxes, hydroptropes, foam inhibitors, silicones, brighteners and Dyes can be combined within the usual customary in rinsing, care, washing and cleaning formulations starting materials.
  • Detergents Part 3, Detergent Ingredients, Part 4, Household Detergents and Part 5, Institutional Detergents in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Version 2.0.
  • Preferred nonionic surfactants are, for example, alkoxylated C 8 -C 22 -alcohols, such as fatty alcohol ethoxylates and oxo alcohol alkoxylates, which are reacted with from 3 to 15 mol of ethylene oxide and optionally additionally with 1 to 4 mol of propylene oxide and / or butylene oxide are alkoxylated, and block polymers of ethylene oxide and propylene oxide having a molecular weight of 900 to 12,000 and a weight ratio of ethylene oxide to propylene oxide of 1 to 20.
  • alkoxylated C 8 -C 22 -alcohols such as fatty alcohol ethoxylates and oxo alcohol alkoxylates, which are reacted with from 3 to 15 mol of ethylene oxide and optionally additionally with 1 to 4 mol of propylene oxide and / or butylene oxide are alkoxylated
  • block polymers of ethylene oxide and propylene oxide having a molecular weight of
  • Particularly preferred nonionic surfactants are C 13 / C 15 oxo alcohol ethoxylates and C 12 / C 14 fatty alcohol ethoxylates which are reacted with 3 to 11 moles of ethylene oxide per mole of alcohol or first with 3 to 10 moles of ethylene oxide and then with 1 to 3 moles of propylene oxide per mole of alcohol are alkoxylated.
  • Preferred anionic surfactants are, for example, alkylbenzenesulfonates having linear or branched C 6 -C 25 -alkyl groups, fatty alcohol and oxoalcohol sulfates having C 8 -C 22 -alcohols and fatty alcohol or oxoalcohol ether sulfates of C 8 -C 22 -alcohols containing from 1 to 5 mol Ethylene oxide per mole of alcohol are ethoxylated and sulfated at the OH end group of the ethoxylate.
  • formulations according to the invention are formulated with low content of anionic surfactants, particularly preferably without anionic surfactants.
  • anionic surfactants are used in the formulations, ether sulfates are preferably used.
  • Preferred solvents are alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and butanediol.
  • Preferred builders are alkali carbonates, phosphates, polyphosphates, zeolites and silicates. Particularly preferred builders are zeolite A, zeolite P, phyllosilicates, soda and trisodium polyphosphate.
  • Preferred complexing agents are nitrilotriacetic acid, methylglycinediacetic acid and ethylenediaminetetraacetate.
  • Preferred co-builders are acrylic acid homopolymers, acrylic acid / maleic acid copolymers, polyaspartic acid and citric acid.
  • Particularly preferred cobuilders are acrylic acid homopolymers of molecular weight 1,500 to 30,000 and acrylic acid / maleic acid copolymers with a molar ratio of the monomers of 10: 1 to 1: 2 and molecular weights of 4,000 to 100,000.
  • Preferred soil-release polyesters are polyesters of terephthalic acid, ethylene glycol and polyethylene glycol, with polyethylene glycols having molecular weights of from 1 000 to 5 000 condensed in, and those polyesters in which terephthalic acid is replaced by up to 50 mol% by sulfocarboxylic acids or sulfodicarboxylic acids.
  • Preferred dye transfer inhibitors are polyvinylpyrrolidone of molecular weights 8,000 to 70,000, vinylimidazole / vinylpyrrolidone copolymers having a molar ratio of the monomers of 1:10 to 2: 1 and molecular weights of 8,000 to 70,000 and poly-4-vinylpyridine N-oxides having molecular weights from 8,000 to 70,000.
  • Preferred enzymes are proteases, lipases, cellulases and amylases.
  • Formulations according to the invention may optionally additionally contain further protective colloids for stabilizing the disperse state. This is particularly important in liquid formulations to prevent coagulation.
  • the protective colloids can also advantageously be added to solid formulations in order to prevent coagulation during use.
  • protective colloids it is possible to use water-soluble polymers, in particular water-soluble nonionic polymers.
  • suitable protective colloids have molecular weights of from 800 to 200,000, more preferably from 5,000 to 70,000, especially from 10,000 to 50,000.
  • Suitable protective colloids are e.g. Polyvinylpyrrolidone, polyethylene glycol, block polymers of ethylene oxide and propylene oxide, enzymatically degraded starches, and polyacrylamides.
  • the anionic dispersions I and IV were used.
  • the dispersion contained 1.25 wt .-% of a Anionic surfactants as emulsifier and 20 wt .-% of a low molecular weight starch as a protective colloid. It had a pH of 4.
  • the anionic dispersion I was brought to a level of 0.040% with deionized water of pH 4. A white cotton fabric was hung in the magnetically stirred liquor for 30 minutes. The extinction of the liquor was measured by means of a Vis spectrometer at 520 nm. Within 30 minutes, no change in absorbance was observed. Electron micrographs showed almost no coverage of the cotton fibers with dispersion particles.
  • the anionic dispersion I was brought to a content of particles of 10% with deionized water of pH 4.
  • the dispersion was metered in with stirring with a magnetic stirrer over the course of 30 minutes to the same volume of a 50 mmol solution of CaCl 2 , pH 4.
  • the dispersion was stable for hours.
  • This dispersion was diluted with 1 mmol of Ca 2+ -containing water of pH 4 to a content of 0.040%.
  • a white cotton fabric was hung in the magnetically stirred liquor for a period of 30 minutes. Over 30 minutes, the extinction of the liquor was measured by means of a Vis spectrometer at 520 nm. A large decrease in absorbance was observed.
  • the anionic dispersion I was brought to a content of 0.040% with 3 mmol of Ca 2+ -containing water of pH 4.
  • a white cotton fabric was hung in the magnetically stirred liquor for 30 minutes.
  • the extinction of the liquor was measured by means of a Vis spectrometer at 520 nm. Within 30 minutes, a large decrease in absorbance was observed.
  • the anionic dispersion I was brought to a content of 0.040% with 3 mmol of Zn 2+ -containing water of pH 4.
  • a white cotton fabric was hung in the magnetically stirred liquor for 30 minutes.
  • the extinction of the liquor was measured by means of a Vis spectrometer measured at 520 nm. Within 30 minutes, a large decrease in absorbance was observed.
  • the anionic dispersion I was brought to a content of 0.040% with 3 mmol of Al 3+ -containing water of pH 4.
  • a white cotton fabric was hung in the magnetically stirred liquor for 30 minutes.
  • the extinction of the liquor was measured by means of a Vis spectrometer at 520 nm. Within 30 minutes, a large decrease in absorbance was observed.
  • Cotton fabric was prewashed with the anionic dispersion I.
  • the dispersion was used in the absence of polyvalent metal salt and cationic surfactant.
  • Ca acetate was added to the dispersion before washing.
  • esterquat methyl quat of di-tallow fatty acid ester of triethanolamine
  • the prewashed fabrics were soiled with lipstick and then washed with a heavy duty detergent (Ariel Futur). To evaluate the soil release effect, the remission of the soiled fabrics was measured before and after the wash and combined in a known manner with the remission value of the white cotton fabric determines the soil release in% oil release.
  • Cotton fabric was washed with commercial detergent and rinsed in the rinse with hard water containing the fluoropolymer dispersion IV. In comparative experiment 5, no dispersion was added in the final rinse bath. In comparative experiment 6, demineralized water containing the fluoropolymer disperse IV was used in the final rinse.
  • the rinsed fabrics were spun, dried and ironed. To test for stain resistance, each fabric was placed flat over the opening of a 5 cm diameter beaker. Then a drop of dirty engine oil was applied centrally. It was checked after every 10 seconds, 180 minutes and 1 day, whether the oil drop had penetrated into the tissue.

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Claims (21)

  1. Utilisation de polymères hydrophobes, particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par recouvrement avec des ions métalliques polyvalents et/ou des agents tensioactifs cationiques et dont la taille de particule est de 10 nm à 100 µm, comme addition à des produits de rinçage, d'entretien, de lavage et de nettoyage.
  2. Utilisation suivant la revendication 1, caractérisée en ce que les polymères hydrophobes, particulaires, modifiés de manière cationique peuvent être obtenus par traitement de dispersions aqueuses de polymères hydrophobes particulaires ayant une taille de particule de 10 nm à 100 µm avec une solution aqueuse de sels métalliques polyvalents, une solution d'un agent tensioactif cationique ou leurs mélanges.
  3. Utilisation suivant la revendication 1 ou 2, caractérisée en ce que les dispersions des polymères hydrophobes particulaires sont stabilisés à l'aide d'un agent émulsionnant anionique et/ou d'un colloïde de protection anionique.
  4. Utilisation suivant l'une des revendications 1 à 3, caractérisée en ce que les polymères hydrophobes contiennent, à l'état copolymérisé, au moins un monomère anionique.
  5. Utilisation suivant l'une des revendications 1 à 4, caractérisée en ce que les dispersions modifiées de manière cationique de polymères hydrophobes particulaires possèdent, dans une dispersion aqueuse à 0,1 % en poids, une tension superficielle de -5 à +50 mV.
  6. Utilisation suivant l'une des revendications 1 à 5, caractérisée en ce que la valeur de pH des dispersions aqueuses des polymères hydrophobes particulaires, modifiés de manière cationique, est de 2 à 12.
  7. Utilisation suivant l'une des revendications 1 à 6, caractérisée en ce que les sels métalliques sont choisis parmi le groupe des sels solubles dans l'eau de Ca, Mg, Al, Zn ou de leurs mélanges.
  8. Utilisation suivant l'une des revendications 1 à 7, caractérisée en ce que la concentration des polymères hydrophobes particulaires, modifiés de manière cationique, est de 0,0002 à 1,0 % en poids lors de l'application dans un bain de rinçage ou d'entretien, dans la lessive de lavage ou le bain de nettoyage.
  9. Utilisation suivant l'une des revendications 1 à 8, caractérisée en ce que la concentration des polymères hydrophobes particulaires, modifiés de manière cationique, est de 0,002 à 0,05 % en poids lors de l'application dans un bain de rinçage ou d'entretien, dans la lessive de lavage ou le bain de nettoyage.
  10. Produit de traitement de linge, de surfaces textiles, de cuir, de bois et de surfaces dures, caractérisé en ce qu'il contient
    (a) 0,05 à 40 % en poids de polymères hydrophobes particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par recouvrement avec des ions métalliques polyvalents et/ou des agents tensioactifs cationiques et dont la taille de particule est de 10 nm à 100 µm,
    (b) 0,01 à 20 % en poids d'au moins un sel soluble dans l'eau de Ca, Mg, Al, Zn et/ou 0,01 à 30 % en poids d'au moins un agent tensioactif cationique,
    (c) 0 à 80 % en poids d'au moins un additif courant, tel que des acides ou des bases, des adjuvants inorganiques, des coadjuvants organiques, d'autres agents tensioactifs, des inhibiteurs de transfert de couleur polymères, des inhibiteurs de passage au gris polymères, des polymères antisalissants, des enzymes, des agents complexants, des inhibiteurs de corrosion, des cires, des huiles de silicone, des agents de protection contre la lumière, des colorants, des solvants, des hydrotropes, des agents épaississants et/ou des alcanolamines, et
    (d) de l'eau pour compléter à 100 % en poids.
  11. Produit suivant la revendication 10, caractérisé en ce que les bains aqueux contiennent au moins 0,5 mmole/l de sels solubles dans l'eau de Ca, Mg ou Zn et/ou au moins 0,05 mmole de sels solubles dans l'eau de Al et/ou au moins 50 ppm d'au moins un agent tensioactif cationique.
  12. Produits de traitement final de linge et d'entretien de linge liquides ou en forme de gels, caractérisés en ce qu'ils contiennent
    (a) 0,1 à 30 % en poids de polymères hydrophobes, particulaires qui contiennent, à l'état copolymérisé, au moins un groupe de monomères anioniques éthyléniquement insaturés, ont une taille de particule de 10 nm à 100 µm et sont dispersés dans l'eau,
    (b) 0,05 à 20 % en poids d'un acide,
    (c) 0,1 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0 à 10 % en poids d'au moins un autre constituant courant, tel que du parfum, d'autres agents tensioactifs, de l'huile de silicone, un agent de protection contre la lumière, un colorant, un complexant, un inhibiteur de passage au gris, un polyester antisalissant, un inhibiteur de transfert de couleur, un solvant non aqueux, un hydrotrope, un agent épaississant et/ou de l'alcanolamine, et
    (e) de l'eau pour compléter à 100 % en poids.
  13. Produits de traitement final de linge et d'entretien de linge liquides ou en forme de gels suivant la revendication 12, caractérisés en ce qu'ils contiennent
    (a) 0,5 à 25 % en poids de polymères hydrophobes particulaires qui contiennent, à l'état copolymérisé, 25 à 60 % en poids d'un monomère éthyléniquement insaturé contenant au moins un groupe d'acide carboxylique, ont une taille de particule de 10 nm à 100 µm et sont dispersés dans l'eau avec un agent émulsionnant anionique et/ou un colloïde de protection anionique,
    (b) 0,05 à 10 % en poids d'au moins un acide,
    (c) 0,1 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0 à 10 % en poids d'au moins un autre constituant courant, tel que du parfum, d'autres agents tensioactifs, de l'huile de silicone, un agent de protection contre la lumière, un colorant, un complexant, un inhibiteur de passage au gris, un polyester antisalissant, un inhibiteur de transfert de couleur, un solvant non aqueux, un hydrotrope, un agent épaississant et/ou de l'alcanolamine, et
    (e) de l'eau pour compléter à 100 % en poids.
  14. Produits de traitement final de linge et d'entretien de linge liquides ou en forme de gels, caractérisés en ce qu'ils contiennent
    (a)0,5 à 25 % en poids de polymères hydrophobes particulaires, qui contiennent, à l'état copolymérisé, 75 à 100 % en poids d'au moins un monomère éthyléniquement insaturé, soluble dans l'eau, ou 10 à 100 % en poids d'un monomère éthyléniquement insaturé, contenant des substituants fluorés, ont une taille de particule de 10 nm à 100 µm et sont dispersés dans l'eau avec un agent émulsionnant anionique et/ou un colloïde de protection anionique,
    (b) 0 à 10 % en poids d'au moins un acide,
    (c) 0,1 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0 à 10 % en poids d'au moins un autre constituant courant, tel que du parfum, d'autres agents tensioactifs, de l'huile de silicone, un agent de protection contre la lumière, un colorant, un complexant, un inhibiteur de passage au gris, un polyester antisalissant, un inhibiteur de transfert de couleur, un solvant non aqueux, un hydrotrope, un agent épaississant et/ou de l'alcanolamine, et
    (e) de l'eau pour compléter à 100 % en poids.
  15. Formulation de nettoyage et d'entretien liquide ou en forme de gel, caractérisée en ce qu'elle contient
    (a) 0,05 à 30 % en poids de polymères hydrophobes particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par recouvrement avec des ions métalliques polyvalents et/ou des agents tensioactifs cationiques et dont la taille de particule est de 10 nm à 100 µm,
    (b) 0,01 à 40 % en poids d'au moins un agent tensioactif non ionique ou anionique,
    (c) 0,01 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0 à 10 % en poids d'au moins un complexant,
    (e) 0 à 20 % en poids d'autres constituants courants, tels que des régulateurs de pH, des additifs, d'autres agents tensioactifs, des épaississants, des solvants, des hydrotropes, des acides polycarboxyliques, des silicones, des générateurs de brillant, du parfum et/ou des colorants, et
    (f) 0 à 90 % en poids d'eau.
  16. Formulation de nettoyage acide liquide ou en forme de gel, caractérisée en ce qu'elle contient
    (a) 0,1 à 30 % en poids de polymères hydrophobes particulaires, qui contiennent, à l'état copolymérisé, au moins un groupe de monomères éthyléniquement insaturés anioniques, ont une taille de particule de 10 nm à 100 µm et sont dispersés dans l'eau,
    (b) 0,05 à 20 % en poids d'un acide,
    (c) 0,1 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (e) 0 à 10 % en poids d'au moins un complexant,
    (f) 0 à 20 % en poids d'autres constituants courants, tels que des régulateurs de pH, des additifs, d'autres agents tensioactifs, des épaississants, des solvants, des hydrotropes, des acides polycarboxyliques, des silicones, des agents générateurs de brillant, du parfum et/ou des colorants, et
    (g) 0 à 90 % en poids d'eau.
  17. Formulation de nettoyage acide liquide ou en forme de gel, caractérisée en ce qu'elle contient
    (a) 0,5 à 25 % en poids de polymères hydrophobes particulaires, qui contiennent, à l'état copolymérisé, 25 à 60 % en poids d'un monomère éthyléniquement insaturé, contenant au moins un groupe d'acide carboxylique, ont une taille de particule de 10 nm à 100 µm et sont dispersés dans l'eau avec un agent émulsionnant anionique et/ou un colloïde de protection anionique,
    (b) 0,1 à 40 % en poids d'au moins un agent tensioactif non ionique ou anionique,
    (c) 0,1 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0,1 à 20 % en poids d'au moins un acide,
    (e) 0 à 10 % en poids d'au moins un complexant,
    (f) 0 à 20 % en poids d'autres constituants courants, tels que des régulateurs de pH, des additifs, d'autres agents tensioactifs, des épaississants, des solvants, des hydrotropes, des acides polycarboxyliques, des silicones, des agents générateurs de brillant, du parfum et/ou des colorants, et
    (g) 0 à 90 % en poids d'eau.
  18. Formulation de nettoyage liquide ou en forme de gel, caractérisée en ce qu'elle contient
    (a) 0,5 à 25 % en poids de polymères hydrophobes particulaires, qui contiennent, à l'état copolymérisé, 75 à 100 % en poids d'au moins un monomère éthyléniquement insaturé, soluble dans l'eau, ou 10 à 100 % en poids d'un monomère éthyléniquement insaturé, contenant des substituants fluorés, ont une taille de particule de 10 nm à 100 µm et sont dispersés dans l'eau avec un agent émulsionnant anionique et/ou un colloïde de protection anionique,
    (b) 0,1 à 40 % en poids d'au moins un agent tensioactif non ionique ou anionique,
    (c) 0,1 à 30 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0 à 20 % en poids d'au moins un acide,
    (e) 0 à 10 % en poids d'au moins un complexant,
    (f) 0 à 20 % en poids d'autres constituants courants, tels que des régulateurs de pH, des additifs, d'autres agents tensioactifs, des épaississants, des solvants, des hydrotropes, des acides polycarboxyliques, des silicones, des agents générateurs de brillant, du parfum et/ou des colorants, et
    (g) 0 à 90 % en poids d'eau.
  19. Produits d'entretien et de traitement final liquides ou en forme de gels, caractérisés en ce qu'ils contiennent
    (a) 0,05 à 15 % en poids de polymères hydrophobes particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par recouvrement avec des ions métalliques polyvalents et/ou des agents tensioactifs cationiques et dont la taille de particule est de 10 nm à 100 µm,
    (b) 0 à 20 % en poids d'au moins un agent tensioactif non ionique, cationique et/ou anionique,
    (c) 0 à 15 % en poids d'au moins un sel soluble dans l'eau de Mg, Ca, Zn ou Al et/ou d'un agent tensioactif cationique,
    (d) 0 à 5 % en poids d'au moins un complexant,
    (e) 0 à 10 % en poids d'autres constituants courants, tels que des régulateurs de pH, des additifs, des épaississants, des solvants, des hydrotropes, des acides polycarboxyliques, des silicones, des agents générateurs de brillant, du parfum et/ou des colorants, et
    (f) 0 à 99,5 % en poids d'eau.
  20. Formulation solide de produit de lavage, caractérisée en ce qu'elle contient
    (a) 0,05 à 20 % en poids de polymères hydrophobes particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par recouvrement avec des ions métalliques polyvalents et/ou des agents tensioactifs cationiques et dont la taille de particule est de 10 nm à 100 µm,
    (b) 0,1 à 40 % en poids d'au moins un agent tensioactif non ionique, cationique et/ou anionique,
    (c) 0 à 50 % en poids d'un adjuvant inorganique,
    (d) 0 à 10 % en poids d'un coadjuvant organique,
    (e) 0 à 60 % en poids d'autres constituants courants, tels que des additifs, des enzymes, du parfum, des complexants, des inhibiteurs de corrosion, des agents de blanchiment, des activateurs de blanchiment, des catalyseurs de blanchiment, des inhibiteurs de transfert de couleur, des inhibiteurs de passage au gris, des polyesters antisalissants, des colorants, des agents améliorant la dissolution et/ou des agents de libération.
  21. Formulation de produit de lavage liquide ou en forme de gel, caractérisée en ce qu'elle contient
    (a) 0,05 à 20 % en poids de polymères hydrophobes particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par recouvrement avec des ions métalliques polyvalents et/ou des agents tensioactifs cationiques et dont la taille de particule est de 10 nm à 100 µm,
    (b) 0,1 à 40 % en poids d'au moins un agent tensioactif non ionique, cationique et/ou anionique,
    (c) 0 à 20 % en poids d'un adjuvant inorganique,
    (d) 0 à 10 % en poids d'un coadjuvant organique,
    (e) 0 à 10 % en poids d'autres constituants courants, tels que de la soude, des enzymes, du parfum, des complexants, des inhibiteurs de corrosion, des agents de blanchiment, des activateurs de blanchiment, des catalyseurs de blanchiment, des inhibiteurs de transfert de couleur, des inhibiteurs de passage au gris, des polyesters antisalissants, des colorants, des solvants non aqueux, des hydrotropes, des agents épaississants et/ou des alcanolamines, et
    (f) 0 à 90 % en poids d'eau.
EP01938247A 2000-06-06 2001-06-02 Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rin age, agents d'entretien, detergents et nettoyants Expired - Lifetime EP1287102B1 (fr)

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DE10027636 2000-06-06
DE10027636A DE10027636A1 (de) 2000-06-06 2000-06-06 Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül-, Pflege-, Wasch- und Reinigungsmitteln
PCT/EP2001/006311 WO2001094515A1 (fr) 2000-06-06 2001-06-02 Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rinçage, agents d'entretien, detergents et nettoyants

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JP2003535986A (ja) 2003-12-02
ATE362971T1 (de) 2007-06-15
ES2286123T3 (es) 2007-12-01
AU2001263948A1 (en) 2001-12-17
US6911054B2 (en) 2005-06-28
DE10027636A1 (de) 2001-12-13
US20040077517A1 (en) 2004-04-22
EP1287102A1 (fr) 2003-03-05
DE50112522D1 (de) 2007-07-05
WO2001094515A1 (fr) 2001-12-13

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