EP1287104B1 - Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rin age ou d'entretien destines a des textiles et comme additif pour detergents - Google Patents

Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rin age ou d'entretien destines a des textiles et comme additif pour detergents Download PDF

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EP1287104B1
EP1287104B1 EP01947335A EP01947335A EP1287104B1 EP 1287104 B1 EP1287104 B1 EP 1287104B1 EP 01947335 A EP01947335 A EP 01947335A EP 01947335 A EP01947335 A EP 01947335A EP 1287104 B1 EP1287104 B1 EP 1287104B1
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polymers
particulate
cationic
hydrophobic polymers
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EP1287104A1 (fr
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Dieter Boeckh
Ralf NÖRENBERG
Sören HILDEBRANDT
Bernhard Mohr
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
    • C11D3/16—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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

Definitions

  • the invention relates to the use of cationically modified, particulate, hydrophobic polymers as an additive to rinse or care products and as an additive to detergents and rinse, care and detergent 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 knife coating, 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 the modification of textile surfaces available.
  • the object is achieved with the use of cationically modified, particulate, hydrophobic polymers whose surface is cationically modified by occupancy with cationic polymers and whose particle size is 10 nm to 100 microns, as an additive to rinse or care products for textiles and as an additive to detergents.
  • 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 or dispersion of a cationic polymer. This is most easily done by combining an aqueous dispersion of particulate hydrophobic polymers having a particle size of 10 nm to 100 ⁇ m with an aqueous solution or dispersion of a cationic polymer.
  • the cationic polymers are preferably used in the form of aqueous solutions, but it is also possible to use aqueous dispersions of cationic polymers whose dispersed particles have an average diameter of up to 1 ⁇ m. Most often, the two components are mixed at room temperature, but mixing at temperatures of e.g. 0 ° to 100 ° C, provided that the dispersions do not coagulate when heated.
  • 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.
  • the particles of the hydrophobic polymers to be used according to the invention exhibit a pH-dependent solubility and swelling behavior.
  • the particles are water-insoluble and retain their particulate character during dispersion in concentrated and 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) on the behavior of particles report from 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 or 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% of anionic monomers are most commonly used 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 of more than 60 ° C.
  • 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.
  • polyethylenically unsaturated monomers are e.g. Allyl esters of unsaturated carboxylic acids, divinylbenzene, methylenebisacrylamide and divinylurea.
  • regulators can be added during the polymerization.
  • typical regulators are mercapto compounds such as mercaptoethanol or thioglycolic acid.
  • anionic protective colloids are water-soluble anionic polymers.
  • Anionically substituted polysaccharides and / or water-soluble anionic copolymers of acrylic acid, methacrylic acid, maleic acid, maleic monoesters, vinylsulfonic acid, styrenesulfonic acid or acrylamidopropanesulfonic acid with other vinylic monomers are preferably used.
  • Suitable anionically substituted polysaccharides are e.g. Carboxymethylcellulose, carboxymethyl starch, oxidized starch, oxidized cellulose and other oxidized polysaccharides and the corresponding derivatives of the partially degraded polysaccharides.
  • esters of ethylenically unsaturated carboxylic acids with amino alcohols such as dimethylaminoethyl, dimethylaminoethyl, diethylaminoethyl, diethylaminoethyl, dimethylaminopropyl, dimethylaminopropyl, diethylaminopropyl, dimethylaminobutyl and diethylaminobutyl acrylate.
  • the basic acrylates can be used in the form of the free bases, the salts with mineral acids such as hydrochloric acid, sulfuric acid or nitric acid, the salts with organic acids such as formic acid, acetic acid, propionic acid or sulfonic acids or in quaternized form.
  • Suitable quaternizing agents are, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or benzyl chloride.
  • Suitable comonomers are amides of ethylenically unsaturated carboxylic acids such as acrylamide, methacrylamide and N-alkyl mono- and diamides of monoethylenically unsaturated carboxylic acids having alkyl radicals of 1 to 6 carbon atoms, e.g.
  • basic (meth) acrylamides such as dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide, diethylaminoethylmethacrylamide, dimethylaminopropylacrylamide, diethylaminopropylacryl
  • N-vinylpyrrolidone N-vinylcaprolactam
  • acrylonitrile methacrylonitrile
  • N-vinylimidazole and also substituted N-vinylimidazoles, such as N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-methylimidazole , N-vinyl-2-ethylimidazole, and N-vinylimidazolines such as N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-ethylimidazoline.
  • N-vinylimidazoles and N-vinylimidazolines are also used, except in the form of the free bases, in neutralized or quaternized form with mineral acids or organic acids, the quaternization preferably being carried out with dimethyl sulfate, diethyl sulfate, methyl chloride or benzyl chloride.
  • diallyldialkylammonium halides such as diallyldimethylammonium chlorides.
  • sulfo-containing monomers such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the alkali metal or ammonium salts of these acids or 3-sulfopropyl acrylate, the content of the amphoteric copolymers of cationic units exceeding the content of anionic units, so that the polymers have a total cationic charge.
  • the hydrolysis of the above-described polymers is carried out by known methods by the action of acids, bases or enzymes. This is formed from the copolymerized monomers of formula I above by cleavage of the moiety wherein R 2 has the meaning given in formula I, polymers, the vinylamine units of the formula contain, in which R 1 has the meaning given in formula I.
  • acids are used as hydrolysis units, the units III are present as ammonium salt.
  • the homopolymers of the N-vinylcarboxamides of the formula I and their copolymers can be hydrolyzed to from 0.1 to 100, preferably from 70 to 100, mol%. In most cases, the degree of hydrolysis of the homopolymers and copolymers is 5 to 95 mol%.
  • the degree of hydrolysis of the homopolymers is synonymous with the content of the polymers of vinylamine units.
  • hydrolysis of the ester groups to form vinyl alcohol units may occur. This is especially the case when carrying out the hydrolysis of the copolymers in the presence of sodium hydroxide solution.
  • the polymers containing vinylamine units are preferably used in salt-free form.
  • Salt-free aqueous solutions of polymers comprising vinylamine units can be prepared, for example, from the above-described salt-containing polymer solutions by means of ultrafiltration on suitable membranes at separation limits of, for example, 1000 to 500,000 daltons, preferably 10,000 to 300,000 daltons.
  • the aqueous solutions of amino and / or ammonium groups described below containing other polymers can be obtained by means of ultrafiltration in salt-free form.
  • Polyethyleneimines are prepared, for example, by polymerization of ethyleneimine in aqueous solution in the presence of acid-releasing compounds, acids or Lewis acids.
  • Polyethyleneimines have, for example, molecular weights of up to 2 million, preferably from 200 to 500,000. Particular preference is given to using polyethyleneimines having molecular weights of from 500 to 100,000.
  • water-soluble crosslinked polyethyleneimines obtainable by reaction of polyethyleneimines with crosslinkers such as epichlorohydrin or bischlorohydrin ethers of polyalkylene glycols having from 2 to 100 ethylene oxide and / or propylene oxide units.
  • amidic polyethyleneimines obtainable, for example, by amidation of polyethylenimines with C 1 -C 22 -monocarboxylic acids.
  • suitable cationic polymers are alkylated polyethyleneimines and alkoxylated polyethyleneimines. In the alkoxylation used, for example, per NH unit in polyethyleneimine 1 to 5 ethylene oxide or propylene oxide.
  • polyamidoamines In the preparation of the polyamidoamines it is also possible to use mixtures of dicarboxylic acids, as well as mixtures of several polyalkylenepolyamines.
  • Suitable polyalkylenepolyamines are, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine and bisaminopropylethylenediamine.
  • the dicarboxylic acids and polyalkylenepolyamines are heated to higher temperatures, for example to temperatures in the range from 120 to 220, preferably 130 to 180 ° C., in order to prepare the polyamidoamines.
  • the water produced during the condensation is removed from the system.
  • lactones or lactams of carboxylic acids having 4 to 8 C atoms in the condensation.
  • from 0.8 to 1.4 mol of a polyalkylenepolyamine is used per mole of a dicarboxylic acid.
  • polymers containing amino groups are polyamidoamines grafted with ethyleneimine. They are obtainable from the polyamidoamines described above by reaction with ethyleneimine in the presence of acids or Lewis acids such as sulfuric acid or boron trifluoride etherates at temperatures of, for example, 80 to 100 ° C. Compounds of this type are described for example in DE-B-24 34 816.
  • the optionally crosslinked polyamidoamines which are optionally additionally grafted before crosslinking with ethyleneimine, are suitable as cationic polymers.
  • the crosslinked polyethyleneamines grafted with ethyleneimine are water-soluble and have e.g. an average molecular weight of 3000 to 1 million daltons.
  • Typical crosslinkers are e.g. Epichlorohydrin or bischlorohydrin ethers of alkylene glycols and polyalkylene glycols.
  • cationic polymers containing amino and / or ammonium groups are polydiallyldimethylammonium chlorides. Polymers of this type are also known.
  • Suitable cationic polymers are copolymers of, for example, 1 to 99 mol%, preferably 30 to 70 mol%, acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol%, of cationic monomers, such as dialkylaminoalkylacrylamide, acrylic esters and / or methacrylamide and / or methacrylic esters.
  • cationic monomers such as dialkylaminoalkylacrylamide, acrylic esters and / or methacrylamide and / or methacrylic esters.
  • the basic acrylamides and methacrylamides are also preferably present in acids neutralized or quaternized form.
  • Examples include N-called Trimethylammoniumethylacrylamidchlorid, N-Trimethylammoniumethylmethacrylamidchlorid, N-Trimethylammoniumethylmethacrylesterchlorid, N-Trimethylammoniumethylacrylesterchlorid, Trimethylammoniumethylacrylamidmethosulfat, Trimethylammoniumethylmethacrylamidmethosulfat, N-Ethyldimethylammoniumethylacrylamidethosulfat, N-Ethyldimethylammoniumethylmethacrylamidethosulfat, Trimethylammoniumpropylacrylamidchlorid, Trimethylammoniumpropylmethacryl - amidchlorid, Trimethylammoniumpropylacrylamidmethosulfat, Trimethylammoniumpropylmethacrylamidmethosulfat and N-Ethyldimethylammoniumpropylacrylamidethosulfat.
  • Preferred is trimethylammonium propylmethacrylamide chloride.
  • Suitable cationic monomers for the preparation of (meth) acrylamide polymers are diallyldimethylammonium halides and basic (meth) acrylates. Suitable examples are copolymers of 1 to 99 mol%, preferably 30 to 70 mol%, acrylamide and / or methacrylamide and 99 to 1 mol%, preferably 70 to 30 mol%, Dialkylaminoalkylacrylaten and / or methacrylates such as copolymers Acrylamide and N, N-dimethylaminoethyl acrylate or copolymers of acrylamide and dimethylaminopropyl acrylate.
  • Basic acrylates or methacrylates are preferably present in acids neutralized or quaternized form. The quaternization can be carried out, for example, with methyl chloride or with dimethyl sulfate.
  • Suitable cationic polymers which have amino and / or ammonium groups are also polyallylamines.
  • Polymers of this type are obtained by homopolymerization of allylamine, preferably in acids neutralized or quaternized form or by copolymerizing allylamine with other monoethylenically unsaturated monomers described above as comonomers for N-vinylcarboxamides.
  • the cationic polymers have e.g. K values of 8 to 300, preferably 100 to 180 (determined according to H. Fikentscher in 5% strength aqueous sodium chloride solution at 25 ° C. and a polymer concentration of 0.5% by weight). At a pH of 4.5, for example, they have a charge density of at least 1, preferably at least 4 meq / g polyelectrolyte.
  • anionic comonomers for example acrylic acid, methacrylic acid, vinyl sulfonic acid or alkali metal salts of said acids.
  • anionically dispersed, particulate, hydrophobic polymers they may additionally be treated with polyvalent metal ions and / or cationic surfactants in addition to a treatment with cationic polymers.
  • An occupancy of the particles with polyvalent metal ions is achieved by adding, for example, 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, wherein the modification of the anionically dispersed hydrophobic particles with cationic polymers either before, simultaneously or after this treatment.
  • 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.
  • Examples of 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.
  • the transhipment of the anionically dispersed hydrophobic polymers also succeeds with cationic polymers and cationic surfactants.
  • cationic surfactants Potentially suitable for this purpose are 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.
  • modifying the properties of textiles with dispersions is important. It is not always possible to modify the surfaces by impregnating, spraying and brushing with concentrated dispersions. It is often desirable to carry out the modification by means of rinsing the textile material to be treated with a highly diluted liquor containing an active substance or by spraying a highly diluted aqueous formulation. It is often desirable to modify the surface of textiles in the context of a laundry, cleaning and / or care or impregnation of the surface to combine. Of the textiles in particular cotton fabric and cotton blends come into consideration. In addition, carpets and furniture covers can be treated according to the invention.
  • the modification of the surfaces of textile materials may consist, for example, in a hydrophobing, soil release equipment, 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 fabric rinse or conditioners, and as laundry detergents. They can be used, for example, as the sole active component in aqueous rinse and care products and, depending on the composition of the polymer, for example, facilitate soil removal in a subsequent wash, lower soil adhesion during use of the textiles, improve the structure retention of fibers, improve the Preservation of texture and structure of fabrics, a hydrophobing of the surface of the laundry and a handle improvement.
  • 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 cationically modified by treatment with water-soluble cationic polymers, or the cationic modification of the dispersions is carried out during the preparation of the rinsing or care agents.
  • 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 solvents are alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and butanediol.
  • Preferred builders are alkali metal carbonates, phosphates, polyphosphates, zeolites and silicates. Particularly preferred builders are zeolite A, zeolite P, phyllosilicates, soda and trisodium polyphosphate.
  • Preferred enzymes are proteases, lipases, cellulases and amylases.
  • Suitable protective colloids are e.g. Polyvinylpyrrolidone, polyethylene glycol, block polymers of ethylene oxide and propylene oxide, enzymatically degraded starches, and polyacrylamides.
  • the dispersion I was used.
  • 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 anionic dispersion I was brought to a content 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.
  • Dispersion I was made with deionized water of pH 4 to a content of particles of 10 wt .-%. This dispersion was metered in with stirring by means of a magnetic stirrer to the same volume of a 1% strength solution of high molecular weight crosslinked polyethyleneimine (molecular weight 2,000,000) adjusted to pH 4 over a period of 30 minutes. The dispersion was stable for hours.
  • This dispersion was diluted with deionized water of pH 4 to a level 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.
  • Example 1 was repeated with the exception that the cationic polymer used was a copolymer of vinylimidazole and vinylpyrrolidone (monomer ratio 1: 1) of molecular weight 10,000 for coating the dispersion particles.
  • the cationic polymer used was a copolymer of vinylimidazole and vinylpyrrolidone (monomer ratio 1: 1) of molecular weight 10,000 for coating the dispersion particles.
  • Example 1 was repeated with the exception that the cationic polymer used was a polycondensate of imidazole and epichlorohydrin (molar ratio of the components 1: 1) of molar mass 12,000 for coating the dispersion particles.
  • Table 1 Extinction of the dispersions measured at 520 nm in a 1 cm cuvette. The values reflect the extinction of the diluted dispersion before dipping the cotton fabric and after 30 minutes. measuring time Comparative Example 1 example 1
  • Cotton fabric was prewashed with Dispersion I.
  • Comparative Experiment 3 the dispersion was used in the absence of cationic polymer.
  • the dispersion particles were initially coated with 10% by weight of the cationic polymers as described in Examples 1 to 3.
  • the prewashed fabrics were soiled with lipstick and then washed with a heavy duty detergent (Ariel Futur).
  • Ariel Futur a heavy duty detergent
  • the dispersion IV was brought with deionized water of pH 6 to a content of 0.4% by weight of particles. This dispersion was added with stirring in 30 min to the same volume of a adjusted to pH 6 0.02 wt .-% solution of polyethyleneimine in the molecular weight M w 25 000 metered. A stable dispersion was obtained.

Claims (17)

  1. Utilisation de polymères hydrophobes, particulaires, modifiés de manière cationique, dont la surface est modifiée de manière cationique par revêtement avec des polymères cationiques et dont la taille de particule est de 10 nm à 100 µm, comme addition à des produits de rinçage ou d'entretien de textiles et comme addition à des produits de lavage.
  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, présentant une taille de particule de 10 nm à 100 µm par une dispersion ou solution aqueuse de polymères cationiques.
  3. Utilisation suivant la revendication 1 ou 2, caractérisée en ce que les dispersions des polymères hydrophobes, particulaires, sont stabilisées 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, un potentiel interfacial 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 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 ou dans une lessive de lavage.
  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 0,002 à 0,05% en poids lors de l'application dans un bain de rinçage ou d'entretien ou dans la lessive de lavage.
  9. Utilisation suivant l'une des revendications 1 à 8, caractérisée en ce que, comme polymères cationiques, on met en oeuvre des polymères contenant des unités vinylamine, des polymères contenant des unités vinylimidazole, des polymères contenant des unités vinylimidazole quaternaires, des produits de condensation d'imidazole et d'épichlorhydrine, des polyamidoamines réticulées, des polyamidoamines réticulées greffées avec de l'éthylèneimine, des polyéthylèneimines, des polyéthylèneimines alcoxylées, des polyéthylèneimines réticulées, des polyéthylèneimines amidées, des polyéthylèneimines alkylées, des polyamines, des produits de polycondensation d'amine et d'épichlorhydrine, des polyamines alcoxylées, des polyallylamines, des chlorures de polydiméthyldiallylammonium, des polymères contenant des unités (méth)acrylamide ou (méth)acrylate basiques, des polymères contenant des unités (méth)acrylamide ou (méth)acrylate quaternaires basiques et/ou des produits de condensation de lysine.
  10. Utilisation suivant l'une des revendications 1 à 9, caractérisée en ce que les polymères hydrophobes, particulaires, modifiés de manière cationique, sont en supplément modifiés de manière cationique par revêtement avec des ions métalliques plurivalent et/ou des agents tensioactifs cationiques.
  11. Produit de traitement de linge et de surfaces textiles, 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 revêtement avec des polymères cationiques et dont la taille de particule est de 10 nm à 100 µm,
    (b) 0,01 à 10 % en poids d'au moins un polymère cationique, et
    (c) 0 à 80 % en poids d'au moins un additif courant, comme des acides ou bases, des adjuvants inorganiques, des coadjuvants organiques, des agents tensioactifs, des inhibiteurs de transfert de couleur polymères, des inhibiteurs de teinte grise polymères, des polymères antisalissants, des enzymes, des complexants, des inhibiteurs de corrosion, des cires, des huiles de silicone, des agents de protection contre la lumière, des colorants, des parfums, des solvants, des hydrotropes, des sels, des épaississants et/ou des alcanolamines.
  12. Produits de post-traitement et d'entretien de linge liquides ou en forme de gel, 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 éthyléniquement insaturés anioniques, présentent 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 10 % en poids d'au moins un polymère cationique,
    (d) 0 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 autre constituant courant, comme du parfum, d'autres agents tensioactifs, de l'huile de silicone, un agent de protection contre la lumière, des colorants, des complexants, un inhibiteur de teinte grise, un polyester antisalissant, un inhibiteur de transfert de couleur, un solvant non aqueux, un hydrotrope, un épaississant et/ou une alcanolamine, et
    (f) de l'eau pour compléter à 100 % en poids.
  13. Produits de post-traitement et d'entretien de linge suivant la revendication 12, caractérisés en ce que, comme composant (a), ils contiennent 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 acide carboxylique, présentent 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.
  14. Produits de post-traitement et d'entretien de linge suivant la revendication 12, caractérisés en ce que, comme composant (a), ils contiennent 0,5 à 25 % en poids de polymères hydrophobes, particulaires qui contiennent à l'état copolymérisé 0,1 à 10 % en poids d'un monomère éthyléniquement insaturé contenant au moins un groupe acide carboxylique et au moins 80 % en poids d'un monomère non ionique, éthyléniquement insaturé, insoluble dans l'eau, présentent 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.
  15. Produits de post-traitement et d'entretien de linge suivant la revendication 12, caractérisés en ce que, comme composant (a), ils contiennent 0,5 à 25 % en poids de polymères hydrophobes, particulaires qui contiennent à l'état copolymérisé 10 à 100 % en poids d'un monomère éthyléniquement insaturé contenant un substituant fluoré, présentent 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.
  16. 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 revêtement avec des polymères cationiques et éventuellement en supplément par des ions métalliques plurivalents 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, et
    (e) 0 à 60 % en poids d'autres constituants courants, comme des additifs, des enzymes, du parfum, d'autres agents tensioactifs, 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 teinte grise, des polyesters antisalissants, des colorants, des agents améliorant la dissolution et/ou des agents de libération.
  17. Formulation de produit de lavage liquide ou en forme de gel, caractérisée en 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 revêtement avec au moins un polymère cationique et éventuellement en supplément par des ions métalliques plurivalents 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, comme du carbonate de sodium, des enzymes, du parfum, d'autres agents tensioactifs, 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 teinte grise, des polyesters antisalissants, des colorants, des solvants non aqueux, des hydrotropes, des épaississants et/ou des alcanolamines, et
    (f) 0 à 90 % en poids d'eau.
EP01947335A 2000-06-06 2001-06-02 Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rin age ou d'entretien destines a des textiles et comme additif pour detergents Expired - Lifetime EP1287104B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10027634A DE10027634A1 (de) 2000-06-06 2000-06-06 Verwendung von kationisch modifizierten, teilchenförmigen, hydrophoben Polymeren als Zusatz zu Spül- oder Pflegemitteln für Textilien und als Zusatz zu Waschmitteln
DE10027634 2000-06-06
PCT/EP2001/006312 WO2001094516A1 (fr) 2000-06-06 2001-06-02 Utilisation de polymeres hydrophobes, particulaires, modifies par voie cationique, comme additif pour agents de rinçage ou d'entretien destines a des textiles et comme additif pour detergents

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EP1287104B1 true EP1287104B1 (fr) 2006-05-24

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US (1) US6908490B2 (fr)
EP (1) EP1287104B1 (fr)
JP (1) JP2003535960A (fr)
AT (1) ATE327308T1 (fr)
AU (1) AU2001269048A1 (fr)
CA (1) CA2410442A1 (fr)
DE (2) DE10027634A1 (fr)
MX (1) MXPA02011216A (fr)
WO (1) WO2001094516A1 (fr)

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WO2001094516A1 (fr) 2001-12-13
ATE327308T1 (de) 2006-06-15
EP1287104A1 (fr) 2003-03-05
JP2003535960A (ja) 2003-12-02
MXPA02011216A (es) 2003-03-10
CA2410442A1 (fr) 2001-12-13
US20030171246A1 (en) 2003-09-11
DE10027634A1 (de) 2001-12-13
AU2001269048A1 (en) 2001-12-17
DE50109880D1 (de) 2006-06-29
US6908490B2 (en) 2005-06-21

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