EP1419231A1 - Additiv für eine zusammensetzung zur behandlung von textilien sowie seine verwendung als pflegemittel - Google Patents

Additiv für eine zusammensetzung zur behandlung von textilien sowie seine verwendung als pflegemittel

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Publication number
EP1419231A1
EP1419231A1 EP02796301A EP02796301A EP1419231A1 EP 1419231 A1 EP1419231 A1 EP 1419231A1 EP 02796301 A EP02796301 A EP 02796301A EP 02796301 A EP02796301 A EP 02796301A EP 1419231 A1 EP1419231 A1 EP 1419231A1
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EP
European Patent Office
Prior art keywords
polymer
additive
weight
preformulated
water
Prior art date
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Granted
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EP02796301A
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English (en)
French (fr)
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EP1419231B1 (de
Inventor
Cédric GEFFROY
Ian Harrison
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Publication of EP1419231A1 publication Critical patent/EP1419231A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules

Definitions

  • the subject of the present invention is a preformulated additive for a composition for treating articles of textile fibers, the compositions comprising said additive; it also relates to the use of said additive, in compositions for the treatment of articles made of textile fibers, as a care agent for said articles, in particular as an anti-creasing agent; it also relates to said treatment compositions.
  • a first subject of the invention consists of a preformulated additive for a composition for treating articles made of textile fibers in an aqueous or humid medium, characterized:
  • said polymer (P) is insoluble and capable of dispersing in said medium in the form of nanoparticles.
  • said preformulated additive comprises, expressed in dry: - from 5 to 90%, preferably from 10 to 60% of its weight of polymer
  • M matrix weight
  • S surfactant
  • said polymer (P) has a glass transition temperature Tg of the order of - 40 ° C to 150 ° C, preferably of the order of - 40 ° C to 100 ° C, very particularly in the range of - 40 ° C to 40 ° C.
  • polymer means both a homopolymer and a copolymer derived from two or more monomers.
  • said polymer (P) comprises:
  • hydrophilic monomer unit (F) chosen from cationic or cationizable monomer units • (F1) at the pH of use of said composition
  • said monomer units (N) and (F) are derived from monoethylenically unsaturated ⁇ - ⁇ monomers.
  • said monomer units (R) are derived from diethylenically unsaturated monomers.
  • the average molar mass of said polymer (measured by gel permeation chromatography (GPC) THF and expressed in polystyrene equivalents) may preferably be at least 20,000.
  • vinyl aromatic monomers such as styrene, vinyl toluene, etc.
  • alkyl esters of monoethylenically unsaturated ⁇ acids such as linear or branched C1-C10 alkyl acrylates and methacrylates, such as those of methyl, ethyl, butyl, isobutyl, heptyl, nonyl, etc.
  • vinyl or allyl esters of saturated carboxylic acids such as acetates, propionates, vinyl or allyl versatates
  • monoethylenically unsaturated ⁇ - ⁇ nitriles such as acrylonitrile .... ⁇ -olefins such as ethylene ...
  • N, N (diall ⁇ ylamino ⁇ alkyl) amides of monoethylenically unsaturated ⁇ - ⁇ carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, NN-dimethylaminoethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, N, N- dimethylaminobutyl acrylamide or methacrylamide.
  • monoethylenically unsaturated ⁇ - ⁇ aminoesters such as dimethyl aminoethyl methacrylate (DMAM), dimethyl aminopropyl methacrylate, ditertiobutylaminoethylmethacrylate, dipentylaminoethylmethacrylate.
  • DMAM dimethyl aminoethyl methacrylate
  • monomers precursors of amino functions such as N-vinyl formamide, N-vinyl acetamide, etc. which generate primary amine functions by simple acid or basic hydrolysis.
  • N N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine
  • SPE N-dimethyl-N-methacryloyloxyethyl-N- (3-sulfopropyl) ammonium sulfobetaine
  • SPP N-methacrylamidoethyl
  • SPP 1-vinyl-3- (3-sulfopropyl) imidazolidium betaine
  • SPV 3-sulfopropyl) -2-vinylpyridinium betaine
  • N (dialkylamino ⁇ alkyl) amides of ethylenically unsaturated ⁇ - ⁇ carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, or ethylenically unsaturated amino esters such as ditertiobutylaminoethylmethacrylate, dipentylaminoethylmethacrylate, with an alkali metal chloroacetate (sodium in particular) or propane sultone.
  • N (dialkylamino ⁇ alkyl) amides of ethylenically unsaturated ⁇ - ⁇ carboxylic acids such as N, N-dimethylaminomethyl acrylamide or methacrylamide, N, N-dimethylamino-3-propyl acrylamide or methacrylamide, or ethylenically unsaturated amino esters such as diter
  • monomers from which the hydrophilic units (F3) anionic or anionizable are derived there may be mentioned: monomers having at least one carboxylic function, such as ethylenically unsaturated ⁇ - ⁇ carboxylic acids or anhydrides, acrylic, methacrylic, maleic, fumaric, itaronic acids or anhydrides, N-methacroyl alanine, N-acryloyl-hydroxy-glycine and their salts soluble
  • monomers having at least one sulphate or sulphonate function such as 2-sulphooxyethyl methacrylate, vinylbenzene sulphonic acid, allyl sulphonic acid, 2-acrylamido-2methylpropane sulphonic, acrylate or sulphoethyl methacrylate, acrylate or sulfopropyl methacrylate and their water-soluble salts
  • monomers having at least one phosphonate or phosphate function such as vinylphosphonic acid, ... the esters of ethylenically unsaturated phosphates such as the phosphates derived from hydroxyethyl methacrylate
  • hydroxyalkylesters of ⁇ - ⁇ ethylenically unsaturated acids such as ⁇ - ⁇ acrylates and methacrylates of hydroxyethyl, hydroxypropyl, etc.
  • amides of ⁇ - ⁇ ethylenically unsaturated acids such as acrylamide
  • ethylenically unsaturated ⁇ - ⁇ monomers carrying a water-soluble polyoxyalkylene segment of the polyethylene oxide type such as polyethylene oxide ⁇ -methacrylates (BISOMER S20W, S10W, ...
  • RHODIA polyoxyethylene ⁇ -tristyrylphenyl methacrylate
  • ethylenically unsaturated ⁇ - ⁇ monomers precursors of hydrophilic units or segments such as vinyl acetate which, once polymerized, can be hydrolysed to generate vinyl alcohol units or polyvinyl alcohol segments
  • the ethylenically unsaturated ⁇ - ⁇ monomers of ureido type and in particular the methacrylamido of 2-imidazolidinone ethyl (Sipomer WAM II from RHODIA).
  • monomers from which the crosslinking units (R) are derived there may be mentioned:
  • polymer nanoparticles is meant, according to the invention, particles with a diameter of the order of 10 to 500 nm, preferably from 20 to 300 nm, very particularly from 20 to 100 nm, even more particularly from 20 to 50 nm.
  • the diameter of said particles can be determined in a well known manner by light scattering or by transmission electron microscopy.
  • Said polymers (P) can be obtained in a known manner by radical polymerization in aqueous medium of the ethylenically unsaturated monomers, in particular by radical polymerization in emulsion in water.
  • the choice and the relative amounts of the monomer (s) from which the unit (s) (N), (F) and (R) of the polymer (P) are derived are such that said polymer (P) has a glass transition temperature Tg of the of the order of - 40 ° C to 150 ° C, preferably of the order of - 40 ° C to 100 ° C, very particularly of the order of - 40 ° C to 40 ° C, and remains insoluble under the conditions of use of the additive of the invention.
  • said polymer (P) is considered to be insoluble when less than 15%, preferably less than 10% of its weight, is soluble in the aqueous or moist medium in which the additive of the invention is used, c that is to say in particular under the temperature and pH conditions of said medium.
  • PE polyelectrolytes
  • PVP polyvinylpyrrolidones
  • PVA polyvinyl alcohols
  • PA ampholyte polymers
  • TA - surfactants
  • water-soluble or water-dispersible synthetic polypeptides mention may be made of homopolymers or copolymers derived from the polycondensation of amino acids or amino acid precursors, in particular aspartic and glutamic acid or their precursors, and hydrolysis .
  • These polymers can be homopolymers derived from aspartic or glutamic acid as well as copolymers derived from aspartic acid and glutamic acid in any proportions, or copolymers derived from aspartic acid and / or glutamic acid and d other amino acids.
  • copolymerizable amino acids there may be mentioned glycine, alanine, leucine, isoleucine, phenyl alanine, methionine, histidine, proline, lysine, serine, threonine, cysteine ...
  • polypeptides (PP) of plant origin mention may be made of proteins of plant origin; these are preferably hydrolyzed, with a degree of hydrolysis less than or equal to 40%, for example from 5 to less than 40%.
  • proteins of vegetable origin mention may be made, by way of indication, of the proteins originating from protein seeds, in particular those of peas, faba beans, lupins, beans, and lentils; proteins from cereal grains, especially those from wheat, barley, rye, corn, rice, oats, and millet; proteins from oil seeds, especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts; proteins from the leaves, especially alfalfa, and nettles; and proteins from plant organs from buried reserves, notably that of potatoes and beets.
  • protein seeds in particular those of peas, faba beans, lupins, beans, and lentils
  • proteins from cereal grains especially those from wheat, barley, rye, corn, rice, oats, and millet
  • proteins from oil seeds especially those from soybeans, peanuts, sunflowers, rapeseed, and coconuts
  • proteins from the leaves especially alfalfa, and nettles
  • proteins of animal origin mention may be made, for example, of muscle proteins, in particular stroma proteins, and gelatin; proteins from milk, in particular casein, lactoglobulin; and fish protein.
  • the protein is preferably of vegetable origin, and more particularly comes from soybeans or wheat.
  • the polyelectrolyte (PE) can be chosen from those resulting from the polymerization of monomers which have the following general formula
  • R represents a hydrocarbon residue containing from 1 to 4 carbon atoms, preferably an alkylene residue containing 1 or 2 carbon atoms, methylene in particular.
  • acrylic, methacrylic, maleic, fumaric, itaconic, crotonic acids examples include acrylic, methacrylic, maleic, fumaric, itaconic, crotonic acids.
  • copolymers obtained from the monomers corresponding to the preceding general formula and those obtained using these monomers and other monomers in particular vinyl derivatives such as vinyl alcohols and copolymerizable amides such as acrylamide or methacrylamide. Mention may also be made of the copolymers obtained from vinyl ether alkyl and maleic acid as well as those obtained from vinyl styrene and maleic acid which are in particular described in the KIRK-OTHMER encyclopedia entitled "ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY "- Volume 18 - 3rd edition - Wiley interscience publication - 1982.
  • the preferred polyelectrolytes have a low degree of polymerization. The molecular mass by weight of the polyelectrolytes is more particularly less than 20,000 g / mole. Preferably, it is between 1000 and 5000 g / mole.
  • An ampholyte polymer is a polymer which comprises anionic or potentially anionic charges depending on the pH and cationic or potentially cationic charges depending on the pH, the potentially anionic or potentially cationic charges being taken into account. account for the calculation of the ratio of the total number of anionic charges to the total number of cationic charges.
  • the film-forming ampholytic polymer (PA) generally has a molecular mass of less than 500,000 g / mol, determined by aqueous gel permeation chromatography (GPC).
  • the film-forming ampholytic polymer (PA) can be obtained from anionic and cationic ethylenically unsaturated monomers. It can also be obtained from a mixture of monomers additionally containing neutral monomers.
  • the anionic ethylenically unsaturated monomers can be chosen from acrylic, methacrylic, fumaric, maleic, itaconic acids or anhydrides, N-methacroyl alanine, N-acryloyl-hydroxy-glycine ...
  • water-soluble, sulfonated or phosphonated ethylenically unsaturated monomers such as sulfopropyl acrylate or its water-soluble salts, water-soluble styrene sulfonates, vinylsulfonic acid and its water-soluble salts or vinylphosphonic acid and its water-soluble salts.
  • the cationic ethylenically unsaturated monomers can be chosen from
  • aminoacryloyl or acryloyloxy monomers such as trimethylaminopropylmethacrylate chloride, trimethylaminoethylacrylamide chloride or bromide, trimethylaminobutylacrylamide methylsulfate or methacrylamide, trimethylaminopropylmethacrylamide methyl methacrylamide (MES) (3-acrylamidopropyl) trimethylammonium chloride (APTAC), methacryloyloxyethyl trimethylammonium chloride or methylsulfate, acryloyloxyethyl trimethylammonium chloride;
  • N, N-dialkyldiallylamine monomers such as N, N-dimethyldiallylammonium chloride (DADMAC); * polyquaternary monomers such as dimethylaminopropylmethacrylamide chloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium (DIQUAT) ...
  • the ethylenically unsaturated neutral monomers can be chosen from acrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, dimethylaminoethylmethacrylate (DMAEMA), dimethylaminopropylmethacrylamide, vinyl alcohol, alkyl acrylates or methacrylates. hydroxyalkyl, polyoxyalkylene glycol acrylates or methacrylates ...
  • PA ampholyte polymer
  • MAPTAC acrylic or methacrylic acid
  • DIQUAT acrylic or methacrylic acid
  • DADMAC acrylic or methacrylic acid
  • oses there may be mentioned aldoses such as glucose, mannose, galactose, ribose and ketoses such as fructose.
  • Osides are compounds which result from the condensation, with elimination of water, of daring molecules between them or even of daring molecules with non-carbohydrate molecules.
  • the holosides which are formed by the combination of exclusively carbohydrate units are preferred, and more particularly the oligoholosides (or oligosaccharides) which contain only a limited number of these units, that is to say a number which is generally lower. or equal to 10.
  • oligoholosides mention may be made of sucrose, lactose, cellobiose, maltose, sucrose and trehalose.
  • the water-soluble or water-dispersible polyholosides are highly depolymerized; they are described for example in the work of P. ARNAUD entitled “course of organic chemistry", Gaultier-Villars editors, 1987. More particularly, these polyholosides have a mass molecular weight less than 500,000 g / mole, preferably less than 20,000 g / mole.
  • polyholosides By way of nonlimiting example of polyholosides, mention may be made of celluloses and cellulose derivatives (carboxy methyl cellulose), carrageenans; among the highly depolymerized polyholosides, mention may be made of dextran, starch, xanthan gum and galactomannans such as guar or carob, these polysaccharides preferably having a melting point above 100 ° C. and a solubility in water between 5 and 500g / l.
  • amino acids there may be mentioned monocarboxylated or dicarboxylated amino acids, diamine monocarboxylated acids and their water-soluble derivatives.
  • Amino acids preferably have a side chain with acid-base properties; they are chosen in particular from arginine, lysine, histidine, aspartic, glutamic and hydroxyglutamic acids; they can also be in the form of derivatives, preferably water-soluble; it can be, for example, sodium, potassium or ammonium salts, such as sodium glutamate, aspartate or hydroxyglutamate.
  • the description of the fluid isotropic phases and rigid liquid crystal of hexagonal or cubic type is given in the work of RG LAUGHLIN entitled “The AQUEOUS PHASE BEHAVIOR OF SURFACTANTS “- ACADEMIC PRESS - 1994. Their identification by diffusion of radiation (X and neutrons) is described in the work of V. LUZZATI entitled” BIOLOGICAL MEMBRANES, PHYSICAL FACT AND FUNCTION "- ACADEMIC PRESS - 1968. More particularly, the phase rigid liquid crystal is stable up to a temperature at least equal to 55 ° C. The fluid isotropic phase can be poured, while the rigid liquid crystal phase cannot.
  • ionic glycolipid surfactants in particular derivatives of uronic acids (galacturonic, glucuronic acids, D-mannuronic, L-iduronic, L-guluronic 10), having a substituted hydrocarbon chain or unsaturated or unsaturated comprising from 6 to 24 carbon atoms and preferably from 8 to 16 carbon atoms, or their salts.
  • uronic acids galacturonic, glucuronic acids, D-mannuronic, L-iduronic, L-guluronic
  • L-iduronic L-iduronic
  • L-guluronic ionic glycolipid surfactants
  • surfactant examples include amphoteric surfactants such as amphoteric derivatives of alkyl polyamines such as amphionic XL®, Mirataine H2C-HA® marketed by Rhône Poulenc as well as Ampholac
  • alkali or alkaline earth metal silicates Sil
  • alkali or alkaline earth metal phosphates Phos
  • sodium hexametaphosphate there may be mentioned in particular sodium hexametaphosphate.
  • the preformulated additive according to the invention further comprises at the matrix (M) / polymer (P) interface at least one nonionic, anionic, cationic or amphoteric surfactant (S).
  • M matrix
  • P polymer
  • S amphoteric surfactant
  • nonionic surfactants mention may be made in particular of polyoxyalkylenated derivatives such as
  • OE and / or oxypropylene (OP) units of these nonionic surfactants usually varies from 2 to 100 depending on the HLB (hydrophilic / lipophilic balance) desired. More particularly, the number of OE and / or OP units is between 5 and 50.
  • Ethoxylated or ethoxy-propoxylated fatty alcohols generally contain from 6 to 22 carbon atoms, the OE and OP units being excluded from these numbers. Preferably, these units are ethoxylated units.
  • the ethoxylated or ethoxy-propoxylated triglycerides can be triglycerides of plant or animal origin (such as lard, tallow, oil peanut, butter oil, cottonseed oil, linseed oil, olive oil, fish oil, palm oil, grape seed oil , soybean oil, castor oil, rapeseed oil, coconut oil, coconut oil and are preferably ethoxylated.
  • the ethoxylated or ethoxy-propoxylated fatty acids are fatty acid esters (such as for example oleic acid, stearic acid), and are preferably ethoxylated.
  • the ethoxylated or ethoxy-propoxylated sorbitan esters are cyclized fatty acid sorbitol esters comprising from 10 to 20 carbon atoms such as lauric acid, stearic acid or oleic acid, and are preferably ethoxylated.
  • ethoxylated triglyceride is intended in the present invention, both the products obtained by ethoxylation of a triglyceride with ethylene oxide as those obtained by transesterification of a triglyceride with a polyethylene glycol.
  • ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by transesterification of a fatty acid with a polyethylene glycol.
  • Ethoxylated or ethoxy-propoxylated fatty amines generally have from 10 to 22 carbon atoms, the OE and OP units being excluded from these numbers, and are preferably ethoxylated.
  • the ethoxylated or ethoxy-propoxylated alkylphenols are generally 1 or 2 alkyl groups, linear or branched, having 4 to 12 carbon atoms. By way of example, mention may in particular be made of octyl, nonyl or dodecyl groups.
  • anionic surfactants mention may be made of the water-soluble salts of alkylsulphates, of alkylethersulphates, alkylisethionates and alkyltaurates or their salts, alkylcarboxylates, alkylsulfosuccinates or alkylsuccinamates, alkylsarcosinates, alkyl derivatives of protein hydrolysates, acylaspartates, phosphates, alkyl esters and / or alkyl ether and / or alkylarylether.
  • the cation is generally an alkali or alkaline-earth metal, such as sodium, potassium, lithium, magnesium, or an ammonium group NR + with R, identical or different, representing an alkyl radical substituted or not by an atom oxygen or nitrogen.
  • amphoteric surfactants mention may be made of alkyl betaines, alkyldimethyl betaines, alkylamidopropyl betaines, alkylamido-propyldimethyl betaines, ali yltrimethyl sulfobetaines, imidazoline derivatives such as alkylamphoacetates, ali ylamphodiacates, ali ylamphodiacates amphodipropionates, alkylsultaines or alkylamidopropyl-hydroxysultaines, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyamines such as Amphionic XL® sold by Rhône-Poulenc, Am
  • R and R similar or different, represent a C 1 -C 20 alkyl group, an aryl or benzyl group
  • R and R similar or different, represent a C1 - alkyl group
  • X " is a solubilizing anion such as halide (for example chloride, bromide, iodide), sulfate or methylsulfate.
  • halide for example chloride, bromide, iodide
  • sulfate or methylsulfate.
  • S surfactant
  • TA surfactant
  • the preformulated additive according to the invention is preferably in the solid form of dry appearance, for example in the form of powder or granules of dry appearance.
  • Said preformulated additive can be obtained by • adding the water-soluble or water-dispersible compound (s) capable of forming the matrix (M) to a polymer nanolatex (P) in the presence of at least one surfactant (S);
  • polymer nanolatex a stable aqueous dispersion of solid polymer nanoparticles having an average size of the order of 10 to 500 nm, preferably preferably from 20 to 300 nm, very particularly from 10 to 200 nm, even more particularly from 20 to 50 nm.
  • Such a dispersion generally has a dry extract of the order of 10 to 50% by weight, preferably of the order of 20 to 40% by weight.
  • the nanolatex polymer particles (P) have at their surface at least one emulsifier (or surfactant (S)) the rate of which is a function of the size of the nanolatex particles.
  • Said nanolatex can optionally be diluted before being used.
  • the respective amounts of nanolatex of polymer (P), surfactant (S) and of water-soluble or water-dispersible compound (s) capable of forming the matrix (M) are such that the dispersion obtained contains, expressed as dry, from - from 5 to 90% by weight, preferably from 10 to 60% by weight of polymer (P) - - from 3 to 90%, preferably from 10 to 80%, very particularly from 15 to 70 % of water-soluble or water-dispersible compound (s) capable of forming the matrix (M) - and from 0.01 to 20%, preferably from 0.02 to 5% by weight of surfactant ( S).
  • the dry extract of the dispersion obtained can be of the order of 5 to 60%, preferably of the order of 10 to 50%.
  • (M) can be carried out by any means known to those skilled in the art, in particular by lyophilization (that is to say freezing, then sublimation) or preferably by spray drying.
  • Spray drying can be carried out in any known device, such as an atomization tower associating a spraying carried out by a nozzle or a turbine with a stream of hot air.
  • the conditions of implementation depend on the type of compound capable of forming the matrix (M) and of the atomizer used; these conditions are generally such that the temperature of the whole product during drying, at least 30 ° C and not more than 150 ° C.
  • - WO 96/17891 drying of a dispersion comprising a non-water-soluble polymer latex, a polysaccharide (lactose) and a compound chosen from alkylaromatic ionic compounds and polyvinylpyrrolidones
  • - WO 97/15617 drying of a dispersion comprising a non-water-soluble polymer latex, a surfactant of the ionic (uronic) glycolipic, amphoteric type (amphoteric derivatives of alkylpolyamines), and a mineral water-soluble compound (silicates, phosphates) or organic (urea, sugars, polyelectrolytes);
  • - WO 97/15616 drying of a dispersion comprising a non-water-soluble polymer latex, a non-ionic polyoxyalkylene surfactant and a polyelectrolyte (weak polyacid);
  • WO 99/38611 targeting water-dispersible granules comprising a hydrophobic active material, a polypeptide (soy protein) and an ionic or amphoteric dispersing agent.
  • Said preformulated additive of the invention may optionally also contain other adjuvants such as anti-caking agents or fillers, such as in particular calcium carbonate, sodium sulfate, a clay such as bentonite or laponite, kaolin, silica ..., which can be added totally or partially either to the aqueous dispersion before removal of the water, or during the atomization step or else after drying.
  • said preformulated additive can also comprise, in the encapsulated state in the polymer nanoparticles (P), at least one hydrophobic active material (MA).
  • hydrophobic active materials mention may be made of those present in the compositions for the treatment of articles made of textile fibers, in particular hydrophobic active detergents.
  • All active materials whether solid, liquid (as such or in solution in a solvent) are suitable insofar as they are not miscible or are only very slightly miscible in water.
  • lightly miscible means active materials whose solubility in water at pH 7 does not exceed 20% by weight, preferably not 10% by weight.
  • active ingredients such as, for example, perfumes, bleaching catalysts, biocidal agents, bleaching activators, anti-UV agents, optical brighteners. , antioxidants, silicones.
  • the amount of active material (MA) that may be present can range from 20 to 70, preferably from 40 to 60 parts by weight of active material (MA) per 100 parts by weight of polymer (P).
  • the encapsulation of the hydrophobic active material (MA) by the polymer nanoparticles (P) can be carried out by introduction of said active material (MA) into said polymer nanoparticles (P) in the form of a nanolatex, the introduction of the active ingredient (MA) which can be carried out either during the actual synthesis of said polymer by polymerization in aqueous emulsion, or after the synthesis of said polymer by polymerization in aqueous emulsion.
  • the introduction of the active material (MA) into the nanolatex of polymer (P) is carried out after the step of polymerization in aqueous emulsion of the monomer composition.
  • the active ingredient (AM) present in the liquid state can be introduced directly into the polymer nanolatex (P), if it is sufficiently “swelling” of the polymer, or assisted if necessary with a swelling "transfer” solvent of the polymer.
  • esters such as ethyl acetate, methyl propionate, the mixture of glutarate / adipate / methyl succinate (solvent "RPDE”) ...
  • ketones such as methyl ethyl ketone, cyclohexanone ...
  • alcohols such as propanol, pentanol, cyclohexanol ...
  • aliphatic and cyclic hydrocarbons such as heptane, decane, cyclohexane, decaline .... chlorinated aliphatic derivatives such as dichloromethane ...
  • aromatic derivatives such as toluene, ethylbenzene ...
  • chlorinated aromatic derivatives such as trichlorobenzene ...
  • the active material (MA) introduced is brought into contact with the nanolatex, with stirring at a temperature of 20 to 50 ° C for 1 to 24 hours.
  • Said "transfer” solvent can optionally be removed by evaporation under vacuum if the active material (MA) is a solid.
  • Said preformulated additive forming the subject of the invention can be used for the preparation of a treatment composition for the care of articles made of textile fibers in an aqueous or humid medium.
  • Said additive can be used in said compositions as a care agent, protecting the fibers from physical or chemical degradation phenomena and / or providing them with benefits such as softening and / or anti-creasing properties; said additive is particularly effective as an anti-creasing agent.
  • a second object of the invention therefore consists in the use, in a composition for the treatment of articles of textile fibers in an aqueous or wet medium, of said preformulated additive, as a care agent, in particular as an anti-creasing agent for said articles .
  • a third object of the invention consists of a composition for caring for articles made of textile fibers comprising said preformulated additive.
  • composition and the conditions of use (or treatment) can be multiple. Said composition can be presented
  • composition of the invention can be:
  • rinsing and / or softening formulation capable of directly forming, by dilution, a rinsing and / or softening bath
  • drying additive a solid material, in particular textile, comprising the additive of the invention, intended to be brought into contact with damp linen in a dryer (said solid material is hereinafter called "drying additive");
  • washing additive intended to be deposited on the dry linen prior to a washing operation using a detergent formulation containing or not containing the preformulated additive according to the invention.
  • the composition of the invention is particularly well suited to the care of articles made of textile fibers, in particular cotton-based, in particular containing at least 35% cotton.
  • the pH of use of the composition of the invention may range from approximately 2 to approximately 12, depending on the use sought. As it's about
  • the pH of the detergent bath is generally of the order of 7 to 11, preferably of 8 to 10.5;
  • - a rinsing and / or softening formulation the pH of the rinsing and / or softening bath is generally of the order of 2 to 8;
  • the pH to be considered is that of residual water, which can be of the order of 2 to 9; - of a washing additive ("prespotter"), the pH to be considered is that of the pH of the washing bath of the following washing operation, namely of the order of 7 to 11, preferably from 8 to 10.5.
  • At least 70% of the total mass of the polymer (P) of the preformulated additive is formed of hydrophobic unit (s) (N).
  • hydrophilic units (F) When hydrophilic units (F) are present, these do not preferably represent more than 30% of the total mass of the polymer
  • crosslinking units (R) When crosslinking units (R) are present, these generally do not represent more than 20%, preferably not more than 10%, especially not more than 5% of the total mass of the polymer (P).
  • a first type of composition of the invention consists of a composition (C1) comprising a preformulated additive in which the polymer (P1) is an uncharged or non-ionizable polymer comprising - at least 70% of its weight of monomer units ( N) hydrophobic
  • said uncharged or non-ionizable polymer (P1) comprises: at least 70% of its weight of hydrophobic monomer units (N)
  • the preformulated additive comprising said uncharged or non-ionizable polymer (P1) can be used in all types of compositions for the care of textile fiber articles mentioned above, the use pH of which can range from 2 to 12, namely, detergent formulations, rinse and / or softening formulations, drying additives or washing additives.
  • a second type of composition of the invention consists of a composition (C2) comprising a preformulated additive in which the polymer (P2) is a polymer having anionic or anionizable units and free of cationic or cationizable units, comprising
  • hydrophilic monomer units (F4) uncharged or non-ionizable.
  • the preformulated additive comprising the polymer (P2) can be used in the compositions for the care of articles made of textile fibers, of non-cationic nature, namely, detergent formulations, drying additives or washing additives.
  • a third type of composition of the invention consists of a composition (C3) comprising a preformulated additive in which the polymer (P3) having amphoteric units, comprising - at least 70% of its weight of hydrophobic monomer units (N)
  • hydrophilic monomer units (F1) all of the hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P3), and the molar ratio of cationic charges to anionic charges may range from 1/99 to 80/20 depending on the desired use of said composition (C3).
  • the preformulated additive comprising the polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in the drying additives.
  • the preformulated additive comprising the polymer (P3) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 60/40, preferably from 5/95 to 50/50, can also be used in the detergent formulations and washing additives.
  • a fourth type of composition of the invention consists of a composition (C4) comprising a preformulated additive in which the polymer (P4) is a polymer having both cationic or cationizable units and anionic or anionizable units, comprising
  • hydrophilic monomer units (F4) uncharged or non-ionizable, all the hydrophilic monomer units (F) preferably representing at least 1% of the weight of the polymer (P4), and the molar ratio of cationic charges to charges anionics which can range from 1/99 to 80/20 depending on the desired use of said composition (C4).
  • the additive comprising the polymer (P4) having a molar ratio of cationic charges to anionic charges ranging from 1/99 to 80/20 can be used in the drying additives.
  • 5/95 to 50/50 can also be used in detergent formulations and washing additives.
  • a fifth type of composition of the invention consists of a composition (C5) comprising a preformulated additive in which the polymer (P5) is a polymer having cationic or cationizable units and free of anionic or anionizable units, comprising
  • hydrophobic monomer units (N) at least 70% of its weight of hydrophobic monomer units (N) - at least 1% of its weight, preferably from 3 to 30% of its weight, very particularly from 1 to 10% of its weight of cationic or cationizable hydrophilic monomer units (F1)
  • hydrophilic monomer units (F4) uncharged or non-ionizable.
  • the preformulated additive comprising the polymer (P5) can be used in all types of compositions for the care of the textile fiber articles mentioned above, the pH of use of which can range from 2 to 12, namely, formulations detergents, rinse and / or softening formulations, drying additives or washing additives.
  • the said monomer units (F1) are cationizable units derived from at least one cationizable monomer having a pKa of less than 11, preferably less than 10.5 . Mention may in particular be made, as examples of polymer (P), of copolymers having units derived from
  • the glass transition temperature Tg of which can range from 10 ° C. to 80 ° C., depending on the composition of said polymer * methyl methacrylate / ethylene glycol dimethacrylate / methacrylic acid, of which the glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
  • the glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
  • the glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer methyl methacrylate / butyl acrylate / hydroxyethylmethacrylate / methacrylic acid / Empicryl 6835 from RHODIA, whose glass transition temperature Tg can range from 10 ° C to 80 ° C, depending on the composition of said polymer
  • the amount of preformulated additive, expressed as dry polymer (P), present in the care composition according to the invention can range from 0.05 to 10% by dry weight of the said composition in dry matter, depending on the 'application sought.
  • the preformulated additive can be implemented as follows:
  • this when it is a detergent formulation, for washing articles made of textile fibers, in particular linen, this generally comprises: - at least one natural and / or synthetic surfactant,
  • the detergent formulation may include surfactants in an amount corresponding to about 3 to 40% by weight based on the detergent formulation, surfactants such as anionic surfactants.
  • methyl ester sulfonates whose radicals R is C-
  • sulfated alkylamides of formula RCONHROSO3M where R represents a C2-C22 alkyl radical. preferably in C6-C20.
  • R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having an average of 0, 5 to 60 OE and / or OP patterns;
  • the salts of C8-C24 preferably C14-C20 saturated or unsaturated fatty acids, C9-C20 alkylbenzenesulfonates, C8-C22 primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB- A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-
  • Nonionic surfactants polyoxyalkylenated (polyoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is CQ-C ⁇ _ and containing from 5 to
  • glucosamide, glucamide, glycerolamide polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of
  • amine oxides such as C1-C6 alkyl oxides
  • alkyldimethylbetaines alkylamidopropyldimethylbetaines, alkyltrimethylsulfobetaines, condensation products of fatty acids and protein hydrolysates; alkylamphoacetates or alkylamphodiacetates in which the alkyl group contains from 6 to 20 carbon atoms.
  • detergency builders improving the properties of the surfactants can be used in amounts corresponding to approximately 5-50%, preferably approximately 5-30% by weight for the liquid detergent formulas or approximately 10 -80%, preferably 15-50% by weight for detergent formulas in powders, detergency builders such as: Inorganic detergency builders
  • polyphosphates tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates of alkali metals, ammonium or alkanolamines. tetraborates or borate precursors;
  • silicates in particular those having a Si ⁇ 2 / Na2 ⁇ ratio of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US-A-4664839; . alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates); . cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868;
  • crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or ammonium such as zeolites A, P, X ...; Zeolite A with a particle size of the order of 0.1-10 microns is preferred.
  • Organic detergency builders water-soluble polyphosphonates (1-hydroxy-1 ethane, 1-diphosphonates, methylene salts diphosphonates ...); the water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as: polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts); hydroxypolycarboxylate ethers; citric acid and its salts, mellitic acid, succinic acid and their salts; the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates); succinic C5-C20 alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates); polyacetal carboxylic esters; polyaspartic acid, polyg
  • the detergent formulation may further comprise at least one oxygen-releasing bleaching agent comprising a percompose, preferably a parsley.
  • Said bleaching agent can be present in an amount corresponding to approximately 1 to 30%, preferably from 4 to 20% by weight relative to the detergent formulation.
  • per-compounds capable of being used as bleaching agents mention should be made in particular of perborates such as sodium perborate monohydrate or tetrahydrate; peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate.
  • Preferred bleaching agents are sodium perborate, mono- or tetrahydrate and / or sodium carbonate peroxyhydrate.
  • Said agents are generally combined with a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid, in an amount corresponding to approximately 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation.
  • a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid, in an amount corresponding to approximately 0.1 to 12%, preferably from 0.5 to 8% by weight relative to the detergent formulation.
  • these activators there may be mentioned, tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluryl, sodium p-acetoxybenzenesulfonate, pentaacetylglucose, octaacetyllactose.
  • Non-oxygenated bleaching agents acting by photoactivation in the presence of oxygen, agents such as sulfonated aluminum and / or zinc phthalocyanines.
  • the detergent formulation may further comprise anti-fouling agents ("soil release"), anti-redeposition, chelating agents, dispersants, fluorescence, foam suppressants, softeners, enzymes and other various additives.
  • Anti-fouling agents oil release
  • They can be used in amounts of approximately 0.01-10%, preferably approximately 0.1-5%, and more preferably of the order of 0.2-3% by weight.
  • agents such as:. cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose;
  • polyvinyl esters grafted on polyalkylene trunks such as polyvinyl acetates grafted on polyoxyethylene trunks (EP-A-219048); . polyvinyl alcohols;
  • polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units with a molar ratio (number of units) ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4 116896, US-A-4702857, US-A-4770 666); .
  • sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol, having from 1 to 4 sulfonated groups (US-A-4968451); .
  • polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl or methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) anionic sulfopolyethoxy (US-A-4,721,580), sulfoaroyl (US-A-4,877,896);
  • the sulfonated polyester copolymers derived from terephthalic, isophthalic and sulfoisophthalic acid, anhydride or diester and a diol FR-A-2 720399.
  • Anti-redeposition agents FR-A-2 720399.
  • ethoxylated monoamines or polyamines polymers of ethoxylated amines
  • polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol
  • the iron and magnesium chelating agents can be present in amounts of the order of 0.1 -10%, preferably of the order of 0.1-3% by weight. Among others, we can mention:
  • aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethylethylenediaminetriacetates, nitrilotriacetates;
  • aminophosphonates such as nitrilotris- (methylenephosphonates); . polyfunctional aromatic compounds such as dihydroxy-disulfobenzenes.
  • polycarboxylic acids of molecular mass of the order of 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates with a molecular mass of the order of 2,000 to 10
  • agents such as: stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes ...
  • agents such as:. C10-C24 monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides;
  • aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons such as paraffins, waxes;
  • N-alkylaminotriazines .
  • monostearylphosphates monostearylalcoholphosphates;
  • polyorganosiloxane oils or resins optionally combined with silica particles.
  • agents such as clays.
  • enzymes such as:. proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,
  • the detergent formulation can be used, in particular in a washing machine, at a rate of 0.5g / l to 20g / l, preferably from 2g / l to 10g / l to carry out washing operations at a temperature of range from 25 to 90 ° C.
  • the preformulated additive according to the invention may be present in a formulation for rinsing and / or softening articles made of textile fibers, in particular linen.
  • cationic surfactants triethanolamine diester quaternized by dimethylsulfate, N-methylimidazoline tallow methyl sulfate ester, dialkyldimethylammonium chloride, alkylbenzyldimethylammonium chloride, methyl and alkylimidazolinium sulfate, methyl and methyl bis bis ( alkylamidoethyl) -2 - hydroxyethylammonium ”) in an amount which can range from 3 to 50%, preferably from 4 to 30% of said formulation optionally associated with nonionic surfactants (ethoxylated fatty alcohols, ethoxylated alkylphenols ...) up to 3%;
  • anti-color transfer agents polyvinylpyrrolidone, polyvinyloxazolidone, polymethacrylamide ... 0.03 to 25%, preferably 0.1 to
  • alcohols methanol, ethanol, propanol, isopropanol, ethylene glycol, glycerin
  • drying additive when it is a laundry drying additive in a suitable drying machine, it comprises a flexible solid support constituted for example by a strip of woven or nonwoven fabric, a cellulose sheet, comprising said additive preformulated comprising the polymer (P); said drying additive is introduced on drying into the damp linen to be dried at a temperature of the order of 50 to 80 ° C for 10 to 60 minutes.
  • Said drying additive may further comprise cationic softening agents (up to 99%) and anti-color transfer agents (up to 80%) such as those mentioned above.
  • pre-spotting additive When it is a washing or pre-spotting additive ("prespotter”), it can be in the form of a solid (stick).
  • composition - anionic surfactants such as those already mentioned above, in an amount of at least 5% of the weight of the composition - nonionic surfactants such as those already mentioned above, in an amount which can range from 15% to 40% of the composition weight
  • Aliphatic hydrocarbons in an amount which can range from 5% to 20% of the weight of the composition.
  • a final object of the invention consists in a process for treating articles made of textile fibers, by treating said articles with the aid of a composition, in an aqueous or wet medium, comprising said preformulated additive.
  • a composition in an aqueous or wet medium, comprising said preformulated additive.
  • P polymer
  • the polymer nanolatex (P) used in the examples for the preparation of a preformulated additive in powder form is an aqueous dispersion of methyl methacrylate / butyl acrylate / hydroxyethylmethacrylate / methacrylic acid copolymer, according to a mass ratio between the different monomers of 37/55/5/3, whose glass transition temperature Tg is of the order of 17 ° C, having an average particle size of 35 nm (determination by light scattering using of a Zetasizer device from Malvern Instrument) and having a dry extract of the order of 30%.
  • Said nanolatex has been stabilized at its synthesis by 5% by weight relative to the dry copolymer of sodium dodecylsulfate.
  • Example 1 A preformulated powder additive is prepared as follows from said nanolatex of polymer (P) above, by processing
  • a 4% aqueous solution of SYNPERONIC A7 is prepared 1), by mixing 0.5 g of SYNPERONIC A7 and 12 g of water; - A dispersion 2) is prepared at 14.5% of active material, by diluting 23 g of said polymer nanolatex (P) in 24.5 g of water with stirring;
  • aqueous polyacrylic acid solution is then added little by little to the preceding mixture with stirring; stirring is continued for 5 minutes after stopping the addition.
  • 100 g of an aqueous dispersion are obtained having:
  • a preformulated powder additive is prepared as follows from said nanolatex of polymer (P) above, by using sucrose as matrix; the amount of sodium dodecyl sulfate from the synthesis of said polymer nanolatex (P) is sufficient to stabilize the dispersion.
  • a washing operation is carried out in a laboratory apparatus Tergotometer well known in the profession of formulators of detergent compositions.
  • the device simulates the mechanical and thermal effects of washing machines of the American type with pulsator, but thanks to the presence of 6 washing pots, it allows to carry out series of simultaneous tests with an appreciable saving of time.
  • test pieces are then crumpled under a 3 kg press for 20 seconds, then allowed to dry vertically overnight.
  • the same operation is carried out using the same detergent formulation but free of preformulated additive.
  • a digital color photograph of the dry specimens is then produced, which is then transformed into 256 gray levels (gray scale from 0 to 255). We count the number of pixels corresponding to each gray level.
  • the standard deviation ⁇ of the distribution of the gray level is measured.
  • * ⁇ l corresponds to the standard deviation obtained with the detergent formulation not containing any preformulated additive.
  • * ⁇ 2 corresponds to the standard deviation obtained with the detergent formulation containing the preformulated additive.
  • the matrix (M) has no impact on the anti-creasing properties of the preformulated additive.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP02796301A 2001-08-22 2002-08-21 Additiv für eine zusammensetzung zur behandlung von textilien sowie seine verwendung als pflegemittel Expired - Lifetime EP1419231B1 (de)

Applications Claiming Priority (3)

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FR0111000 2001-08-22
FR0111000A FR2828887B1 (fr) 2001-08-22 2001-08-22 Additif preformule pour composition de traitement des articles en fibres textiles et utilisation dudit comme agent de soin
PCT/FR2002/002917 WO2003018736A1 (fr) 2001-08-22 2002-08-21 Additif preformule pour composition de traitement des articles en fibres textiles et utilisation dudit additif comme agent de soin

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FR2820747B1 (fr) * 2001-02-15 2005-10-07 Rhodia Chimie Sa Composition a base de polysaccharide non-ionique pour le soin des articles en fibres textiles
GB2408267A (en) * 2003-11-21 2005-05-25 Reckitt Benckiser Inc Treatment block composition for toilets
DE102004038218A1 (de) * 2004-08-05 2006-03-16 Basf Ag Verfahren zur Ausrüstung von saugfähigen Materialien
JP5596557B2 (ja) * 2008-01-18 2014-09-24 ロディア オペレーションズ ラテックスバインダー、凍結融解安定性を有する水性コーティング及び塗料並びにそれらの使用法
UA108951C2 (uk) 2011-08-31 2015-06-25 Акцо Нобель Кемікалз Інтернешнл Б.В. Пральні мийні композиції, які містять брудовідштовхувальну речовину
KR102654867B1 (ko) 2016-09-01 2024-04-05 삼성전자주식회사 양극 보호층을 포함하는 3차원 전고체 리튬 이온 전지 및 그 제조방법
EP3656838B1 (de) 2018-11-26 2021-05-12 Global Cosmed Group spolka akcyjna Flüssiges waschmittel

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GB985503A (en) * 1963-02-15 1965-03-10 Ici Ltd Detergent compositions
US3606992A (en) * 1967-08-28 1971-09-21 Warnaco Inc Abrasion and wrinkle resistant cotton containing fabric and method of manufacture
US3956163A (en) * 1973-08-20 1976-05-11 The Dow Chemical Company Pigmented detergents
CA2127919A1 (en) * 1993-09-03 1995-03-04 Jessie Alvin Binkley Process for producing ultrafine sized latexes
AU730956B2 (en) * 1996-12-23 2001-03-22 Ciba Specialty Chemicals Water Treatments Limited Particles containing absorbed liquids and methods of making them
ATE240386T1 (de) * 1997-06-30 2003-05-15 Ciba Spec Chem Water Treat Ltd Polymere materialien und ihre verwendung
FR2774311B1 (fr) * 1998-02-02 2000-03-17 Rhodia Chimie Sa Granules dispersables dans l'eau comprenant une matiere active hydrophobe
GB9910389D0 (en) * 1999-05-05 1999-07-07 Unilever Plc Laundry compositions
FR2813312B1 (fr) * 2000-08-25 2006-07-14 Rhodia Chimie Sa Composition a base de nanolatex de polymeres pour le soin du linge

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DE60206777D1 (de) 2006-03-02
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US20060194711A1 (en) 2006-08-31
ATE307190T1 (de) 2005-11-15
US20030050218A1 (en) 2003-03-13
FR2828887B1 (fr) 2003-12-05
DE60206777T2 (de) 2006-07-06
JP2005501183A (ja) 2005-01-13
FR2828887A1 (fr) 2003-02-28
WO2003018736A1 (fr) 2003-03-06

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