WO2004046288A2 - Produit d'entretien doux pour textiles - Google Patents

Produit d'entretien doux pour textiles Download PDF

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Publication number
WO2004046288A2
WO2004046288A2 PCT/EP2003/012484 EP0312484W WO2004046288A2 WO 2004046288 A2 WO2004046288 A2 WO 2004046288A2 EP 0312484 W EP0312484 W EP 0312484W WO 2004046288 A2 WO2004046288 A2 WO 2004046288A2
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WO
WIPO (PCT)
Prior art keywords
acid
textile
weight
copolymer
agents
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PCT/EP2003/012484
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German (de)
English (en)
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WO2004046288A3 (fr
Inventor
Christian Block
Josef Penninger
Evelyn Langen
Konstanze Mayer
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to DE50310385T priority Critical patent/DE50310385D1/de
Priority to EP03767523A priority patent/EP1563046B1/fr
Priority to AU2003292000A priority patent/AU2003292000A1/en
Publication of WO2004046288A2 publication Critical patent/WO2004046288A2/fr
Publication of WO2004046288A3 publication Critical patent/WO2004046288A3/fr
Priority to US11/135,123 priority patent/US20050215449A1/en

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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
    • C11D3/3788—Graft 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin

Definitions

  • the invention relates to a textile care product containing a copolymer of unsaturated carboxylic acids and / or their salts with carbohydrates and a washing method for washing textiles using the textile care product in a household washing machine.
  • the invention further relates to the use of the textile care agent to reduce the formation of creases, improve the ironing properties and reduce the formation of pills.
  • WO 99/16956 A1 describes the removal of fluff or pills by using cellulases.
  • the cellulases digest microfibers protruding from the textile fabrics and thus ensure a smooth and therefore pill-free textile surface.
  • WO 97/00272 A1 describes a polymer which has at least one carbohydrate unit and at least one 2-hydroxy-2-carboxaethylene unit. These polymers are produced by polymerizing at least one vinyl monomer A, which is primarily an ⁇ -haloacrylic acid, and at least one further vinyl monomer B, in the presence of at least one optionally modified carbohydrate. The polymers are used in bleach-containing agents for textile pretreatment and paper bleaching.
  • WO 96/37530 A1 describes water-soluble graft copolymers of monosaccharides, oligosaccharides and polysaccharides and their derivatives which can be obtained by free-radical copolymerization of A) monomer mixtures of a) more than 40-100% by weight of at least one ⁇ - ⁇ -unsaturated aldehyde, b) 0-60% by weight of a) different unsaturated monomers which are copolymerizable with a), and c) 0-5% by weight of at least two monomers having ethylenically, non-conjugated double bonds in the molecule, in the presence of B) Mono-, oligo-, or polysaccharides and C) one or more oxidizing agents.
  • WO 94/01476 describes graft copolymers of mono-, di- and oligosaccharides which can be obtained by radical graft copolymerization from a monomer mixture
  • graft copolymers are used, inter alia, as additives in detergents and cleaning agents.
  • EP 0 465 287 A1 discloses graft polymers based on polysaccharides which are at least partially biodegradable and have a polydextrose with an average molecular weight below 10,000 g / mol, which is characterized by a water-soluble unsaturated is grafted monomer.
  • the graft polymers are used in detergents because of their builder properties.
  • the object of the present invention is to provide a textile care agent that considerably reduces the formation of fluff and pills in textile fabrics.
  • the present invention therefore relates in a first embodiment to a textile care composition
  • a copolymer obtainable by copolymerizing a component (a) comprising one or more ethylenically unsaturated carboxylic acid (s) and / or salts thereof with a component (b) comprising carbohydrates , in the presence of optionally component (c), comprising one or more oxidizing agents, and additionally optionally one or more complexing agents.
  • textile care agents are understood to mean both washing and cleaning agents and pre-treatment agents and agents for conditioning textile fabrics, such as mild detergents and post-treatment agents, such as fabric softener.
  • conditioning is understood to mean the finishing treatment of textile fabrics, fabrics, yarns and fabrics.
  • the conditioning gives the textiles positive properties, such as an improved soft feel, increased gloss and color brilliance, a fragrance refreshment and a reduction in the creasing behavior and the static charge.
  • the textile care agents according to the invention contain a copolymer as an essential component.
  • the copolymer can be obtained by copolymerizing a component (a) comprising one or more ethylenically unsaturated carboxylic acid (s) and / or their salts with one
  • Component (b) comprising carbohydrates in the presence of optionally
  • Component (c) comprising one or more oxidizing agents.
  • component (a) ethylenically unsaturated carboxylic acids and / or their salts for example, ethylenically unsaturated C 3 - C-io-carboxylic acids, C preferably 3 -C 6 carboxylic acid, more preferably ⁇ -ß-unsatu- saturated carboxylic acids, especially ⁇ - ⁇ -unsaturated C 3 -G 6 carboxylic acids and / or their
  • ethylenically unsaturated carboxylic acids which are fed to the copolymerization as monomers are acrylic acid, meth-
  • acrylic acid ethyl acrylic acid, allylacetic acid and vinyl acetic acid. From this group of monomers, preference is given to using acrylic acid, methacrylic acid, their mixtures and the sodium, potassium or ammonium salts or mixtures thereof.
  • the monomers of group a) which can optionally be used in the copolymerization include, for example, C to C 6 alkyl and / or hydroxyalkyl esters of the compounds mentioned, for example methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate, Maleic acid monomethyl ester, maleic acid diethyl ester, hydroxyethyl acrylate, hydroxypropyl acrylates, hydroxybutyl acrylates, hydroxyethyl methacrylate and hydroxypropyl methacrylate and esters of acrylic acid and methacrylic acid with polyhydric alcohols, for example
  • the amides and N-substituted alkylamides of the compounds mentioned can be considered as monomers of group a), for example acrylamide, methacrylamide, N-alkylacrylamides having 1 to 18 carbon atoms in the alkyl group, such as N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide, N-octadecylacrylamide, maleic acid monoethylhexylamide, maleic acid monododecylamide, dimethylaminopropylmethacrylamide and acrylamidoglycolic acid.
  • group a for example acrylamide, methacrylamide, N-alkylacrylamides having 1 to 18 carbon atoms in the alkyl group, such as N-methylacrylamide, N, N-dimethylacrylamide, N-tert-butylacrylamide, N-octadecylacrylamide, maleic acid monoethylhexylamide, maleic acid
  • alkylaminoalkyl (meth) acrylates e.g. Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate and / or dimethylaminopropyl methacrylate.
  • suitable as component (b), optionally modified, carbohydrates which contain at least three carbon atoms and have a polyol character, i.e. contain at least three hydroxyl groups per carbon chain or ring, and are soluble, suspendable or swellable in water.
  • carbohydrates are natural saccharides or modification products thereof, that is to say saccharides which are obtained from animal or vegetable products (for example from the processing of milk, honey or parts of plants), or a fold modification products thereof, for example enzymatically or chemically modified (for example by hydrolysis, hydrogenation, oxidation, partial etherification or esterification and / or derivatization), provided that the essential polyol character of the saccharide is retained.
  • synthetic saccharides can also be used, primarily polymerization products of mono- and / or disaccharides, as can be prepared by polymerization in aqueous solution, but the carbohydrates are preferably natural saccharides or simple modification products thereof:
  • Suitable carbohydrates are advantageously oligosaccharides or polysaccharides, the monomer units of which contain 4 to 7, preferably 5 or 6, carbon atoms.
  • the modified carbohydrates are primarily those carbohydrates in which one or two functional groups have been chemically modified, for example by alkylation, for example with unsubstituted or substituted low molecular weight alkyl, especially alkylation with unsubstituted C 4 alkyl, in particular methyl or butyl , Boxyalkylation, primarily carboxymethylation (for example by reaction with chloroacetic acid), addition of epoxides (for example ethylene oxide or propylene oxide) to oxyalkylation products, or reaction with optionally substituted chlorohydrins, or by acylation, for example with ⁇ cyl radicals of low molecular weight carboxylic acids, primarily of C 2 , 4- carboxylic acids, especially acetyl, or derivatization, provided that at least three hydroxyl groups with carbohydrate character are present per carbon
  • Modification products are also to be understood as meaning cationically modified polysaccharides, for example starches reacted with 2,3-epoxypropyltrimethylammonium chloride, as described, for example, in US Pat. No. 3,649,616.
  • Chemically modified polysaccharides also include, for example, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, sulfoethyl cellulose, carboxymethyl sulfoethyl cellulose, hydroxypropyl sulfoethyl cellulose, hydroxyethyl sulfoethyl cellulose, methyl sulfoethyl cellulose and ethyl sulfo.
  • Any oligosaccharides or polysaccharides or simple modification products thereof or mixtures thereof can be considered as carbohydrates.
  • Carbohydrates are, for example, starch, pectin, algin, chitin, chitosan, heparin, carrageenan, agar, gum arabic, tragacanth, karaya gum, ghatti gum, locust bean gum, guar gum, tara gum, inulin, xanthan, dextran, sucrose , Nigeran and pentosans such as xylan and araban, the main components of which are D-glucuronic acid, D-Ga lacturonic acid, D-galacturonic acid methyl ester, D-mannuronic acid, L-guluronic acid, D- and
  • L-galactose 3,6-anhydro-D-galactose, L-arabinose, L-rhamnose, D-glucoronic acid, D-, xylose, L-fucose, D-mannose, D-fructose and D-glucose, 2-amino -2-des'oxy-Q-glucose and 2-amino-2-deoxy-D-galactose and their N-acetyl derivatives.
  • oligosaccharides are open-chain or cyclic oligosaccharides, e.g. Lactose, maltose, cellobiose, raffinose, gentiobiose, trehalose, melezitose,
  • Dextrins and cyclodextrins ⁇ , ⁇ and / or ⁇
  • carbohydrates which are present as polysaccharides those which are soluble, suspendable or swellable in water, especially starch polysaccharides, and / or essentially linear polysaccharides which are found in starches, in particular amylose, and degradation products (preferably hydrolysis products) are particularly suitable.
  • starch polysaccharides, and / or essentially linear polysaccharides which are found in starches, in particular amylose, and degradation products (preferably hydrolysis products) are particularly suitable.
  • syrup or dextrins and mixtures of such polysaccharides, and / or essentially linear other polysaccharides and branched polysaccharides, for example cellulose, xylans, arabanes and galactans.
  • the carbohydrates used are particularly preferably polysaccharides which are particularly suitable for graft copolymerization.
  • starch thermally and / or mechanically treated starch, oxidatively, hydrolytically or oxidized enzymatically degraded starches, oxidized hydrolytically or oxidized enzymatically degraded starches and chemically modified starches are used as the carbohydrates.
  • all strengths are suitable.
  • starches from corn, wheat, rice, tapioca and in particular starch from potatoes are preferred.
  • starches are practically insoluble in water and can be converted into a water-soluble form in a known manner by thermal and / or mechanical treatment or by enzymatic or acid-catalyzed degradation.
  • the following compounds may be mentioned as starch breakdown products, which are obtainable either by oxidative, hydrolytic or enzymatic breakdown of starch: dextrins such as white and yellow dextrins, maltodextrins, glucose syrups, maltose syrups, hydrolysates with a high content of D-glucose, starch saccharification products and maltose and D. -Glucose and its isomerization product fructose.
  • Starch components such as those found in conventional starch flours (eg obtained from parts of plants, such as legumes, cereals, tuber roots), are particularly advantageously used as carbohydrates for the polymers to be used according to the invention.
  • Palm pulp or algae for example rice starch, corn starch, potato starch, tapio starch, soy starch guaran, carrageenan, carubin, agar or ghatti gum and mixtures thereof.
  • the process for the preparation of the copolymer or a mixture to be used according to the invention is preferably carried out in a suitable solvent, preferably in a polar solvent, in particular in an aqueous medium.
  • the polymerization takes place at pH values which are preferably in the acid range, particularly preferably below a pH value of 6, in particular below a pH value of 5 and in particular within a pH value of 0.1 to 4 , lie.
  • Aqueous media with the aforementioned pH value ranges have proven to be advantageous in the context of the present invention.
  • the pH is advantageously adjusted with a strong mineral acid, for example phosphoric acid or preferably sulfuric acid> or a strong carboxylic acid, for example citric acid.
  • component (b) The polymerization of the monomers of component (a) with the carbohydrates (component (b)) takes place, depending on the nature, concentration and pretreatment of the components, preferably in such a way that the reaction mixture is in the form of a real or colloidal solution.
  • the carbohydrates can be in suspended or swollen, dispersed form, but it is advantageous that the mixture is stirrable.
  • component (b) is at least partially soluble in the reaction medium.
  • Component (b) can therefore preferably already be a modification product of the natural carbohydrates, for example products of the metabolism of microorganisms, which ensure that the carbohydrates are already soluble and / or dispersed in water.
  • an enzymatic pretreatment for example of oligosaccharides or polysaccharides or of pectins, can also precede the above-mentioned polymerization in one operation, in the same reaction vessel.
  • the enzymatic reaction can then expediently be stopped by adding acids.
  • the molar ratio of component (a) to component (b) can vary within a wide range, expediently such that on average at least one basic unit of component (a) is present per basic carbohydrate molecule in the end product.
  • a carbohydrate unit in the optionally modified starting carbohydrate is understood to mean an open-chain or preferably cyclic, optionally modified carbohydrate group which carries at least three hydroxyl groups as substituents per group of connected carbon atoms and, if it is cyclic, one (preferably furanoside or pyranoside) oxygen atom as a ring member contains, and wherein the carbohydrate units can optionally be bridged together via oxygen (for example a glucoside ring, as occurs in oligo- or polyglucosides).
  • the copolymer to be used according to the invention is in the form of a graft copolymer.
  • Graft copolymers are formed, for example, when monomers are preferably radically polymerized in the presence of prefabricated polymers which serve as macroinitiators and thus simultaneously as graft substrates. 1
  • the carbohydrates as component (b) form the graft substrate onto which the monomers of component (a) can be grafted.
  • graft copolymers which have a high graft density and short graft branches have been found to be particularly suitable for the effect of lint reduction and the reduction of creasing.
  • the average degree of substitution is preferably above 1.5, preferably above 2 and in particular above 2.5. Also particularly suitable are those graft copolymers in which each graft site has on average more than one monomer, preferably more than 2 monomers, particularly preferably 2.5 to 5 monomer units, component (a).
  • the degree of substitution and length of the graft branches can be determined, for example, by NMR measurements in comparison with corresponding standards.
  • the reaction temperature for the polymerization is mainly values in the range from 20 to 150 ° C, advantageously 40 to 100 ° C, preferably 60 to 98 ° C, in particular 70 to 90 ° C.
  • component (c) comprising one or more oxidizing agents.
  • component (c) is preferably in the weight ratio of component (c) to components (a) + (b) from (1: 100) to (1: 1), particularly preferably from (1: 70) to (1: 2), in particular from (1:50) to (1:10), component (c) preferably having a sufficient oxidizing power to oxidize carbonyl groups and also oxidize and degrade the ones used To effect component (b), preferably a polysaccharide, and thus to initiate a polymerization of the reaction mixture starting from component (b).
  • component (c) all oxidizing agents familiar to the person skilled in the art are possible.
  • Hydrogen peroxide is preferably used as the oxidizing agent.
  • the hydrogen peroxide can be used as such or as an H 2 O 2 -releasing compound, for example as potassium peroxide or in the form of an organic peracid, but is preferably used directly as H 2 O 2 . Mixtures of several oxidizing agents are also possible.
  • the oxidizing agent is free of transition metal ions.
  • the respective reactants and optionally component (c) can be added all at once or in stages; Good reaction control can be achieved, for example, by gradually adding component (c).
  • the degree of polymerization of the components (a) and (b) used can be controlled, for example, by means of the amount of component (c), in a manner familiar to those skilled in the art.
  • the copolymers to be used according to the invention are advantageously obtainable by free-radical polymerization, it may be expedient to carry out the copolymerization in the presence of free-radical initiators or under the action of suitable high-energy radiation.
  • the following initiators or catalysts are particularly suitable: water-soluble azo compounds, for example 4,4'- Azobis (4-cyanopentanoic acid), 2,2'-azobis (2-aminodipropane) dihydrochloride or azobisisobutyric acid dinitrile, .redox systems or peroxy compounds (in particular diacetyl peroxide, di-tert.butyl peroxide, tert.butylhydr ⁇ peroxide) Butyl perpivalate, cumene hydroperoxide, benzoyl hydroperoxide, dibenzoyl peroxide, diisopropylperoxydicarbonate, sodium perborate, hydrogen peroxide or ammonium or alkali metal peroxydisulfate
  • Suitable basic components are, for example, ammonia, alkali metal hydroxides and / or low molecular weight mono-, di- or tri-alkylamines or alkanolamines, in particular triethanolamine or triisopropanolamine, and / or buffering alkali metal salts, including alkali metal hydroxides (lithium, sodium - or potassium hydroxide) are preferred, especially sodium hydroxide and potassium hydroxide.
  • the length and distribution of the (co) polymer chains can be determined by the choice of the proportions and the reaction conditions.
  • the copolymers may contain component (a) attached or incorporated to form copolymers and / or graft copolymers.
  • carbohydrate units can also be attached or installed at the corresponding point.
  • the average molecular weight Mw of the copolymers to be used according to the invention is, for example, in the range from above 1000, preferably above 5000, particularly preferably above 10000, in particular above 15000, advantageously between 18000 and 70,000, most preferably between 20,000 and 65,000 g / mol.
  • the molecular weight can be determined by gel permeation chromatography against standardized polyacrylic acid standards.
  • graft copolymers are already known in the prior art, for example from US 3,558,499 and DE 40 03 172 A1.
  • the preparation of graft copolymers which are preferably to be used according to the invention is illustrated by way of example. Preparation of the graft copolymer A:
  • a mixture of 20 to 45 parts by weight of an acidic complexing agent and approximately the same amount of starch is dissolved in warm water and then the same amount by weight of acrylic acid and simultaneously 1 to 10 parts by weight of hydrogen peroxide in combination with a radical initiator, diluted as an aqueous solution, slowly added with cooling and Temperaturko ⁇ stanz, the polymerization takes place.
  • the product can optionally be diluted with water to the desired concentration and / or adjusted to a desired pH using suitable bases.
  • the textile care agent according to the invention contains the copolymers to be used according to the invention in an effective amount, preferably above 0.05% by weight, particularly preferably from 0.1 to 10% by weight, in particular from 1 to 5% by weight, in each case based on the entire mean.
  • the textile care agents additionally contain complexing agents.
  • complexing agents organic, advantageously water-soluble, complexing agents can be incorporated particularly well into the textile care products according to the invention and, in particular together with the copolymers to be used according to the invention, impart increased stability to the textile care products, in particular the liquid textile care products.
  • the complexing agents improve the stability of the agents and protect, for example, against the decomposition of certain ingredients of active detergent formulations catalyzed by heavy metals. Together with the copolymers to be used according to the invention, they contribute to the inhibition of incrustations.
  • the polymerization reaction for the preparation of the copolymers is carried out in the presence of the complexing agent.
  • coplexing agents which have acid groups and which can additionally take on a pH-controlling function.
  • the group of complexing agents includes, for example, the alkali metal salts of nitrilotriacetic acid (NTA) and their derivatives and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.
  • NTA nitrilotriacetic acid
  • Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids and their derivatives and mixtures of these are also suitable.
  • Preferred compounds include in particular organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.
  • Particularly preferred within the scope of the present invention is the citric acid ⁇ '' A and
  • the textile care agents contain complexing agents in an amount of up to 20% by weight, preferably from 0.01 to 15% by weight, particularly preferably from 0.1 to 10% and in particular from 0.3 to 5.0% by weight. -%, advantageously from 1, 5 to 3 wt .-%, each based on the total agent.
  • the textile care agents according to the invention can be present in solid form, for example as powder, granulate, extrudate, pressed and / or melted shaped bodies, for example as tablets or preferably in liquid form, for example as a dispersion, suspension, emulsion, solution, microemulsion, gel or paste.
  • the textile care agents according to the invention additionally contain nonionic surfactants.
  • nonionic surfactants not only increases the washing performance of the agents according to the invention, but also supports the dispersion and homogeneous distribution of the copolymer to be used according to the invention.
  • Preferred nonionic surfactants are alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO ) per mole of alcohol.
  • Particularly preferred are C 8 -C 16 alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C 10 -C 10 alcohol alkoxylates, in particular C 12 -C 4 alcohol alkoxylates, with a degree of ethoxylation between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1, 5 and 5.
  • the alcohol radical can preferably be methyl-branched linearly or particularly preferably in the 2-position or contain linear and methyl-branched radicals in the mixture, as is usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 2 . 14 alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C 13 - 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 .
  • alkoxylated amines advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines with preferably 1 to 18 C atoms per alkyl chain and an average of 1 to 12 mol ethylene oxide (EO) and / or 1 to 10 mol propylene oxide (PO ) per mole of amine.
  • EO mol ethylene oxide
  • PO mol propylene oxide
  • the end-capped alkoxylated fatty amines and fatty alcohols have proven to be particularly advantageous, particularly for use in the non-aqueous formulations according to the invention.
  • the terminal hydroxyl groups of the fatty alcohol alkoxylates and fatty amine alkoxylates in the end-capped fatty alcohol alkoxylates and fatty amine alkoxylates are etherified by C 1 -C 20 alkyl groups, preferably methyl or ethyl groups.
  • alkyl glycosides of the general formula RO (G) Xf can also be used as further nonionic surfactants, for example as compounds, especially with anionic surfactants, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched, aliphatic radical having 8 to 22 preferably means 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which are two hydrophilic groups and two have hydrophobic groups per molecule. These groups are generally separated from one another by a so-called “spacer”. This spacer is generally a carbon chain which should be long enough that the hydrophilic groups are sufficiently spaced so that they can act independently of one another. Such surfactants are distinguished generally due to an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water, but in exceptional cases the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE-A-43 21 022 or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to international patent application WO-A-96/23768.
  • End group-capped dimeric and trimeric mixed ethers according to German patent application DE-A-195 13 391 are distinguished in particular by their beta and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini-polyhydroxy fatty acid amides or poly-poly-hydroxy fatty acid amides can also be used.
  • Suitable surfactants are polyhydroxy fatty acid amides of the following formula,
  • R-CO-N- [Z] in the RCO for an aliphatic acyl radical with 6 to 22 carbon atoms R 5 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 up to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the following formula
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example gl.ucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example gl.ucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants selected from the group of alkoxylated fatty alcohols and / or alkyl glycosides, in particular mixtures of alkoxylated fatty alcohols and alkyl glycosides, are used.
  • the textile care agents according to the invention contain nonionic surfactants in amounts of up to 35% by weight, preferably from 5 to 25% by weight, particularly preferably from 10 to 20% by weight, in each case based on the total agent ,
  • the textile care agents according to the invention can additionally contain anionic surfactants.
  • anionic surfactants significantly increases the dirt-removing behavior of the agents according to the invention during the washing process without significantly impairing the effect of the copolymers to be used according to the invention as a lint reduction component and anti-crease component.
  • anionic surfactants are those of the sulfonate type. and sulfates used.
  • the Te ⁇ sides of the sulfonate type are preferably C 9 .i 3 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from C 12 . 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates made from Gi 2 . 18 alkanes, for example
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 2 -C 16 alkyl sulfates and C 2 -C 1 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched with an average of 3.5 moles of ethylene oxide (EO) or C 12 .
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol radicals or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated pick r Fettalko, which represent non-ionic surfactants considered for.
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from. natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants' including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the ammonium salts in particular the salts of organic bases, such as isopropylamine, are preferred.
  • Ether carboxylic acids are insensitive to water hardness and have excellent surfactant properties . Production and application are, for example, in soaps, oils, fats, waxes 101, 37 (1975); 115, 235 (1989) and Tenside Deterg. 25, 308 (1988).
  • the textile cleaning agents according to the invention contain anionic surfactants, preferably selected from the group of fatty alcohol holsulfates and / or fatty alcohol ether sulfates and / or alkylbenzenesulfonates and / or
  • the content of anionic surfactants can vary considerably. If the textile care agents are present as mild detergents or aftertreatment agents, for example as fabric softeners, the amounts are below 10% by weight, preferably below 5% by weight and in particular below 1% by weight, in each case based on the total Medium. >
  • Heavy duty detergents for example as a non-aqueous liquid detergent, can contain anionic surfactants in amounts of up to 65% by weight, preferably in amounts of up to 50% by weight, particularly preferably in amounts of 5 to 35% by weight, based in each case on the entire means.
  • the textile care agents according to the invention can additionally contain enzymes.
  • Enzymes support the washing processes in a variety of ways, in particular in the removal of badly bleachable contaminants, such as protein soiling.
  • the incorporation of enzymes in detergent formulations, in particular in liquid textile care products often causes problems, since there may be incompatibilities with other detergent components, which in turn can cause a loss of activity of the enzymes.
  • the stability of the enzymes in wash liquor or textile care agent formulation, in particular in liquid textile care agent formulations can be improved by using the copolymers to be used according to the invention.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Active ingredients. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, Lipase or lipolytic enzymes and cellulase; in particular, however, protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed onto carrier substances as molded bodies or embedded in order to protect them against premature decomposition.
  • the textile care agents according to the invention contain enzymes, preferably selected from the group of proteases and / or amylases and / or cellulases.
  • the textile care agents according to the invention are present as mild detergents or aftertreatment agents, for example as fabric softeners, in a preferred embodiment they can contain cellulase, preferably in an amount of 0.005 to 2% by weight, particularly preferably 0.01 to 1% by weight, in particular from 0.02 to 0.5% by weight, based in each case on the total composition.
  • the textile care products according to the invention are in liquid form and advantageously have a viscosity of 50 to 5000 mPas, particularly preferably 50 to 3000 mPas and in particular 500 to 1500 mPas (measured at 20 ° C. with a rotary viscometer (Brookfield RV, spindle 2) at 20 rpm (rpm: revolutions per minute)).
  • Preferred liquid textile care agents contain in a preferred embodiment
  • Solvents which can be used in the agents according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol tiethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n -butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, butoxy propoxy propanol (BPP), dipropylene glycol monomethyl or ethyl ether, diisopropylene
  • glycol ethers are available under the trade names Arcosolv ® (Arco Chemical Co.) or Cellosolve ® , Carbitol ® or Propasol ® (Union Carbide Corp.); This also includes, for example, ButylCarbitol ® , HexylCarbitol ® , MethylCarbitol ® , and Carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • Arcosolv ® Arco Chemical Co.
  • Cellosolve ® Carbitol ®
  • Propasol ® Union Carbide Corp.
  • ButylCarbitol ® HexylCarbitol ®
  • MethylCarbitol ® MethylCarbitol ®
  • Carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • the choice of the glycol ether can be easily made by those skilled in the art based on its volatility,
  • Pyrrolidone solvents such as N-alkylpyrrolidones, for example N-methyl-2-pyrrolidone or NC 8 -C 12 alkylpyrrolidone, or 2-pyrrolidone, can also be used.
  • Alcohols can furthermore preferably be used. They include liquid polyethylene glycols with a low molecular weight, for example polyethylene glycols with a molecular weight of 200, 300, 400 or 600.
  • suitable other alcohols are, for example, lower alcohols such as ethanol, propanol, isopropanol and n-butanol, C 2 -C -polyols , such as diols or triols, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof.
  • lower alcohols such as ethanol, propanol, isopropanol and n-butanol
  • C 2 -C -polyols such as diols or triols, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof.
  • the textile care agents according to the invention contain up to 95% by weight, particularly preferably 20 to 90% by weight and in particular 50 to 80% by weight of one or more solvents, preferably water-soluble solvents, in a preferred embodiment and especially water.
  • the textile care agents additionally contain plasticizer components, preferably Kationte.nside.
  • additional plasticizer components has proven to be extremely advantageous in particular when the textile care agents according to the invention are present as mild detergents or textile aftertreatment agents, for example as fabric softeners. Especially when washing delicate textiles, such as silk, wool or linen, at low
  • plasticizer components facilitate : Copolymers additionally 'iron the textiles and reduce the static charge of the textile materials.
  • fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile finishing products.
  • Suitable examples are quaternary ammonium compounds of the formulas (I) and (II),
  • R and R 1 are an acyclic alkyl radical having 12 to 24 carbon atoms
  • R 2 is a saturated CC 4 alkyl or hydroxyalkyl radical
  • R 3 is either R, R 1 or R 2 or is an aromatic radical
  • X " stands for either a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.
  • Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, ditallow gdimethylammonium chloride or dihexadecylammonium chloride.
  • Ester quats are so-called ester quats. Esterquats are characterized by excellent biodegradability and are particularly preferred in the context of the present invention.
  • R 4 represents an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 5 stands for H, OH or 0 (CO) R 7
  • R 6 stands independently of R 5 for H, OH or O (CO) R 8
  • R 7 and R 8 each independently represent an aliphatic alkyl radical with 12 to 22 coal atoms with 0, 1, 2 or 3 double bonds
  • m, n and p can each independently
  • ⁇ 'A dependent on each other have the value 1, 2 or 3.
  • X can either be a halide
  • Compounds are preferred which contain the group O (CO) R 7 for R 5 and alkyl radicals having 16 to 18 carbon atoms for R 4 and R 7 .
  • Compounds in which R 6 is also OH are particularly preferred.
  • Examples of compounds of the formula (II) are methyl-N- (2-hydroxyethyl) -N, N-di (tallowacyI-oxyethyl) ammonium methosulfate, bis- (palmitoyl) -ethyl-hydroxyethyl-methyl-ammonium methosulfate or Methy!
  • acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30.
  • methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex ® or the products from Cognis known under Dehyquart ® or the products from Goldschmidt-Witco known under Rewoquat ® .
  • Further preferred compounds are the diesterquats of the formula (III), which are available under the name Rewoquat® W '222 LM or CR 3099 and, in addition to the softness, also ensure stability and color protection.
  • R 21 and R 22 each independently represent an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • R 9 is H or a saturated alkyl radical with 1 to 4 carbon atoms
  • R 10 and R 11 independently of one another each represent an aliphatic, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms
  • R 10 alternatively also for O (CO) R 20
  • R 20 is an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms
  • Z is an NH group or oxygen
  • q can have integer values between 1 and 4.
  • R 12, R 13 and R 14 independently represents a C ⁇ alkyl, alkenyl or hydro xyalkyl distr
  • R 15 and R 16 are each independently selected a C 8 - 28 alkyl group
  • r represents a number between 0 and 5 is.
  • short-chain, water-soluble, quaternary ammonium compounds such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.
  • Protonated alkylamine compounds which have a plasticizing effect and the non-quaternized, protonated precursors of the cationic emulsifiers are also suitable.
  • the quaternized protein hydrolyzates are further cationic compounds which can be used according to the invention.
  • Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., ', 1997), in particular the polyquaternium-6, polyquaterium-7 also referred to as merquats -, Polyquaternium-10 polymers (Ucare Polymer IR 400; Amerchol), polyquaterium-4 copolymers, such as graft copolymers with a cellulose skeleton and quaternary ammonium groups which are bonded via allyl dimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar -hydrqxypropyltriammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polygluco
  • Polyquaternized polymers for example Luviquat Care from BASF
  • cationic biopolymers based on chitin and derivatives thereof for example, under the trade designation chitosan ® (manufacturer: Cognis) polymer obtainable.
  • cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, which is also known as amodimethicone) ), SM-2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquartary polydimethylsiloxanes, Quaternium-80), and Siliconquat Rewoquat ® SQ 1 (Tegopren ® 6922, manufacturer: Goldschmidt-Rewo).
  • Q2-7224 commercially available products
  • Dow Corning a stabilized trimethylsilylamodimethicone
  • Dow Corning 929 emulsion containing a hydroxylamino-modified silicone, which is
  • the alkylamidoamines can be in their non-quaternized or, as shown, their quaternized form.
  • R 17 can be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5.
  • R 18 and R 19 each independently represent H, C 1-4 alkyl or hydroxyalkyl.
  • fatty acid amidoamines such as the stearylamidopropyldimethylamine available under the name Tego Amid ® S 18 or the 3-tallowamidopropyl trimethylammonium methosulfate available under the name Stepantex ® X 9124, which, in addition to having a good conditioning effect, also have a color transfer inhibiting effect and are special are characterized by their good biodegradability.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate and / or N- methyl-N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium methosulfate.
  • nonionic plasticizers are polyoxyalkylene glycerol alkanoates, as described in British Patent GB 2,202,244, polybutylenes, as described in British Patent GB 2,199,855, long-chain fatty acids as described in EP 13 780, ethoxylated fatty acid ethanolamides as described in EP 43 547, Alkyl polyglycosides, in particular sorbitan mono, di and triester, as described in EP 698 140 and fatty acid esters of polycarboxylic acids, as described in German Patent DE 28 22 891.
  • the mild detergents according to the invention contain cationic surfactants, preferably alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular 'N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl ) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoylethyl) ammonium methosulfate.
  • cationic surfactants preferably alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular 'N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl ) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (
  • the textile care agents according to the invention contain plasticizer components in an amount of up to 35% by weight, preferably from 0.1 to 25% by weight, particularly preferably from 0.5 to 15% by weight and in particular from 1 to 10 wt .-%, each based on the total agent.
  • the textile care agents according to the invention are present as mild detergents or fabric softeners, containing plasticizers, preferably cationic plasticizers, particularly preferably esterquats.
  • the textile care agents according to the invention can contain pearlescent agents. Pearlescent agents give the textiles an additional gloss and are therefore preferably used in the. .
  • suitable pearlescent agents are: alkylene glycol esters; Fatty acid alkolamides; partial glycerides; Esters of polyvalent, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances such as fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers 1 and fatty carbonates, which have a total of at least 24 carbon atoms; Ring opening products of olefin epoxides with 12 to 22 carbon atoms with fatty alcohols with 12 to 22 carbon atoms, fatty acids and / or polyols with 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.
  • the textile care products according to the invention can also contain thickeners.
  • the use of thickeners in the textile care agents according to the invention, which are present as liquid detergents, has proven to be particularly advantageous. In order to increase consumer acceptance, the use of thickeners has proven particularly useful in the case of gel-shaped liquid detergents.
  • the thickened consistency of the agent simplifies the application of the agent directly to the stains to be treated. This prevents a run, as is usual with low-viscosity agents.
  • Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
  • Modified natural products mainly come from the group of modified starches and celluloses, examples include carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
  • thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
  • Thickeners from the classes of substances mentioned are widely available commercially and are sold, for example, under the trade names Acusol ® -820 (methacrylic acid (ste- aryl alcohol-20-EO) ester-acrylic acid copolymer, 30%. in water, Rohm & Haas), Dapral ® -GT-282-S (alkyl polyglycol ether, Akzo), Deuterol ® -Polymer-11 (dicarboxylic acid copolymer, Schönes GmbH), Reuteron ® -XG (anionic heteropolysaccharide based on ß -D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron ® -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ® -thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA ® -81
  • a preferred polymeric polysaccharide thickener is xanthan, a microbial anionic heteropolysaccharide that is produced by Xanthomonas campestris and some other species under aerobic conditions and has a molecular weight of 2 to 15 million g / mol.
  • Xanthan is formed from a chain with ⁇ -1,4-linked glucose (cellulose) with side chains.
  • the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
  • Xanthans and modified xanthans can be used with particular advantage on account of their extensive acid stability and oxidation stability.
  • Xanthan can be described by the following formula:
  • the textile care agents according to the invention additionally contain thickeners, preferably in amounts of up to 10% by weight, particularly preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total Medium.
  • the textile care agents according to the invention can additionally contain odor absorbers and / or color transfer inhibitors.
  • color transfer inhibitors has proven particularly useful for the textile care products according to the invention, which are present as fine, post-treatment and liquid detergents.
  • odor absorbers has proven to be very helpful for the deodorization of malodorous formulation components, such as amine-containing components, but also for the sustainable deodorization of the washed textiles.
  • the textile care agents according to the invention optionally contain 0.1% by weight to 2% by weight, preferably 0.2% by weight to 1% by weight of color transfer inhibitor, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone , Vinyl imidazole, vinyl pyridine N-oxide or a copolymer of these.
  • Both the polyvinylpyrrolidones known from European patent application EP 0 262 897 with molecular weights of 15,000 to 50,000 and the polyvinylpyrrolidones known from international patent application WO 95/06098 with molecular weights over 1,000,000, in particular from 1,500,000 to 4, can be used 000 000, the N-vinylimidazole / N-vinylpyrrolidone copolymers known from German patent applications DE 28 14 287 or DE 38 03 630 or international patent applications WO 94/10281, WO 94/26796, WO 95/03388 and WO 95/03382 , the polyvinyloxazolidones known from German patent application DE 28 14 329, which from European patent application EP 610 846 known copolymers based on vinyl
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which supplies hydrogen peroxide in water, as are known, for example, from international patent applications WO 92/18687 and WO 91/05839.
  • a mediator compound for peroxidase for example an acetosyringone known from international patent application WO 96/10079, a phenol derivative known from international patent application WO 96/12845 or a phenotiazine or phenoxazine known from international patent application WO 96/12846 is shown in preferred in this case, it also being possible to use the above-mentioned polymeric color transfer inhibitor active ingredients.
  • polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 to 60,000, in particular in the range from 25,000 to 50,000.
  • copolymers those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 with an average molecular weight in the range from 5,000 to 50,000, in particular 10,000 to 20,000, are preferred.
  • Preferred deodorant substances for the purposes of the invention are one or more metal salts of an unbranched or branched, unsaturated or saturated, mono- or polydroxyated fatty acid with at least 16 carbon atoms and / or a resin acid with the exception of the alkali metal salts and any mixtures thereof.
  • a particularly preferred unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 16 carbon atoms is ricinoleic acid.
  • a particularly preferred resin acid is abietic acid.
  • Preferred metals are the transition metals and the lanthanoids, in particular the .. " " A
  • the cobalt, nickel and copper salts and the zinc salts have a similar effect, but the zinc salts are preferred for toxicological reasons.
  • One or more metal salts of ricinoleic acid and / or abietic acid preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate, are to be used as advantageous and therefore particularly preferred as deodorising substances.
  • Cyclodextrins as well as any mixtures of the above-mentioned metal salts with cyclodextries, preferably in a weight ratio of 1:10 to 10: 1, particularly preferably from 1: 5 to 5:, 1 and in particular of prove to be further suitable deodorant substances in the sense of the invention 1: 3 to 3: 1.
  • the term "cyclodextrin” includes all known cyclodextrins, i.e. both unsubstituted cyclodextrins with 6 to 12 glucose units, in particular alpha, beta and gamma cyclodextrins and their mixtures and / or their derivatives and / or their mixtures.
  • the textile care agents according to the invention can additionally contain further surfactants, for example amphoteric surfactants.
  • amphoteric surfactants which can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which betaines are particularly preferred in the context of the teaching according to the invention.
  • Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy formula I,
  • R 1 - [CO-X- (CH 2 ) n ] x -N + (R 2 ) (R 3 ) - (CH 2 ) m - [CH (OH) -CH 2 ] y -Y- (I) in R 1 is a saturated or unsaturated C 6 . 22 -alkyl radical, preferably C 8 .
  • alkyl radical particularly a saturated C 0 - 1 6 alkyl group, for example a saturated C 12th 1 -alkyl radical, X NH, NR 4 with the C- M -alkyl radical R 4 , O or S
  • n is a number from 1 to 10, preferably 2 to 5, in particular 3, x 0 or 1, preferably 1
  • R 2 , R 3 independently of one another are a C 1 -C 4 -alkyl radical, optionally hydroxy-substituted, such as, for example, a hydroxyethyl radical, but in particular a methyl radical
  • m is a number from 1 to 4, in particular 1, 2 or 3, y 'O or 1 and Y COO , SO 3 , OPO (OR 5 ) O or P (O) (OR 5 ) O, where R 5 is a hydrogen atom
  • alkyl and alkyl amido betaines, betaines of formula I with a carboxylate group are also called carbobetaines.
  • Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamido betaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (I),
  • R 1 has the same meaning as in formula I.
  • amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formula (Ia) and (Ib), most preferably the alkylamidobetaines of the formula (Ib).
  • betaines and sulfobetaines are the following compounds named in accordance with INCl: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamido propyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, capryl / capramidopropyl betaines, carnitines, carnitines, C Cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, coco betaine, coco hydroxysultaine, coco / oleamidopropyl betaine, coco sultaine, decyl betaine, dihydroxyethyl oleyl glycinate, dihydroxyethyl soy glycinate, dihydroxyethyl dihydroxy talle
  • amine oxides suitable according to the invention include alkylamine oxides, in particular
  • Alkyldimethylamine oxides alkylamidoamine oxides and alkoxyalkylamine oxides.
  • Preferred amine oxides satisfy formula II
  • R 6 [CO-NH- (CH 2 ) w ] z -N + (R 7 ) (R 8 ) -O- (II) in which R 6 is a saturated or unsaturated C 6 . 22 -alkyl radical, preferably C 8 . 18 alkyl radical, in particular a saturated C 0 - 16 alkyl radical, for example a saturated C 2 .
  • -Alkylrest which is bonded to the nitrogen atom N in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH 2 ) 2 - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH 2 ) z , z each for a number from 1 to 10, preferably 2 to 5, in particular 3,
  • R 7 , R 8 independently of one another, is a C 1 -C 4 alkyl radical, optionally hydroxyl-substituted, such as, for example, a hydroxyethyl radical, in particular a methyl radical.
  • Suitable amine oxides are the following compounds named according to INCl: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminoproxyimidine Oxide, Caminopyrimidine Oxide Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Tal- Iowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Hydroxyethylamine Alkoxypropylamine Oxide, Isosteara
  • alkylamidoalkylamines are amphoteric surfactants of the formula (III)
  • R 10 is a hydrogen atom H or a C 1-4 alkyl radical, preferably H, i is a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,
  • R 11 is a hydrogen atom H or CH 2 COOM (to M su), j is a number from 1 to 4, preferably 1 or 2, in particular 1, k is a number from 0 to 4, preferably 0 or 1,
  • M is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine.
  • alkylamidoalkylamines are the following INCI named compounds according to: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, disodium coco amphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoampho - Dipropionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-lsodeceth-7 Carboxyamphodia
  • Alkyl-substituted amino acids preferred according to the invention are monoalkyl-substituted amino acids according to formula (IV),
  • M ' is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, e.g. protonated mono-, di- or triethanolamine,
  • Alkanolamine e.g. protonated mono-, di- or triethanolamine
  • M "in the two arboxy groups can have the same or two different meanings, e.g. hydrogen and sodium or twice sodium
  • alkyl-substituted amino acids are the aminopropionates according to formula (IVa)
  • alkyl-substituted amino acids are the following compounds named according to INCl: aminopropyl laurylglutamine, cocaminobutyric acid, cocaminopropionic acid, DEA lauraminopropionate, disodium cocaminopropyl iminodiacetate, disodium dicarboxyethyl cocopropylenediamine, disodium laurododipropionate, aminodropropionate, disodium steariminodimine, disodium steariminodimine, disodium stearin imidodiphenate, disodium steariminodimine, disodium stearin imidodipinate, disodium stearin imidodiphenate, disodium stearin imidodiphenate, disodium stearin imidodiphenate, disodium stearin imidodipinate , Lauryl Diethylenediaminoglycine, Myristaminopropi
  • Acylated amino acids are amino acids, especially the 20 natural ⁇ -amino acids, which carry the acyl residue R 19 CO of a saturated or unsaturated fatty acid R 19 COOH on the amino nitrogen atom, where R 19 is a saturated or unsaturated C 6 . 22 -alkyl radical, preferably C 8 -18 alkyl group, preferably a saturated C 10-16 alkyl group, for example a saturated C 12th 14 alkyl radical.
  • the acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt.
  • acylated amino acids are the acyl derivatives summarized according to INCl under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.
  • the total surfactant content of the textile care products according to the invention, without the amount of fatty acid soap is below 55% by weight, preferably below 50% by weight, particularly preferably between 38 and 48% by weight, in each case based on the total Medium.
  • the textile care agents according to the invention can additionally contain further detergent additives, for example from the group of builders, bleaching agents, bleach activators, electrolytes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, graying inhibitors, anti-crease agents, antimicrobial agents, germicides, antifungal agents, antioxidants, antioxidants, antioxidants, antioxidants , Ironing aids, UV absorbers, optical brighteners, anti-redeposition agents, viscosity regulators, anti-shrink agents, corrosion inhibitors, preservatives, phobing and impregnating agents.
  • further detergent additives for example from the group of builders, bleaching agents, bleach activators, electrolytes, pH adjusting agents, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, graying inhibitors, anti-crease agents, antimicrobial agents, germicides, antifungal agents, antioxidants, antioxidants, antioxidants, antioxidants , Ironing aids, UV absorbers, optical brighteners, anti-redeposition agents,
  • the agents according to the invention can contain builders.
  • All builders commonly used in detergents and cleaning agents can be incorporated into the agents according to the invention, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 »H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 • yH 2 O are preferred, with ⁇ -Na- trium disilicate can be obtained, for example, by the method described in international patent application WO-Ar91 / 08171.
  • the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compaction / compaction, or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the zeolites can also be used as over-dried zeolites with lower water contents and are then suitable due to their hygroscopicity for removing unwanted traces of free water.
  • phosphates As builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV- 1 detector being used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group.
  • Suitable polymers can also comprise substances which consist partly or completely of units of vinyl alcohol or its derivatives.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which are 50 contain up to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / molj, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol:
  • the (co) polymeric polycarboxylates can can be used either as an aqueous solution or preferably as a powder.
  • the polymers can also contain allylsulfonic acid, such as, for example, EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as the monomer.
  • allylsulfonic acid such as, for example, EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as the monomer.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-19540 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • Polyvinylpyrrolidones, polyamine derivatives such as quaternized and / or ethoxylated hexamethylene diamines are also suitable.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • a preferred dextrin is described in British patent application 9419 091.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0427 349, EP-A-0472 042 and EP-A-0 542 496 and the international patent applications WO-A -92- / 18542, WO-A-93/08251, WO-A- 93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A- 95/20608 known.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylene diamine N, N'-disuccinate (EDDS) the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccihates and glycerol trisuccinates as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and in Japanese patent application JP-A-93/339 896 become.
  • Suitable amounts for use in zeolite-containing and / or silicate-containing formulations are 3 to 15% by weight.
  • Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and at most two acid groups. Such cobuilders are described, for example, in international patent application WO 95/20029.
  • the agents according to the invention can optionally builders in amounts of 1 to 30 wt .-%, preferably 10 to 25 wt .-%.
  • the agents according to the invention can contain bleaching agents.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxopyro- phosphates, citrate perhydrates and H 2 O 2 delivering peracidic salts or peracids, such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide can also be used, which can be described by the formula H 2 N-CO-NH 2 -H 2 O 2 .
  • the agents for cleaning hard surfaces for example in automatic dishwashing
  • they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is in principle also possible for agents for textile washing.
  • Typical organic bleaching agents are the dacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are the peroxysuric acids, the alkyl peroxy acids and the aryl peroxy acids being mentioned as examples.
  • Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxyimidoperacid, porepoxy (phyto), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydiperoxybiperylacid, 1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic
  • the agents according to the invention can contain bleach activators.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, especially triacetin, triethyl (TEAC), Ethylenglykoidiacetat, 2 , 5-diacetoxy-2,5-di
  • hydrophilically substituted acyl acetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE 4443 177 can also be used.
  • Another class of preferred liquid bleach activators are the liquid imide bleach activators of the formula below.
  • the agents according to the invention can contain electrolytes.
  • a wide number of different salts can be used as electrolytes from the group of inorganic salts.
  • Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl 2 in the agents according to the invention is preferred.
  • the proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.
  • the agents according to the invention can contain pH adjusting agents.
  • pH adjusting agents In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or bases can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation.
  • the agents according to the invention can contain colorants and fragrances.
  • Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the washing or cleaning performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • perfume oils or fragrances individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde type; Ketones, alcohols and hydrocarbons are used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropylatelionylateylateylatepylpropylatepylionate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyd, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc-isomethylionone and methyl -cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the agents according to the invention can contain UV absorbers.
  • the agents can contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of the other formulation components.
  • UV absorbers are understood to mean organic substances (light protection filters) which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat.
  • Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
  • substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotri- azol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ® Fast H), 3-position into Phe nyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid are suitable.
  • UV-B absorbers are ⁇ -benzylidene camphor and 3-benzylidene norcampher and their derivatives, for example 3- (4 methylbenzylidene) camphor, as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phen
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenon-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-benzylidene camphor such as 4- (2-oxo-3-bornylidenemethyl) benzene-sulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and their salts.
  • UV-A filters Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert, are particularly suitable as typical UV-A filters.
  • -Butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds as described in DE 19712033 A1 (BASF).
  • the UV-A and UV-B filters can of course also be used in mixtures.
  • insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and in addition oxides of iron, zirconium, silicon, manganese, aluminum and cerium as well as their mixtures.
  • Silicates (talc), barium sulfate or zinc stearate can be used as salts.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 'nm and in particular between 15' and 30 nm.
  • the pigments can also be surface-treated, ie hydrophilized or hydrophobic.
  • Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by P.Finkel in S ⁇ FW-Journal 122, 543 (1996).
  • the UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.
  • the agents according to the invention can contain anti-crease agents. Since textile fabrics, in particular made from rayon, wool, cotton and their mixtures, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, the compositions can contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.
  • the agents according to the invention can contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Let continue soluble starch preparations and starch products other than those mentioned above are used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • ceilulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl ⁇ 'hydroxypropyl cellulose, methyl carboxymethyl cellulose are preferred.
  • the textile care agents according to the invention are present as a portion in a completely or partially water-soluble coating.
  • the portioning makes it easier for the consumer to dose.
  • the textile care products are packaged, for example, in foil bags.
  • Foil bags made of water-soluble foil make it unnecessary for the consumer to tear open the packaging. In this way, it is convenient to dose a single portion measured for one wash cycle by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or in the hand wash or Sink, possible.
  • the foil pouch surrounding the washing portion dissolves without residue when a certain temperature is reached.
  • Detergents packaged in bags made of water-soluble film are also described in large numbers in the prior art.
  • the older patent application DE 198 31 703 discloses a portioned detergent or cleaning agent preparation in a pouch made of water-soluble film, in particular in a pouch made of (optionally acetalized) polyvinyl alcohol (PVAL), in which at least 70% by weight of the particles of the detergent or detergent preparation have particle sizes> 800 ⁇ m.
  • PVAL polyvinyl alcohol
  • thermoforming process deep-drawing process
  • the water-soluble casings do not necessarily have to consist of a film material, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.
  • a known process for the production of water-soluble hollow injection moldings containing detergents and / or cleaning agents is described, for example, in WO-A1 01/36290.
  • a process for the production of water-soluble capsules, in which the filling and then the sealing takes place, is disclosed in WO 01/64421.
  • the manufacturing process is based on the so-called Bottle-Pack ® method, as described, for example, in German Offenlegungsschrift DE 14 114 69.
  • a tube-like preform is guided into a two-part cavity. The cavity is closed, the lower tube section being sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
  • the shell material used for the production of the water-soluble portion is preferably a water-soluble polymer thermoplastic, particularly preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives , Blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethyl cellulose and / or polyvinyl alcohol blends.
  • the covering material consists entirely or partially of the copolymers to be used in the textile care products according to the invention.
  • polyvinyl alcohols described above are commercially available under the trademark Mowiol beispiels- as ® (Clariant).
  • particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88, Mowiol ® 8-88 and Clariant L648.
  • ELVANOL ® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
  • ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
  • Gohsenol ® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK ).
  • the water-soluble thermoplastic used to prepare the portion according to the invention can additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol, the molecular weight of which is in the range from 10,000 to 100,000 gmol "1 , preferably from 11,000 to 90,000 gmol " 1 , particularly preferably from 12,000 to 80,000 gmol "1 and in particular from 13,000 to 70% 000 gmol "1 . It is further preferred if the thermoplastics in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the Weight of the water-soluble polymeric thermoplastic is present.
  • the polymeric thermoplastics can contain plasticizers to improve their machinability. This can be particularly advantageous if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been selected as the polymer material for the portion. Glycerin, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proven particularly useful as plasticizers.
  • the polymeric thermoplastics plasticizers in amounts of at least> 0% by weight, preferably of ⁇ 10% by weight, particularly preferably of ⁇ 20% by weight and in particular of ⁇ 30% by weight, in each case based on the weight of the wrapping material.
  • Another object of the invention is the use of a copolymer to be used according to the invention in a textile care agent to reduce the formation of fluff.
  • Another object of the invention is the use of a copolymer to be used according to the invention in a textile care agent to reduce the pill formation of textile fabrics.
  • Another object of the invention is the use of a copolymer to be used according to the invention in a textile care agent for facilitating the ironing of textile fabrics.
  • copolymers to be used according to the invention not only reduce the formation of creases and ensure a smooth textile surface, but also considerably improve the soft hand of the treated textiles.
  • Another object of the invention is therefore the use of a copolymer to be used according to the invention in a textile care agent for reducing creases, smoothing and improving the soft feel of textile fabrics.
  • Another object of the invention is a conditioning substrate, which is a substrate that is impregnated and / or impregnated with the textile care agent according to the invention.
  • the substrate material consists of porous materials that are capable of a soaking liquid reversible up 'and leave.
  • Both three-dimensional structures such as sponges, but preferably porous, flat cloths are suitable for this. They can consist of a fibrous or cellular flexible material which has sufficient thermal stability for use in the dryer and which can retain sufficient amounts of an impregnating or coating agent in order to effectively condition substances without any significant leakage or bleeding during storage By means of.
  • wipes include wipes made of woven and non-woven synthetic and natural fibers, felt, paper or foam, such as hydrophilic polyurethane foam.
  • Nonwovens are generally defined as adhesively bonded fibrous products which have a mat or layered fiber structure, or those which comprise fiber mats in which the fibers are randomly or randomly distributed.
  • Fibers can be natural, such as wool, silk, jute, hemp, cotton, flax, sisal or ramie; or synthetic, such as rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides, viscose or polyester. In general, any fiber diameter or titer is suitable for the present invention.
  • Preferred conditioning substrates according to the invention consist of a nonwoven material which contains cellulose. Due to the random or statistical arrangement of fibers in the non-woven material, which give excellent strength in all directions, the non-woven fabrics used here do not tend to tear or disintegrate, for example, if they are used in a household dryer.
  • non-woven fabrics which are suitable as substrates in the present invention are known, for example, from WO 93/23603.
  • Preferred porous and flat conditioning wipes consist of one or different fiber materials, in particular cotton, refined cotton, polyamide, polyester or mixtures of these.
  • the conditioning substrates in cloth form preferably have an area of 0.2 to 0.005 m 2 , preferably 0.15 to 0.01 m 2 , in particular 0.1 to 0.03 cm 2 and particularly preferably 0.09 to 0, 06 m 2 .
  • the grammage of the material is usually between 20 and 500 g / m 2 , preferably from 25 to 200 g / m 2 , in particular from 30 to 100 g / m 2 and particularly preferably from 40 to 80 g / m 2 .
  • Another object of the invention is a conditioning method for conditioning moist textiles by means of the conditioning substrate according to the invention.
  • the conditioning process is carried out by the conditioning substrate according to the invention together with moist textiles, for example from a previous one
  • Washing process originate, is used in a textile drying process.
  • the textile drying process usually takes place in a device for drying textiles, preferably in a household clothes dryer.
  • Another object of the invention is a method for reducing the lint formation of textile fabrics by bringing textile fabrics into contact with a textile care agent and / or a conditioning substrate according to the invention in a textile cleaning process and / or textile drying process.
  • the conditioning substrates according to the invention can be placed directly with the damp laundry in a household dryer and / or a washing machine.
  • the textile care products according to the invention are produced by simple mixing and stirring of the individual components, which is familiar to the person skilled in the art.
  • the copolymers to be used according to the invention can be admixed with the agent as a solution, preferably as an aqueous solution and / or as a dried powder, preferably applied to a detergent component as a carrier, compounded or granulated, mixed or tableted or pelletized.
  • the esterquats are first melted and the melt is worked into a preferably aqueous, preferably preheated, formulation with a highly dispersing stirring tool.
  • Table 1 shows the formulation E1 according to the invention and the comparison formulation V1. All data are given in percent by weight, in each case based on the total composition.
  • a commercially available iron from Rowenta P2 Professional was pulled by a Zwick universal testing machine (type 2.5 / TN1 P) over a pulley in the longitudinal direction at a speed of 800 mm per minute over the fabric.
  • the temperature of the iron was set to level III.
  • the weight of the 1680 g iron was increased to 2940 g by additional weights.
  • the force required to move the iron was measured in [N].
  • the test fabrics (textile: bleaching nettle; 100% cotton; 1, 2 * 0.2 m) were with the
  • the washing and drying cycles were repeated 3 times each.
  • Table 2 shows the measured sliding friction forces as a function of the test fabric treated with the formulations:
  • the determination of the creasing is based on the AATCC Test 124 (Ameri-, can Association of Textile and Color Chemistry).
  • the creasing is assessed after the washing and subsequent drying process, with a panel of five people assessing the creasing of the test fabric against crumpled standard fabric (AATCC124).
  • the grade 5 is given for crease-free fabrics and the grade 1 for heavily crumpled fabrics.
  • the overall grade represents the arithmetic mean of the ratings.
  • test fabrics (textile: bleaching nettle; 100% cotton; 1.0 m * 0.9 m) were treated with the formulations E1 and the comparison formulation without textile care component V1 as follows:
  • Table 3 shows the evaluation of the creases of the test fabrics as a function of the formulations: Table 3,
  • the formulation E1 according to the invention shows a significantly reduced wrinkling compared to V1.
  • Textile care agents according to the invention which are present as liquid detergents are, for example, E3 to E5, the compositions of which are shown in Table 4.
  • Table 5 shows the formulation of a textile care agent according to the invention which is present as a mild detergent E6.
  • Table 6 shows a textile care agent according to the invention, which is formulated as a non-aqueous liquid detergent E7.
  • agents E3 to E7 according to the invention showed reduced fluff formation and pill formation compared to agents not according to the invention which did not contain any copolymers to be used according to the invention.
  • a textile care agent according to the invention which is formulated as a fabric softener, is, for example, E8, a comparison recipe is V1, the compositions of which are shown in Table 7.
  • the formulation E8 was prepared by melting the ester quat in water. The melted ester quat is then stirred with a highly dispersing device and the remaining active substances are added. The perfume was added after the mixture had cooled to below 30 ° C.
  • nonwovens made of cellulose were impregnated with 20 g of the fabric softener E8 according to the invention.
  • a reference substrate with the formulation V2 was produced analogously.
  • washing-drying-weighing cycles were repeated 10 times under the following conditions: a) the textiles were dried without a conditioning substrate b) the textiles were placed in the domestic dryer with a conditioning substrate V1. c) the textiles were placed in the household dryer using a conditioning substrate E8
  • the weight of the fluff was determined after each drying cycle and added over the 10 cycles. It was found to be 7.58 g for a), 8.39 g for b) and 5.51 g for c).
  • Pill formation studies were performed under the same conditions as listed above. The investigations were carried out in instructions to DIN EN ISO 12945 part 2 "Determination of the tendency of textile fabrics to form fluff on the surface and the tendency to pills" with the aid of a Martindale scrubbing and pilling testing device model 404 ° C, 65% relative humidity)
  • the principle of the Martindale test is that test specimens are rubbed against a defined tissue in a constantly changing movement, which ensures that the surface fibers of the samples are bent in all directions Pills on the surface of the test specimens are evaluated after a defined number of tours by visual comparison against a standard set.
  • the abrasive discs with a diameter of 140 mm are clamped over the chafing tables, backed by standard felt discs.
  • the test specimens (diameter 140 mm) are fixed in special sample holders and placed with the right side to the counter textile.
  • the guide plate of the device is attached above, and weighted spindles are inserted through the guide plate into the sample holder below.
  • the drive mechanism consists of two outer and one inner drive, which forces the guide plate of the sample holder to describe a Lissajous figure.
  • the Lissajous movement changes into a circular movement towards gradually narrowing ellipses until it becomes a straight line from which progressively expanding ellipses develop in a diagonally opposite direction before the pattern is repeated.
  • the degree of pill is determined by comparing the test specimen with prepared photographs of standard goods.
  • the measurement has shown that the pill formation of the textiles, which is significantly reduced with the conditioning substrate c) in comparison to the samples from a) and b).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Details Of Garments (AREA)

Abstract

L'invention concerne un produit d'entretien pour textiles visant à ménager les textiles, ainsi que l'utilisation de ce produit pour réduire les peluches et la formation de bouloches, ainsi que pour faciliter le repassage. L'invention concerne également un substrat de conditionnement qui contient un agent de conditionnement, ainsi qu'un procédé de conditionnement utilisant le substrat de conditionnement ou un produit d'entretien pour textiles dans un processus de séchage ou de lavage de textiles.
PCT/EP2003/012484 2002-11-20 2003-11-08 Produit d'entretien doux pour textiles WO2004046288A2 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE50310385T DE50310385D1 (de) 2002-11-20 2003-11-08 Textilschonendes textilpflegemittel
EP03767523A EP1563046B1 (fr) 2002-11-20 2003-11-08 Produit d'entretien doux pour textiles
AU2003292000A AU2003292000A1 (en) 2002-11-20 2003-11-08 Textile care product
US11/135,123 US20050215449A1 (en) 2002-11-20 2005-05-20 Textile care product

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10253975 2002-11-20
DE10253975.8 2002-11-20

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/135,123 Continuation US20050215449A1 (en) 2002-11-20 2005-05-20 Textile care product

Publications (2)

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WO2004046288A2 true WO2004046288A2 (fr) 2004-06-03
WO2004046288A3 WO2004046288A3 (fr) 2004-08-12

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EP (1) EP1563046B1 (fr)
AT (1) ATE405626T1 (fr)
AU (1) AU2003292000A1 (fr)
DE (1) DE50310385D1 (fr)
ES (1) ES2309356T3 (fr)
WO (1) WO2004046288A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006116507A1 (fr) * 2005-04-26 2006-11-02 The Procter & Gamble Company Produit utilise dans un seche-linge pour eviter le depot de fibres ou de cheveux sur les tissus
DE102005044514A1 (de) * 2005-09-16 2007-03-22 Henkel Kgaa Wasch- und Reinigungsmittel mit hautpflegenden Inhaltsstoffen

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
US5223171A (en) * 1990-07-02 1993-06-29 Rhone Poulenc Chimie Detergent composition containing a biodegradable graft polysaccharide
DE4233497A1 (de) * 1992-10-06 1994-04-07 Basf Ag Verwendung von wäßrigen Polymerisatdispersionen als Textilhilfsmittel zur pflegeleichten Veredlung von Textilien
WO2001088075A1 (fr) * 2000-05-09 2001-11-22 Unilever Plc Polymeres eliminant les salissures et compositions de detergents de blanchisserie les contenant
DE10112318A1 (de) * 2001-02-05 2002-08-14 Henkel Kgaa Konditioniermittel
WO2002070574A2 (fr) * 2001-03-02 2002-09-12 Unilever Plc Polymeres facilitant le lavage et compositions de detergent a lessive contenant ceux-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0441197A2 (fr) * 1990-02-03 1991-08-14 BASF Aktiengesellschaft Copolymère greffé à base de monosaccharides, oligosaccharides, polysaccharides et de polysaccharides modifiées, procédé de fabrication de celle-ci et son utilisation
US5223171A (en) * 1990-07-02 1993-06-29 Rhone Poulenc Chimie Detergent composition containing a biodegradable graft polysaccharide
DE4233497A1 (de) * 1992-10-06 1994-04-07 Basf Ag Verwendung von wäßrigen Polymerisatdispersionen als Textilhilfsmittel zur pflegeleichten Veredlung von Textilien
WO2001088075A1 (fr) * 2000-05-09 2001-11-22 Unilever Plc Polymeres eliminant les salissures et compositions de detergents de blanchisserie les contenant
DE10112318A1 (de) * 2001-02-05 2002-08-14 Henkel Kgaa Konditioniermittel
WO2002070574A2 (fr) * 2001-03-02 2002-09-12 Unilever Plc Polymeres facilitant le lavage et compositions de detergent a lessive contenant ceux-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006116507A1 (fr) * 2005-04-26 2006-11-02 The Procter & Gamble Company Produit utilise dans un seche-linge pour eviter le depot de fibres ou de cheveux sur les tissus
DE102005044514A1 (de) * 2005-09-16 2007-03-22 Henkel Kgaa Wasch- und Reinigungsmittel mit hautpflegenden Inhaltsstoffen

Also Published As

Publication number Publication date
ATE405626T1 (de) 2008-09-15
AU2003292000A1 (en) 2004-06-15
DE50310385D1 (de) 2008-10-02
EP1563046B1 (fr) 2008-08-20
EP1563046A2 (fr) 2005-08-17
ES2309356T3 (es) 2008-12-16
WO2004046288A3 (fr) 2004-08-12
AU2003292000A8 (en) 2004-06-15

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