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WO2006117056A1 - Polymeres pour la lessive - Google Patents

Polymeres pour la lessive Download PDF

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Publication number
WO2006117056A1
WO2006117056A1 PCT/EP2006/003262 EP2006003262W WO2006117056A1 WO 2006117056 A1 WO2006117056 A1 WO 2006117056A1 EP 2006003262 W EP2006003262 W EP 2006003262W WO 2006117056 A1 WO2006117056 A1 WO 2006117056A1
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WO
WIPO (PCT)
Prior art keywords
group
use according
cellulose
alkyl
polymer
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PCT/EP2006/003262
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English (en)
Inventor
Christopher David Gibbs
Patricia Revell
Susanne Henning Rogers
Original Assignee
Unilever Plc
Unilever Nv
Hindustan Unilever Limited
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Application filed by Unilever Plc, Unilever Nv, Hindustan Unilever Limited filed Critical Unilever Plc
Priority to CA002599356A priority Critical patent/CA2599356A1/fr
Publication of WO2006117056A1 publication Critical patent/WO2006117056A1/fr

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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
    • C11D3/20—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
    • C11D3/228—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with phosphorus- or sulfur-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents

Definitions

  • the present invention relates to the use of certain sulphoalkyl-substituted polysaccharides for promoting antiredeposition during laundering of a textile fabric, the use of such polysaccharides in the manufacture of a laundry cleaning composition and laundry cleaning compositions containing such polysaccharides.
  • the washing of soiled fabrics with a laundry detergent composition is essentially a two step process.
  • the detergent In the first stage the detergent must remove the soil particles from the fabric and suspend them in the soil solution.
  • the detergent composition In the second stage the detergent composition must prevent the soil particles and other insolubles from redepositing on the cloth before and after the fabric is removed from the soil solution or the rinse solution.
  • Polymers are known to aid both processes, soil release polymers enhance soil removal from the fabric whilst anti-redeposition polymers prevent the deterged soil from depositing on the fabric.
  • Laundry detergent compositions traditionally contain among other chemicals sodium carboxy methyl cellulose (SCMC) as an antiredeposition agent.
  • SCMC carboxy methyl cellulose
  • US 4 235 735 (Macro et al Miliken) discloses cellulose acetates with a defined degree of substitution as antiredeposition agents in laundry detergent compositions . — 9 —
  • cellulosic materials have also been used in laundry detergent compositions for a variety of benefits, for example soil release and fabric care benefits.
  • WO 00/18861A (Unilever) and WO 00/18862A (Unilever) disclose cellulosic compounds having a benefit agent attached so that the benefit agent will be deposited on the fibres of the washed textiles during the laundry process.
  • a polymer should be sufficiently water soluble.
  • many unmodified polysaccharides, especially unmodified celluloses are insoluble in water.
  • the solubility of cellulose ethers in water, aqueous base or organic solvents depends on the DS value. Ethers become soluble in aqueous alkali for example 5 % to 8 % NaOH.
  • Branched ⁇ - 1, 4 polysaccharides such as galactomannans, glucomannans or xyloglucans are water soluble or swell in water giving colloidal, highly viscous solutions or dispersions.
  • the solubility properties of these materials depends on factors such as the frequency of branching sites and the length of the side chain.
  • cellulose In contrast to this unmodified cellulose is not water soluble.
  • linear ⁇ - 1, 4 polysaccharides such as cellulose and chitin are completely insoluble in water.
  • a first aspect of the present invention provides use of a compound for promoting antiredeposition during laundering of a textile fabric, in which the compound is a polymer comprising a polysaccharide backbone substituted by one or more groups -L-R 1 , where L represents an ester, amide or ether linkage and R 1 represents a sulphoalkyl group or a salt thereof, and having a degree of substitution of from 0.2 to 1.5.
  • a second aspect of the invention provides use of a compound in the manufacture of a laundry cleaning composition for promoting antiredeposition during laundering of a textile fabric, in which the compound is a polymer as defined above.
  • the invention provides a laundry cleaning composition which comprises from 0.01 to 50% by weight based on the total weight of the composition of a polymer as defined above.
  • cleaning or "laundering” mean “washing and/or rinsing”.
  • alkyl refers to a branched or unbranched saturated hydrocarbon group which may contain from 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl etc. More preferably, an alkyl group contains from 1 to ⁇ , preferably 1 to 4 carbon atoms. Ethyl and propyl groups are especially preferred. "Substituted alkyl” refers to alkyl substituted with one or more substituent groups. Preferably, alkyl and substituted alkyl groups are unbranched.
  • alkenyl is a branched or unbranched unsaturated hydrocarbon containing 1 to 12, preferably 1 to 6 and especially 1 to 4 carbon atoms.
  • alkenyl and substituted alkenyl groups are unbranched.
  • a halogen atom may be a fluorine, chlorine, bromine or iodine atom and any group which contains a halo moiety, such as a haloalkyl group, may thus contain any one or more of these halogen atoms.
  • the term "degree of substitution” refers to substitution of the functional groups on the repeating sugar unit.
  • DS refers to substitution of the three hydroxyl groups on the repeating sugar unit.
  • the maximum degree of substitution is 3.
  • DS values do not generally relate to the uniformity of substitution of chemical groups along the polysaccharide molecule and are not related to the molecular weight of the polysaccharide backbone.
  • the degree of substitution (DS) can be determined using NMR spectroscopy after acid degradation of the polysaccharide backbone.
  • polysaccharides includes natural polysaccharides, synthetic polysaccharides, polysaccharide derivatives and modified polysaccharides.
  • Suitable polysaccharides for use in preparing the compounds of the present invention include, but are not limited to, gums, arabinans, galactans, seeds and mixtures thereof as well as cellulose and derivatives thereof. It is especially preferred that the polysaccharide backbone is cellulose, especially unmodified cellulose.
  • Suitable polysaccharides that are useful in the present invention include polysaccharides with a degree of polymerisation (DP) over 10, preferably from about 10 to about 100,000, more preferably from about 500 to about 50,000.
  • Constituent saccharides preferably include, but are not limited to, one or more of the following saccharides: isomaltose, isomaltotriose, isomaltotetraose, isomaltooligosaccharide, fructooligosaccharide, levooligosaccharides, galactooligosaccharide, xylooligosaccharide, gentiooligosaccharides, disaccharides, glucose, fructose, galactose, xylose, mannose, sorbose, arabinose, rhamnose, fucose, maltose, sucrose, lactose, maltulose, ribose, lyxose, allose, altrose, gulose
  • the polysaccharides can be extracted from plants, produced by organisms, such as bacteria, fungi, prokaryotes, eukaryotes, extracted from animal and/or humans.
  • xanthan gum can be produced by Xanthomonas campestris, gellan by Sphingomonas pauc ⁇ mobilis, xyloglucan can be extracted from tamarind seed.
  • the polysaccharides can be linear, or branched in a variety of ways, such as 1-2, 1-3, 1-4, 1-6, 2-3 and mixtures thereof. Many naturally occurring polysaccharides have at least some degree of branching, or at any rate, at least some saccharide rings are in the form of pendant side groups on a main polysaccharide backbone.
  • the polysaccharides of the present invention have a molecular weight in the range of from about 5,000 to about 10,000,000, more preferably from about 50,000 to about 1,000,000, most preferably from about 50,000 to about 500,000.
  • the polysaccharide is selected from the group consisting of: tamarind gum (preferably consisting of xyloglucan polymers) , guar gum, locust bean gum (preferably consisting of galactomannan polymers) , and other industrial gums and polymers, which include, but are not limited to, Tara, Fenugreek, Aloe, Chia, Flaxseed, Psyllium seed, quince seed, xanthan, gellan, welan, rhamsan, dextran, curdlan, — 1 —
  • Polysaccharides can be used which have an ⁇ - or ⁇ -linked backbone. However, more preferred polysaccharides have a ⁇ - linked backbone, preferably a ⁇ -1,4 linked backbone. It is preferred that the ⁇ -l,4-linked polysaccharide is cellulose; a cellulose derivative, particularly cellulose sulphate, cellulose acetate, cyanoethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose; a xyloglucan, particularly one derived from Tamarind seed gum; a glucomannan, particularly Konjac glucomannan; a galactomannan, particularly Locust Bean gum and Guar gum; a side chain branched galactomannan, particularly Xanthan gum; chitosan or a chitosan salt.
  • cellulose a cellulose derivative, particularly cellulose sulphate, cellulose a
  • ⁇ -l,4-linked polysaccharides such as mannan
  • the natural polysaccharides can be modified with amines (primary, secondary, tertiary) , amides, esters, ethers, urethanes, alcohols, carboxylic acids, tosylates, sulfonates, sulfates, nitrates, phosphates and mixtures thereof. Such a modification can take place in position 2, 3 and/or 6 of the saccharide unit.
  • Such modified or derivatised polysaccharides can be included in the compositions of the present invention in addition to the natural polysaccharides.
  • Nonlimiting examples of such modified polysaccharides include: carboxyl and hydroxymethyl substitutions (e.g. glucuronic acid instead of glucose) ; amino polysaccharides (amine substitution, e.g. glucosamine instead of glucose); Ci-C ⁇ alkylated polysaccharides; acetylated polysaccharide ethers; polysaccharides having amino acid residues attached (small fragments of glycoprotein) ; polysaccharides containing silicone moieties.
  • modified polysaccharides are commercially available from Carbomer and include, but are not limited to, amino alginates, such as hexanediamine alginate, amine functionalised cellulose-like 0-methyl- (N-I, 12- dodecanediamine) cellulose, biotin heparin, carboxymethylated dextran, guar polycarboxylic acid, carboxymethylated locust bean gum, carboxymethylated xanthan, chitosan phosphate, chitosan phosphate sulfate, diethylaminoethyl dextran, dodecylamide alginate, sialic acid, glucuronic acid, galacturonic acid, mannuronic acid, guluronic acid, N-acetylgluosamine, N-acetylgalactosamine, and mixtures thereof.
  • amino alginates such as hexanediamine alginate, amine functionalised cellulose-like 0-methyl- (N-I, 12- do
  • the polysaccharide has a total number of sugar units from 10 to 7000, although this figure will be dependent on the type of polysaccharide chosen, at least to some extent.
  • the total number of sugar units is preferably from 10 to 1000, more preferably 10 to 750 and especially 25 to 300.
  • the preferred molecular weight of such polysaccharides is from 2 000 to 1 000 000, preferably from 3 000 to 500 000, more preferably from 4 000 to 300 000.
  • the total number of sugar units is preferably from 50 to 7000.
  • the preferred molecular weight is from 10 000 to 1000 000.
  • the total number of sugar units is preferably from 1000 to 3000.
  • the preferred molecular weight is from 200 000 to 600 000.
  • the polysaccharide can be linear, like in hydroxyalkyl cellulose, it can have an alternating repeat like in carrageenan, it can have an interrupted repeat like in pectin, it can be a block copolymer like in alginate, it can be branched like in dextran, or it can have a complex repeat like in xanthan. Descriptions of the polysaccharides are given in "An introduction to Polysaccharide Biotechnology", by M. Tombs and S. E. Harding, T.J. Press 1998. The Polymers
  • the polymers utilised in the invention are polysaccharides in which at least one sugar unit of the polysaccharide has been substituted by a group of the general formula -L-R 1 in which L and R 1 are as defined above.
  • each SU represents a sugar unit in a polysaccharide backbone
  • a represents the number of unsubstituted sugar units as a percentage of the total number of sugar units and is in the range from 0 to 99.9%, preferably 0 to 95%;
  • b represents the number of substituted sugar units as a percentage of the total number of sugar units and is in the range from 0.1 to 100%, preferably 5 to 100%;
  • n represents the degree of substitution per sugar unit and is from 0.2 to 1.5;
  • L represents an ester, amide or ether linkage
  • R 1 represents a sulphoalkyl group or a salt thereof.
  • L represents a group -0-C0- or -0-.
  • R 1 is an alkyl group substituted by a group of formula -SO 3 -R 2 where R 2 represents a hydrogen atom or an alkali metal, preferably a sodium or potassium, atom.
  • the alkyl group is a Ci_ 6 alkyl, more preferably a Ci_ 4 alkyl, group. More preferably, R 1 represents a sulpho C2- 4 alkyl, preferably a sulphoethyl or sulphopropyl group or a sodium salt thereof.
  • -L-R 1 represents a group selected from -0-CH 2 CH 2 SO 3 H and -0- CH 2 CH 2 CH 2 SO 3 H and sodium salts thereof.
  • polysaccharide backbone in the polymers is ⁇ -linked, preferably ⁇ -1, 4-linked.
  • the polysaccharide backbone is selected from the group consisting of cellulose, cellulose derivatives (preferably cellulose sulphate, cellulose acetate, cyanoethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethylcellulose, hydroxyethylcellulose or hydroxypropylcellulose) , xyloglucans (preferably those derived from Tamarind seed gum) , glucomannans (preferably Konjac glucomannan) , galactomannans (preferably Locust Bean gum, Guar gum and Xanthan gum), chitosan and chitosan salts. It is especially preferred that the polysaccharide backbone is cellulose, especially unmodified cellulose.
  • the polymers have the general formula:
  • L and R 1 are as defined above and at least one or more R groups are independently selected from hydrogen atoms and groups of formulae :-
  • each R 8 is independently selected from Ci-2 0 (preferably Ci- 6 ) alkyl, C 2 - 20 (preferably C 2 - 6 ) alkenyl (e.g. vinyl) and C 5 - 7 aryl (e.g. phenyl) any of which is optionally substituted by one or more substituents independently selected from C 1 - 4 alkyl, C 1 -. 12 (preferably C 1 - 4 ) alkoxy, hydroxyl, vinyl and phenyl groups; each R 9 is independently selected from hydrogen and groups R 8 as hereinbefore defined;
  • R 10 is a bond or is selected from C 1 - 4 alkylene, C2- 4 alkenylene and C 5 _ 7 arylene (e.g. phenylene) groups, the carbon atoms in any of these being optionally substituted by one or more substituents independently selected from Ci-12 (preferably C 1 -. 4 ) alkoxy, vinyl, hydroxyl, halo and amine groups;
  • each R 11 is independently selected from hydrogen, counter cations such as alkali metal (preferably Na) or 2 Ca or 2Mg, and groups R 8 as hereinbefore defined;
  • R 12 is selected from C 1 -.20 (preferably Ci_ 6 ) alkyl, C2-20 (preferably C 2 - ⁇ ) alkenyl (e.g. vinyl) and C 5 _ 7 aryl (e.g. phenyl) , any of which is optionally substituted by one or more substituents independently selected from Ci_4 alkyl, C1-.12 (preferably C 1 - 4 ) alkoxy, hydroxyl, carboxyl, cyano, sulfonato, vinyl and phenyl groups;
  • x is from 1 to 3;
  • any remaining R groups being selected from hydrogen and ether substituents.
  • R 12 is a methyl, ethyl, phenyl, hydroxyethyl, hydroxypropyl, carboxymethyl, sulphoethyl or cyanoethyl group.
  • R groups may optionally have one or more structures, for example as hereinbefore described.
  • one or more R groups may simply be hydrogen or an alkyl group.
  • Preferred groups may for example be independently selected from one or more of acetate, propanoate, trifluoroacetate, 2- (2-hydroxy-l-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate cinnamate, formate, salicylate, carbamate, methylcarbamate, benzoate, gluconate, methanesulphonate, toluene, sulphonate, groups and hem ⁇ ester groups of fumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric, aspartic, glutamic, and malic acids.
  • Particularly preferred such groups are the monoacetate, hemisuccinate, and 2- (2-hydroxy-l-oxopropoxy) propanoate.
  • the term "monoacetate” is used herein to denote those acetates with a degree of substitution of about 1 or less on a cellulose or other ⁇ -1,4 polysaccharide backbone.
  • cellulose monoacetate refers to a molecule that has acetate esters in a degree of substitution of about 1.1 or less, preferably about 1.1 to about 0.5.
  • Cellulose esters of hydroxyacids can be obtained using the acid anhydride in acetic acid solution at 20-30 0 C and in any case below 50 0 C. When the product has dissolved the liquid is poured into water. Tri-esters can be converted to secondary products as with the triacetate. Glycollic and lactic ester are most common.
  • Cellulose glycollate may also be obtained from cellulose chloracetate (GB-A-320 842) by treating 100 parts with 32 parts of NaOH in alcohol added in small portions.
  • An alternative method of preparing cellulose esters consists in the partial displacement of the acid radical in a cellulose ester by treatment with another acid of higher ionisation constant (FR-A-702 116) .
  • the ester is heated at about 100 0 C with the acid which, preferably, should be a solvent for the ester.
  • the acid which, preferably, should be a solvent for the ester.
  • cellulose acetate- oxalate, tartrate, maleate, pyruvate, salicylate and phenylglycollate have been obtained, and from cellulose tribenzoate a cellulose benzoate-pyruvate .
  • a cellulose acetate-lactate or acetate-glycollate could be made in this way also.
  • cellulose acetate (1O g.) in dioxan (75 ml.) containing oxalic acid (10 g.) is heated at 100 0 C for 2 hours under reflux.
  • esters are prepared by variations of this process.
  • a simple ester of cellulose e.g. the acetate, is dissolved in a mixture of two (or three) organic acids, each of which has an ionisation constant greater than that of acetic acid (1.82 x 10 "5 ) .
  • suitable solvents such as propionic acid, dioxan and ethylene dichloride are used. If a mixed cellulose ester is treated with an acid this should have an ionisation constant greater than that of either of the acids already in combination.
  • a cellulose acetate-lactate-pyruvate is prepared from cellulose acetate, 40 per cent acetyl (100 g) , in a bath of 125 ml pyruvic acid and 125 ml of 85 per cent lactic acid by heating at 100 0 C for 18 hours.
  • the product is soluble in water and is precipitated and washed with ether-acetone M. p. 230-250°C.
  • m (the degree of substitution) is from 0.2 to 1.2, more preferably from 0.2 to 1.1, especially 0.2 to 1.0.
  • m can be from 0.2 to 0.8, especially 0.2 to 0.6.
  • the resultant modified polysaccharide is substantially water soluble.
  • polymers used in the present invention may be synthesised by a variety of routes which are well known to those skilled in the art of polymer chemistry.
  • sulphoalkyl ether-linked polymers can be made by reacting a polysaccharide with a suitable alkenyl sulphonic acid in a Michael addition reaction or by reacting a polysaccharide with a suitable chloro alkyl sulphonate.
  • sulphoethyl cellulose can be prepared by the following methods :-
  • the substituted polysaccharide according to the first aspect of the present invention may be incorporated into compositions containing only a diluent (which may comprise solid and/or liquid) and/or also comprising an active ingredient.
  • the compound is typically included in said compositions at levels of from 0.01% to 50%, particularly from 0.01% to 25% by weight, preferably from 0.05% to 15%, more preferably from 0.1% to 10%, especially from 0.1% to 5% and most preferably from 0.2 % to 1.5%.
  • the active ingredient in the compositions is preferably a surface active agent or a fabric conditioning agent. More than one active ingredient may be included. For some applications a mixture of active ingredients may be used.
  • compositions of the invention may be in any physical form e.g. a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an aqueous based liquid.
  • a solid such as a powder or granules, a tablet, a solid bar, a paste, gel or liquid, especially, an aqueous based liquid.
  • the compositions may be used in laundry compositions, especially in liquid, powder or tablet laundry composition.
  • compositions of the present invention are preferably laundry compositions, especially main wash (fabric washing) compositions or rinse-added softening compositions.
  • the main wash compositions may include a fabric softening agent and rinse-added fabric softening compositions may include surface-active compounds, particularly non-ionic surface- active compounds, if appropriate.
  • the organic detergent surfactant is the organic detergent surfactant
  • the detergent compositions of the invention may contain a surface-active compound (surfactant) which may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof.
  • surfactant may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof.
  • surface-active compound surfactant
  • surfactant may be chosen from soap and non-soap anionic, cationic, non-ionic, amphoteric and zwitterionic surface-active compounds and mixtures thereof.
  • the preferred detergent-active compounds that can be used are soaps and synthetic non-soap anionic and non-ionic compounds.
  • the total amount of surfactant present is suitably within the range of 5 to 60 wt%, preferably from 5 to 40 wt%.
  • compositions of the invention may contain anionic surfactants.
  • alkylbenzene sulphonates such as linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of Cg- Ci 5 . It is preferred that the level of linear alkylbenzene sulphonate is from 0 wt% to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
  • compositions of the invention may contain other anionic surfactants in amounts additional to the percentages quoted above.
  • Suitable anionic surfactants are well-known to those skilled in the art. Examples include primary and secondary alkyl sulphates, particularly C 8 -C2o primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • compositions of the invention may also contain non-ionic surfactant.
  • Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the Cs-C 2O aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the Cio-C ⁇ s primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide) .
  • the level of non-ionic surfactant is from 0 wt% to 30 wt%, preferably from 1 wt% to 25 wt%, most preferably from 2 wt% to 15 wt%.
  • Cationic surfactants which can be used in main-wash compositions for fabrics.
  • Cationic surfactants that may be used include quaternary ammonium salts of the general formula R 1 R 2 R 3 R 4 N 4" X " wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which Ri is a C 8 -C22 alkyl group, preferably a C 8 -CiO or Ci 2 -Ci 4 alkyl group, R 2 is a methyl group, and R 3 and R 4 , which may be the same or different, are methyl or hydroxyethyl groups) ; and cationic esters (for example, choline esters) .
  • Amphoteric and zwitterionic surfactants that may be used include alkyl amine oxides, betaines and sulphobetaines .
  • the detergent surfactant (a) most preferably comprises an anionic sulphonate or sulphonate surfactant optionally in admixture with one or more cosurfactants selected from ethoxylated nonionic surfactants, non-ethoxylated nonionic surfactants, ethoxylated sulphate anionic surfactants, cationic surfactants, amine oxides, alkanolamides and combinations thereof.
  • cosurfactants selected from ethoxylated nonionic surfactants, non-ethoxylated nonionic surfactants, ethoxylated sulphate anionic surfactants, cationic surfactants, amine oxides, alkanolamides and combinations thereof.
  • the choice of surface-active compound (surfactant) and the amount present, will depend on the intended use of the detergent composition
  • the total amount of surfactant present will also depend on the intended end use and may be as high as 60 wt%, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wt% is generally appropriate. Typically the compositions will comprise at least 2 wt% surfactant e.g. 2- 60%, preferably 15-40% most preferably 25-35%.
  • Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap.
  • any conventional fabric conditioning agent may be used in the compositions of the present invention.
  • the conditioning agents may be cationic or non-ionic. If the fabric conditioning compound is to be employed in a main wash detergent composition the compound will typically be non- ionic. For use in the rinse phase, typically they will be cationic. They may for example be used in amounts from 0.5% to 35%, preferably from 1% to 30% more preferably from 3% to 25% by weight of the composition.
  • the fabric conditioning agent (s) have two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to Ci 5 . Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of Ci ⁇ or above. It is preferred that the long chain alkyl or alkenyl groups of the fabric conditioning agents are predominantly linear.
  • the fabric conditioning agents are preferably compounds that provide excellent softening, and are characterised by a chain melting L ⁇ to La transition temperature greater than 25 0 C, preferably greater than 35 0 C, most preferably greater than 45 0 C.
  • This L ⁇ to La transition can be measured by DSC as defined in ⁇ v Handbook of Lipid Bilayers, D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337) .
  • Substantially insoluble fabric conditioning compounds in the context of this invention are defined as fabric conditioning compounds having a solubility less than 1 x 10 "3 wt % in deminerailised water at 20 0 C.
  • the fabric softening compounds have a solubility less than 1 x 10 "4 wt %, most preferably less than 1 x 10 ⁇ 8 to 1 x 10 ⁇ 6 .
  • Preferred cationic fabric softening agents comprise a substantially water insoluble quaternary ammonium material comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C 2 o or, more preferably, a compound comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to Ci 4 .
  • the cationic fabric softening agent is a quaternary ammonium material or a quaternary ammonium material containing at least one ester group.
  • the quaternary ammonium compounds containing at least one ester group are referred to herein as ester-linked quaternary ammonium compounds .
  • ester group' includes an ester group which is a linking group in the molecule.
  • ester-linked quaternary ammonium compounds it is preferred for the ester-linked quaternary ammonium compounds to contain two or more ester groups.
  • ester group (s) is a linking group between the nitrogen atom and an alkyl group.
  • the ester groups (s) are preferably attached to the nitrogen atom via another hydrocarbyl group.
  • quaternary ammonium compounds containing at least one ester group, preferably two, wherein at least one higher molecular weight group containing at least one ester group and two or three lower molecular weight groups are linked to a common nitrogen atom to produce a cation and wherein the electrically balancing anion is a halide, acetate or lower alkosulphate ion, such as chloride or methosulphate .
  • the higher molecular weight substituent on the nitrogen is preferably a higher alkyl group, containing 12 to 28, preferably 12 to 22, e.g.
  • the lower molecular weight substituents are preferably lower alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or substituted lower alkyl.
  • One or more of the said lower molecular weight substituents may include an aryl moiety or may be replaced by an aryl, such as benzyl, phenyl or other suitable substituents.
  • the quaternary ammonium material is a compound having two C 12 -C 22 alkyl or alkenyl groups connected to a quaternary ammonium head group via at least one ester link, preferably two ester links or a compound comprising a single long chain with an average chain length equal to or greater than C 2 O-
  • the quaternary ammonium material comprises a compound having two long chain alkyl or alkenyl chains with an average chain length equal to or greater than C 3.4 . Even more preferably each chain has an average chain length equal to or greater than Ci ⁇ - Most preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of Ci 8 . It is preferred if the long chain alkyl or alkenyl groups are predominantly linear.
  • ester-linked quaternary ammonium material that can be used in laundry rinse compositions according to the invention is represented by the formula (A) : TR ,21
  • T is -O-C- or -C-O- ; each R 20 group is independently selected from Ci_ 4 alkyl, hydroxyalkyl or C 2 -4 alkenyl groups; and wherein each R 21 group is independently selected from Cs- 28 alkyl or alkenyl groups;
  • Y ⁇ is any suitable counter-ion, i.e. a halide, acetate or lower alkosulphate ion, such as chloride or methosulphate;
  • w is an integer from 1-5 or is 0; and y is an integer from 1-5.
  • each R 20 group is methyl and w is 1 or 2.
  • the quaternary ammonium material is biologically degradable.
  • Preferred materials of this class such as 1,2 bis [hardened tallowoyloxy] -3-trimethylammonium propane chloride and their method of preparation are, for example, described in US-A-4 137 180.
  • these materials comprise small amounts of the corresponding monoester as described in US-A-4 137 180 for example 1-hardened tallowoyloxy-2 ⁇ hydroxy-3- trimethylammonium propane chloride.
  • Another class of preferred ester-linked quaternary ammonium materials for use in laundry rinse compositions according to the invention can be represented by the formula:
  • T is -O-C- or -C-O- ;
  • R 20 , R 21 , w, and Y ⁇ are as defined above.
  • di- (tallowyloxyethyl) - dimethyl ammonium chloride available from Hoechst, is the most preferred.
  • Di- (hardened tallowyloxyethyl) dimethyl ammonium chloride, ex Hoechst and di- (tallowyloxyethyl) - methyl hydroxyethyl methosulphate are also preferred.
  • Another preferred class of quaternary ammonium cationic fabric softening agent is defined by formula (C):-
  • a preferred material of formula (C) is di-hardened tallow- diethyl ammonium chloride, sold under the Trademark Arquad 2HT.
  • the optionally ester-linked quaternary ammonium material may contain optional additional components, as known in the art, in particular, low molecular weight solvents, for instance isopropanol and/or ethanol, and co-actives such as nonionic softeners, for example fatty acid or sorbitan esters.
  • low molecular weight solvents for instance isopropanol and/or ethanol
  • co-actives such as nonionic softeners, for example fatty acid or sorbitan esters.
  • compositions of the invention when used as main wash fabric washing compositions, will generally also contain one or more detergency builder.
  • the total amount of detergency builder in the compositions will typically range from 0 to 80 wt%, preferably from 0 to 60 wt% .
  • Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever) ; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel) , amorphous aluminosilicates as disclosed in GB 1 473 202 (Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble) ; and layered silicates as disclosed in EP 164 514B (Hoechst) .
  • Inorganic phosphate builders for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.
  • compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder.
  • Sodium aluminosilicates may generally be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) , preferably from 10 to 50 wt%, especially from 25 to 50 wt% .
  • the alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na 2 O. Al 2 O 3 . 0.8-6 SiO 2
  • the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.
  • the zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders.
  • the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) .
  • Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.
  • zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00, is especially preferred.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • the zeolites may be supplemented by other inorganic builders, for example, amorphous aluminosilicates, or layered silicates such as SKS-6 ex Clariant.
  • the zeolite may be supplemented by organic builders.
  • Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuecinates, carboxymethyloxy succinates, carboxymethyloxymalonates , dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.
  • polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates
  • monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuecinates, carboxymethyloxy succinates, carboxymethyloxymalonates , dipicolinates,
  • Especially preferred organic builders are citrates, suitably- used in amounts of from 1 to 30 wt%, preferably from 5 to 30 wt%, more preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.
  • Builders both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.
  • Builders are suitably present in total amounts of from 10 to 80 wt%, more preferably from 20 to 60 wt%. Builders may be inorganic or organic.
  • a built composition in accordance with the invention may most preferably comprise from 10 to 80 wt% of a detergency builder (b) selected from zeolites, phosphates, and citrates .
  • a detergency builder selected from zeolites, phosphates, and citrates .
  • the laundry detergent composition will generally comprises other detergent ingredients well known in the art. These may suitably be selected from bleach ingredients, enzymes, sodium carbonate, sodium silicate, sodium sulphate, foam controllers, foam boosters, perfumes, fabric conditioners, soil release polymers, dye transfer inhibitors, photobleaches, fluorescers and coloured speckles.
  • compositions according to the invention may also suitably contain a bleach system.
  • Fabric washing compositions may desirably contain peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, capable of yielding hydrogen peroxide in aqueous solution.
  • Suitable peroxy bleach compounds include organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates .
  • organic peroxides such as urea peroxide
  • inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates .
  • Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate .
  • sodium percarbonate having a protective coating against destabilisation by moisture Especially preferred is sodium percarbonate having a protective coating against destabilisation by moisture.
  • Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044B (Kao) .
  • the peroxy bleach compound is suitably present in an amount of from 0.1 to 35 wt%, preferably from 0.5 to 25 wt%.
  • the peroxy bleach compound may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures.
  • the bleach precursor is suitably present in an amount of from 0.1 to 8 wt%, preferably from 0.5 to 5 wt%.
  • Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors and pernonanoic acid precursors.
  • Especially preferred bleach precursors suitable for use in the present invention are N, N, N' ,N 1 , -tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulphonate (SNOBS) •
  • TAED -tetracetyl ethylenediamine
  • SNOBS sodium nonanoyloxybenzene sulphonate
  • the novel quaternary ammonium and phosphonium bleach precursors disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company) and EP 402 971A (Unilever) and the cationic bleach precursors disclosed in EP 284 292A and EP 303 520A (Kao) are also of interest.
  • the bleach system can be either supplemented with or replaced by a peroxyacid.
  • peracids can be found in US 4 686 063 and US 5 397 501 (Unilever) .
  • a preferred example is the imido peroxycarboxylic class of peracids described in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325 289.
  • a particularly preferred example is phthalimido peroxy caproic acid (PAP) .
  • PAP phthalimido peroxy caproic acid
  • Such peracids are suitably present at 0.1 - 12%, preferably 0.5 - 10%.
  • a bleach stabiliser may also be present.
  • Suitable bleach stabilisers include ethylenediamine tetra-acetate (EDTA) , diethylenetriamine pentaacetate (DTPA) , the polyphosphonates such as Dequest (Trade Mark) , ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphate (DETPMP) and non-phosphate stabilisers such as EDDS (ethylene diamine disuccinate) .
  • EDTA ethylenediamine tetra-acetate
  • DTPA diethylenetriamine pentaacetate
  • DETPMP diethylenetriamine pentamethylene phosphate
  • non-phosphate stabilisers such as EDDS (ethylene diamine disuccinate) .
  • These bleach stabilisers are also useful for stain removal especially in products containing low levels of bleaching species or no bleaching species.
  • An especially preferred bleach system comprises a peroxy bleach compound (preferably sodium percarbonate optionally together with a bleach activator) , and a transition metal bleach catalyst as described and claimed in EP 458 397A, EP 458 398A and EP 509 787A (Unilever) .
  • the compositions according to the invention may also contain one or more enzyme (s).
  • Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions.
  • Preferred proteolytic enzymes are, catalytically active protein materials which degrade or alter protein types of stains when present as in fabric stains in a hydrolysis reaction. They may be of any suitable origin, such as vegetable, animal, bacterial or yeast origin.
  • proteolytic enzymes or proteases of various qualities and origins and having activity in various pH ranges of from 4-12 are available and can be used in the instant invention.
  • suitable proteolytic enzymes are the subtilins which are obtained from particular strains of B. Subtilis B. licheniformis , such as the commercially available subtilisins Maxatase (Trade Mark), as supplied by Gist Brocades N. V., Delft, Holland, and Alcalase (Trade Mark) , as supplied by Novo Industri A/S, Copenhagen, Denmark.
  • protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available, e.g. from Novo Industri A/S under the registered trade-names Esperase (Trade Mark) and Savinase (Trade-Mark) .
  • Esperase Trade Mark
  • Savinase Trade-Mark
  • Other commercial proteases are Kazusase (Trade Mark obtainable from Showa-Denko of Japan) , Optimase (Trade Mark from Miles Kali-Chemie, Hannover, West Germany) , and Superase (Trade Mark obtainable from Pfizer of U.S.A.).
  • Detergency enzymes are commonly employed in granular form in amounts of from about 0.1 to about 3.0 wt%. However, any suitable physical form of enzyme may be used.
  • compositions of the invention may contain alkali metal, preferably sodium, carbonate, in order to increase detergency and ease processing.
  • Sodium carbonate may suitably be present in amounts ranging from 1 to 60 wt%, preferably from 2 to 40 wt%.
  • compositions containing little or no sodium carbonate are also within the scope of the invention.
  • Powder flow may be improved by the incorporation of a small amount of a powder structurant, for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
  • a powder structurant for example, a fatty acid (or fatty acid soap) , a sugar, an acrylate or acrylate/maleate copolymer, or sodium silicate.
  • fatty acid soap suitably present in an amount of from 1 to 5 wt%.
  • the amount of sodium silicate may suitably range from 0.1 to 5 wt% .
  • compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; soil release polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers.
  • sodium silicate such as cellulosic polymers
  • soil release polymers such as sodium sulphate
  • inorganic salts such as sodium sulphate
  • lather control agents or lather boosters as appropriate
  • proteolytic and lipolytic enzymes such as sodium sulphate
  • dyes coloured speckles
  • perfumes foam controllers
  • fluorescers and decoupling polymers include sodium silicate; antiredeposition agents such as cellulosic polymers; soil release polymers; inorganic salts such as sodium sulphate; lather control agents or lather boosters as appropriate; proteolytic and lipo
  • the detergent composition when diluted in the wash liquor will typically give a pH of the wash liquor from 7 to 10.5 for a main wash detergent.
  • Particulate detergent compositions are suitably prepared by spray-drying a slurry of compatible heat-insensitive ingredients, and then spraying on or post-dosing those ingredients unsuitable for processing via the slurry.
  • the skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not.
  • Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/llitre, more preferably at least 500 g/litre. Especially preferred compositions have bulk densities of at least 650 g/litre, more preferably at least 700 g/litre.
  • Such powders may be prepared either by post-tower densification of spray-dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP 340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever) .
  • Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations.
  • Liquid compositions according to the present invention can also be in compact form which means it will contain a lower level of water compared to a conventional liquid detergent.
  • DS (B / 2) /(A / 6)
  • DS (B / 2) / C
  • Mn Molecular weight (Mn) using SEC-MALLS (Size Exclusion Chromatography-Multiangle Laser Light Scattering)
  • a 0.15% solution of polymer was prepared by dissolving in 0.001M sodium carbonate.
  • the column used was a Waters Ultrahydrogel mixed with guard.
  • MALLS detector and RI detector used to detect polymers.
  • the method involved the use of a tergotometer and multiple washing in order to simulate the redeposition process that occurs with repeated washing either under difficult wash conditions or with low efficiency wash products.
  • Test formulations were used to wash pre-soiled "test cloths” together with clean fabrics (redeposition monitors) under standard conditions.
  • the soiled fabrics were used to supply soil to the system and also to measure the cleaning efficiency of the formulations.
  • the clean fabrics were used to "collect” soil from the liquor and were used to quantify the level of soil redeposition.
  • the test cloths and redeposition monitors were dried and their reflectance measured.
  • a new batch of test cloths was then washed together with the redeposition monitors from the original wash cycle and the process repeated to give information on the level of redeposition after two wash cycles. This process was then repeated for a third, fourth (etc) wash cycle:
  • Cycle 1 test cloths, clean antiredeposition monitors
  • Cycle 2 test cloths, antiredeposition monitors from Cycle 1
  • Cycle 3 test cloths, antiredeposition monitors from Cycle 2
  • Cycle 4 test cloths, antiredeposition monitors from Cycle
  • Cycle n test cloths, antiredeposition monitors from Cycle n-1 This protocol allows both the detergency and the redeposition process to be followed as a function of cycle number.
  • the reflectance value falls with successive cycles as more soil is present in the system: the smaller the reflectance decrease, the better the antiredeposition properties of the formulation.
  • a stock solution was prepared, using water of 40 degrees French hardness, containing 2 g/1 of the following notional formulation (equivalent to 1.77 g/1 of the specified ingredients the rest comprising other detergent ingredients such as water, enzyme, fluorescer, perfume etc.
  • Sodium carboxymethyl cellulose was selected as an appropriate comparative compound since it is an antiredeposition agent which is commonly utilised in laundry detergent compositions.
  • the soiled test cloths were 7.5 cm x 7.5 cm squares as follows:
  • the clean test cloths were 10 cm x 10 cm squares of the following fabrics:
  • the tergotometer pots containing the test formulations, soiled and clean test cloths at 25°C were agitated at 90 rpm for 15 minutes.
  • the fabric bundles were then removed from the pots and rinsed twice in water (40 degrees French hard) .
  • the fabrics were then dried in the dark for at least 12 hours .
  • the reflectance values of the redeposition monitors were measured (full spectrum with ultraviolet excluded) before and after the wash.
  • the following table shows mean reflectance values after 3 wash cycles for sulphoethyl cellulose polymers with a slightly higher degree of substitution (DS) than in the previous example.

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Abstract

L'invention concerne l'utilisation d'un composé permettant de promouvoir l'antiredéposition pendant le lavage d'un tissu en textile. Le composé est un polymère contenant un squelette de polysaccharide substitué par un ou plusieurs groupes - L-R1, L représentant un ester, un amide ou une liaison d'éther et R1 représentant un groupe sulphoalkyle ou un sel de celui-ci, et possédant un degré de substitution compris entre 0,2 et 1,5. L'invention porte aussi sur l'utilisation de ces polymères dans la fabrication d'une composition de lessive ainsi que sur des compositions de lessive contenant ces polymères.
PCT/EP2006/003262 2005-04-29 2006-03-30 Polymeres pour la lessive WO2006117056A1 (fr)

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GB0508882A GB0508882D0 (en) 2005-04-29 2005-04-29 Polymers for laundry applications
GB0508882.8 2005-04-29

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DE102013202269A1 (de) 2013-02-12 2014-08-14 Henkel Ag & Co. Kgaa Vergrauungsinhibierende Waschmittel
WO2018172503A3 (fr) * 2017-03-24 2019-03-07 Basf Se Détergent pour lessive liquide comprenant un saccharide ou un polysaccharide modifié
DE102020201317A1 (de) 2020-02-04 2021-08-05 Henkel Ag & Co. Kgaa Chitosanderivate als schmutzablösevermögende Wirkstoffe
CN116209417A (zh) * 2020-08-21 2023-06-02 陶氏环球技术有限责任公司 非皂洗涤剂皂条组合物
DE102022200126A1 (de) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Fucoidane als vergrauungsinhibierende Wirkstoffe
WO2023131542A1 (fr) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Ulvanes utilisés comme agents inhibiteurs de décoloration
DE102022200269A1 (de) 2022-01-13 2023-07-13 Henkel Ag & Co. Kgaa Saccharosederivate als vergrauungsinhibierende Wirkstoffe
EP4321604A1 (fr) 2022-08-08 2024-02-14 The Procter & Gamble Company Tissu et composition de soins à domicile comprenant un tensioactif et un polyester
WO2024094803A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Composition d'entretien textile et ménager
WO2024094800A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Composition d'entretien textile et ménager
WO2024094802A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Tissu et composition d'entretien ménager
WO2024119298A1 (fr) 2022-12-05 2024-06-13 The Procter & Gamble Company Composition de soin textile et ménager comprenant un composé de carbonate de polyalkylène
EP4386074A1 (fr) 2022-12-16 2024-06-19 The Procter & Gamble Company Composition de soin pour le linge et le domicile
WO2024129520A1 (fr) 2022-12-12 2024-06-20 The Procter & Gamble Company Composition de soin textile et ménager
EP4458932A1 (fr) 2023-05-04 2024-11-06 The Procter & Gamble Company Tissu et composition de soins à domicile
EP4458933A1 (fr) 2023-05-05 2024-11-06 The Procter & Gamble Company Composition de tissu et de soins à domicile comprenant un polyol propoxylé
EP4484536A1 (fr) 2023-06-26 2025-01-01 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4549541A1 (fr) 2023-11-02 2025-05-07 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4549540A1 (fr) 2023-11-02 2025-05-07 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4553137A1 (fr) 2023-11-08 2025-05-14 The Procter & Gamble Company Composition de soin domestique et de tissu comprenant un polyester
EP4570893A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4570892A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de détergent à lessive

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013202269A1 (de) 2013-02-12 2014-08-14 Henkel Ag & Co. Kgaa Vergrauungsinhibierende Waschmittel
WO2014124872A1 (fr) 2013-02-12 2014-08-21 Henkel Ag & Co. Kgaa Détergent inhibant le grisonnement
US20150368591A1 (en) * 2013-02-12 2015-12-24 Henkel Ag & Co. Kgaa Anti-greying detergent
US9523064B2 (en) 2013-02-12 2016-12-20 Henkel Ag & Co. Kgaa Anti-greying detergent
WO2018172503A3 (fr) * 2017-03-24 2019-03-07 Basf Se Détergent pour lessive liquide comprenant un saccharide ou un polysaccharide modifié
DE102020201317A1 (de) 2020-02-04 2021-08-05 Henkel Ag & Co. Kgaa Chitosanderivate als schmutzablösevermögende Wirkstoffe
CN116209417A (zh) * 2020-08-21 2023-06-02 陶氏环球技术有限责任公司 非皂洗涤剂皂条组合物
DE102022200126A1 (de) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Fucoidane als vergrauungsinhibierende Wirkstoffe
WO2023131542A1 (fr) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Ulvanes utilisés comme agents inhibiteurs de décoloration
WO2023131527A1 (fr) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Fucoïdanes utilisés en tant qu'agents d'inhibition du grisaillement
DE102022200127A1 (de) 2022-01-07 2023-07-13 Henkel Ag & Co. Kgaa Ulvane als vergrauungsinhibierende Wirkstoffe
DE102022200269A1 (de) 2022-01-13 2023-07-13 Henkel Ag & Co. Kgaa Saccharosederivate als vergrauungsinhibierende Wirkstoffe
EP4321604A1 (fr) 2022-08-08 2024-02-14 The Procter & Gamble Company Tissu et composition de soins à domicile comprenant un tensioactif et un polyester
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WO2024129520A1 (fr) 2022-12-12 2024-06-20 The Procter & Gamble Company Composition de soin textile et ménager
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WO2025096272A1 (fr) 2023-11-02 2025-05-08 The Procter & Gamble Company Composition d'entretien textile et ménager
WO2025096273A1 (fr) 2023-11-02 2025-05-08 The Procter & Gamble Company Composition pour l'entretien ménager et des textiles
EP4553137A1 (fr) 2023-11-08 2025-05-14 The Procter & Gamble Company Composition de soin domestique et de tissu comprenant un polyester
WO2025101680A1 (fr) 2023-11-08 2025-05-15 The Procter & Gamble Company Composition d'entretien textile et ménager comprenant un polyester
EP4570893A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4570892A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de détergent à lessive
WO2025128415A1 (fr) 2023-12-15 2025-06-19 The Procter & Gamble Company Composition de détergent à lessive
WO2025128416A1 (fr) 2023-12-15 2025-06-19 The Procter & Gamble Company Tissu et composition d'entretien ménager

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CA2599356A1 (fr) 2006-11-09
AR053244A1 (es) 2007-04-25

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