EP1442109B1 - Polymeres pour applications de blanchissage - Google Patents

Polymeres pour applications de blanchissage Download PDF

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Publication number
EP1442109B1
EP1442109B1 EP02774634.6A EP02774634A EP1442109B1 EP 1442109 B1 EP1442109 B1 EP 1442109B1 EP 02774634 A EP02774634 A EP 02774634A EP 1442109 B1 EP1442109 B1 EP 1442109B1
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group
alkyl
cellulose
compositions
use according
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EP02774634.6A
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German (de)
English (en)
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EP1442109A1 (fr
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S. H. Unilever Research Port Sunlight ROGERS
M. S. Unilever Research Port Sunlight WHITE
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—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
    • C11D3/226—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin esterified
    • 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
    • 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
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • 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

Definitions

  • the present invention relates to substituted polysaccharides which are used in laundry cleaning products, for instance, for incorporation in products for dosing in the wash and/or rinse. These polymers are intended for, but not limited to, soil release benefits in such products.
  • a laundry cleaning composition comprises a graft polysaccharide polymer benefit agent capable of imparting a benefit such as soil release or fabric care, and at least one additional laundry cleaning ingredient.
  • WO 2000/65015 discloses a surface care composition, preferably a fabric care composition to be applied on a new and/or clean surface, preferably fabric surface, fully or in discrete regions thereof, comprising a film-forming polymer and providing superior soil removal performance while maintaining the particulate stain removal performance.
  • the present invention further relates to a process of treating a new and/or clean surface, preferably fabric surface, fully or in discrete regions thereof with such composition, to impart soil release properties thereto.
  • GB 1 537 287 discloses cellulose-based soil release ethers are used in detergent compositions containing C 10 -C 13 alkyl sulfate surfactants, and substantially free from interfering amounts of longer-chain length alkyl sulfates, to provide optimal soil release performance.
  • soil release polymer is used in the art to cover polymeric materials which assist release of soil from fabrics, e.g. cotton or polyester based fabrics. For example, it is used in relation to polymers which assist release of soil direct from fibres. It is also used to refer to polymers which modify the fibres so that dirt adheres to the polymer-modified fibres rather than to the fibre material itself. Then, when the fabric is washed the next time, the dirt is more easily removed than if it was adhering the fibres. Although not wishing to be bound by any particular theory or explanation, the inventors believe that the soil release polymers utilised in the present invention probably exert their effect mainly by the latter mechanism.
  • the compounds utilised by the present invention have been found, dependent upon the structure of the compound in question, to deliver a soil release, fabric care and/or other laundry cleaning benefit.
  • a benefit agent onto a substrate such as a fabric
  • a substrate such as a fabric
  • typical "benefit agents” include fabric softeners and conditioners, soil release polymers, sunscreens; and the like.
  • Deposition of a benefit agent is used, for example, in fabric treatment processes such as fabric softening to impart desirable properties to the fabric substrate.
  • the deposition of the benefit agent has had to rely upon the attractive forces between the oppositely charged substrate and the benefit agent.
  • this requires the addition of benefit agents during the rinsing step of a treatment process so as to avoid adverse effects from other charged chemical species present in the treatment compositions.
  • cationic fabric conditioners are incompatible with anionic surfactants in laundry washing compositions.
  • Such adverse charge considerations can place severe limitations upon the inclusion of benefit agents in compositions where an active component thereof is of an opposite charge to that of the benefit agent.
  • cotton is negatively charged and thus requires a positively charged benefit agent in order for the benefit agent to be substantive to the cotton, i.e. to have an affinity for the cotton so as to absorb onto it.
  • the substantivity of the benefit agent is reduced and/or the deposition rate of the material is reduced because of the presence of incompatible charged species in the compositions.
  • the compounds used by the present invention for soil-release and/or other benefits are substituted polysaccharide structures, especially substituted cellulosic structures.
  • US-A-4 235 735 discloses cellulose acetates with a defined degree of substitution as anti-redeposition agents in laundry products.
  • Cellulosic esters are also known for use in non-laundry applications, as described in WO-A-91/16359 and GB-A-1 041 020 .
  • cellulose based materials adhere to cotton fibres.
  • WO 00/18861 and WO 00/18862 disclose cellulosic compounds having a benefit agent attached, so that the benefit agent will be attached to the fibre. See also WO 99/1-4925 .
  • polysaccharide, especially cellulose, based materials to adhere has not been fully investigated, and a need exists to find polysaccharide based materials that are of commercial significance.
  • the present invention provides use according to claim 1.
  • cleaning or "laundering” mean “washing and/or rinsing”.
  • group -L-R 1 is a relatively small substituent of relatively low molecular weight compared to many of the groups which have been used as substituents for polysaccharides in the prior art.
  • 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 anhydroglucose unit.
  • the average degree of substitution groups is preferably from 0.1 to 3 (eg. from 0.3 to 3), more preferably from 0.1 to 1 (eg. from 0.3 to 1).
  • 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.
  • Suitable polysaccharides that are useful in the present invention include polysaccharides with a degree of polymerisation (DP) over 40, preferably from about 50 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, gu
  • 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 paucimobilis, 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 10,000 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, pullulan, scleroglucan, schizophyllan, chitin, hydroxyalkyl cellulose, arabinan (preferably from sugar beets), de-branched arabinan (preferably from sugar beets), arabinoxylan (preferably from rye and wheat flour), galactan (preferably from lupin and potatoes), pectic galactan (preferably from potatoes), galactomannan (preferably from carob, and including both low and high viscosities),
  • 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 ⁇ -1,4-linked polysaccharide is cellulose; a cellulose derivative, particularly cellulose sulphate, cellulose acetate, sulphoethyl cellulose, 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.
  • 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.
  • 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); C 1 -C 6 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 O-methyl-(N-1,12-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 O-methyl-(N-1,12-
  • Especially preferred polysaccharides include cellulose, ether, ester and urethane derivatives of cellulose, particularly cellulose monoacetate, xyloglucans and galactomannans, particularly Locust Bean gum.
  • 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 50 to 1000, more preferably 50 to 750 and especially 200 to 300.
  • the preferred molecular weight of such polysaccharides is from 10 000 to 150 000.
  • the total number of sugar units is from 10 to 200, preferably 100 to 150.
  • the preferred molecular weight is from 10 000 to 20 000.
  • 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 250 000 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 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 in which m, L and R 1 are as defined below.
  • L represents a group -O-CO- or -O-.
  • 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, sulphoethyl cellulose, 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 Locust Bean gum or xyloglucan.
  • the polymers have the general formula: wherein at least one or more -OR groups of the polymer are independently replaced by a group -L-R 1 in which L and R 1 are as defined above and at least one or more R groups are independently selected from groups of formulae:-
  • 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-1-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate cinnamate, formate, salicylate, carbamate, methylcarbamate, benzoate, gluconate, methanesulphonate, toluene, sulphonate, groups and hemiester groups of fumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric, aspartic, glutamic, and malic acids.
  • 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 triacetate refers to a molecule that has acetate esters in a degree of substitution of about 2.7 to 3.
  • Cellulose esters of hydroxyacids can be obtained using the acid anhydride in acetic acid solution at 20-30°C and in any case below 50°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°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 (10 g.) in dioxan (75 ml.) containing oxalic acid (10 g.) is heated at 100°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°C for 18 hours. The product is soluble in water and is precipitated and washed with ether-acetone. M.p. 230-250°C.
  • m is from 1 to 2, preferably 1.
  • 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.
  • carboxyalkyl ether-linked polymers can be made by reacting a polysaccharide with a suitable haloalkanoic acid
  • carboxyalkyl ester-linked polymers can be made by reacting a polysaccharide with a suitable anhydride, such as succinic anhydride
  • sulfoalkyl ether-linked polymers can be made by reacting a polysaccharide with a suitable alkenyl sulphonic acid.
  • the substituted polysaccharide according to 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 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 0.5% to 3%.
  • 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 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.
  • compositions of the invention may contain linear alkylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 . It is preferred if 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 -C 15 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 C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 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%.
  • 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 C 16 . Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of C 18 or above. It is preferred if 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 L ⁇ transition temperature greater than 25°C, preferably greater than 35°C, most preferably greater than 45°C.
  • This L ⁇ to L ⁇ transition can be measured by DSC as defined in " 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°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 20 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 C 14 .
  • 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. In both monoester and the diester quaternary ammonium compounds it is preferred if the 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 20 .
  • 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 14 . Even more preferably each chain has an average chain length equal to or greater than C 16 . Most preferably at least 50% of each long chain alkyl or alkenyl group has a chain length of C 18 . 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) :
  • 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:
  • 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):- where R 20 , R 21 and Y - are as hereinbefore defined.
  • 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 builders.
  • the total amount of detergency builder in the compositions will typically range from 5 to 80 wt%, preferably from 10 to 60 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 + 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 R 1 is a C 8 -C 22 alkyl group, preferably a C 8 -C 10 or C 12 -C 14 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).
  • surfactant surface-active compound
  • amount present will depend on the intended use of the detergent composition.
  • surfactant systems may be chosen, as is well known to the skilled formulator, for handwashing products and for products intended for use in different types of washing machine.
  • 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.
  • compositions of the invention when used as main wash fabric washing compositions, will generally also contain one or more detergency builders.
  • the total amount of detergency builder in the compositions will typically range from 5 to 80 wt%, preferably from 10 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 10 to 70% by weight (anhydrous basis), preferably 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.
  • the calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material.
  • 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 trisuccinates, 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 trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethy
  • Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, 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%.
  • 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 pernoanoic acid precursors.
  • Especially preferred bleach precursors suitable for use in the present invention are N,N,N',N',-tetracetyl ethylenediamine (TAED) and sodium nonanoyloxybenzene sulphonate (SNOBS).
  • TAED N,N,N',N',-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), the polyphosphonates such as Dequest (Trade Mark) and non-phosphate stabilisers such as EDDS (ethylene diamine di-succinic acid). 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 ).
  • a peroxy bleach compound preferably sodium percarbonate optionally together with a bleach activator
  • a transition metal bleach catalyst as described and claimed in EP 458 397A , EP 458 398A and EP 509 787A (Unilever ).
  • 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%.
  • detergent 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; foam controllers and decoupling polymers.
  • Further additional ingredients include surfactants, detergency builders, bleaches, transition metal sequestrants, enzymes, fabric softening and/or conditioning agents, lubricants for inhibition of fibre damage and/or for colour care and/or for crease reduction and/or for ease of ironing, UV absorbers such as fluorescers and photofading inhibitors, for example sunscreens/UV inhibitors and/or anti-oxidants, fungicides, insect repellents and/or insecticides, perfumes, dye fixatives, waterproofing agents, deposition aids, flocculants, anti-redeposition agents and soil release agents.
  • UV absorbers such as fluorescers and photofading inhibitors
  • sunscreens/UV inhibitors and/or anti-oxidants for example sunscreens/UV inhibitors and/or anti-oxidants
  • fungicides fungicides, insect repellents and/or insecticides
  • perfumes dye fixatives
  • waterproofing agents for example sunscreens/UV inhibitors and/or anti-oxidants
  • deposition aids for example, water
  • 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 4.00 g/1litre, 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.
  • the substrate may be any substrate onto which it is desirable to deposit a polymer and which is subjected to treatment such as a washing or rinsing process.
  • the substrate may be a textile fabric, fabric, preferably of cotton.
  • the treatment of the substrate with the material of the invention can be made by any suitable method such as washing, soaking or rinsing of the substrate.
  • the treatment will involve a washing or rinsing method such as treatment in the main wash or rinse cycle of a washing machine and involves contacting the substrate with an aqueous medium comprising the material of the invention.
  • Locust Bean Gum (MUD 246B, ex Rhodia) (5g, 30.84 mmol of anhydrosugar units) was dispersed in a mixture of demineralised water (12 ml) and propan-2-ol (30 ml) with vigorous stirring in a 2-necked 100ml round bottom flask fitted with a mechanical stirrer. After heating the solution to 70°C, sodium hydroxide (0.625g, 15.6 mmol) was added and the mixture stirred for 15 minutes at the reaction temperature. Sodium chloroacetate (1.8g, 15 mmol) was then added as a solution in demineralised water (2 ml) and the reaction mixture vigorously stirred for 15 minutes at 70°C.
  • Locust Bean Gum (MUD 246B, ex Rhodia) (5g, 30.84 mmol of anhydrosugar units) was dispersed in a mixture of demineralised water (12 ml) and propan-2-ol (30 ml) with vigorous stirring in a 2-necked 100ml round bottom flask fitted with a mechanical stirrer. After heating the solution to 70°C, sodium hydroxide (0.625g, 15.6 mmol) was added as a solution in water (2 ml) and the mixture stirred for 15 minutes at the reaction temperature. Vinyl sulfonic acid (8 ml of a 25% aqueous solution, 15.6 mmol) was added and the reaction mixture vigorously stirred for 15 minutes at 70°C.
  • a 9% w/v solution of lithium chloride in anhydrous dimethylsulfoxide (DMSO) was prepared by heating 100 ml of the solvent to 150°C in a 2-necked round bottom flask fitted with a mechanical stirrer.
  • Locust Bean Gum (MUD 246B, ex Rhodia) (5g, 30.84 mmol of anhydrosugar units) was added whilst maintaining the temperature until a highly viscous, homogeneous solution had formed.
  • Locust Bean Gum-succinate as prepared above (1.355g) was added to a conical flask, to which 25ml of 1M sodium hydroxide solution was added. This was repeated with a sample of the unmodified Locust Bean Gum (0.5g) as a blank. The flasks were stoppered and left at ambient temperature overnight. Each flask was then titrated with 1M hydrochloric acid solution using phenolphthalein as indicator. The amount of acid required for neutralisation allows the number of the succinic acid molecules present to be calculated. For this example, the Locust Bean Gum derivative was found to be 53% succinoylated.
  • copolymer with a backbone of (1,4)-linked ⁇ -D-mannose units having side stubs of (1,6)-linked ⁇ -D-galactose groups in a ratio of mannose to galactose 4 :1

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Claims (7)

  1. Utilisation d'un polymère pour promouvoir la libération de saleté pendant le lavage d'un tissu textile, caractérisée en ce que le polymère présente la formule générale I :
    Figure imgb0020
    où chaque SU représente une unité de sucre dans un squelette de polysaccharide ; le squelette de polysaccharide étant choisi dans le groupe constitué de xyloglucanes, glucomannanes, galactomannanes ;
    a représente le nombre d'unités de sucre non substitué comme un pourcentage du nombre total d'unités de sucre et se trouve dans l'intervalle de 0 à 99,9 %, de préférence de 65 à 99 %, encore mieux de 80 à 99 % ;
    b représente le nombre d'unités de sucre substitué comme un pourcentage du nombre total d'unités de sucre et se trouve dans l'intervalle de 0,1 à 100 %, de préférence de 1 à 35 %, encore mieux de 1 à 20 % ;
    m représente le degré de substitution par unité de sucre et est de 1 à 3 ;
    L représente une liaison ester ou éther ; et
    R1 représente un groupe alkyle, lequel est un groupe hydrocarboné saturé ramifié ou non ramifié qui contient de 1 à 12 atomes de carbone substitué par un groupe choisi parmi -OH, -CO-OR2 où R2 représente un atome d'hydrogène ou un métal alcalin, de préférence un atome de sodium ou de potassium.
  2. Utilisation selon la revendication 1, caractérisée en ce que L représente un groupe -O-CO- ou -O-.
  3. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le groupe alkyle est un groupe alkyle en C1-6, de préférence un groupe alkyle en C1-4.
  4. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que R1 représente un groupe hydroxyalkyle en C1-4, de préférence un groupe hydroxyméthyle, un groupe carboxyalkyle en C1-6, de préférence un groupe carboxyalkyle en C1-4, ou un groupe sulfoalkyle en C2-4, de préférence un groupe sulfoéthyle ou un sel de sodium de celui-ci.
  5. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que -L-R1 représente un groupe choisi parmi -O-CH2OH, -O-CH2CH2SO3H, -O-CH2-CO2H et -O-CO-CH2CH2CO2H et des sels de sodium de ceux-ci.
  6. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le squelette de polysaccharide est β-1,4-lié.
  7. Utilisation selon l'une quelconque des revendications précédentes, caractérisée en ce que le squelette de polysaccharide présente une masse moléculaire moyenne en nombre de 10 000 à 1 000 000.
EP02774634.6A 2001-11-09 2002-09-20 Polymeres pour applications de blanchissage Expired - Lifetime EP1442109B1 (fr)

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Families Citing this family (206)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0313900D0 (en) 2003-06-16 2003-07-23 Unilever Plc Laundry treatment compositions
GB0508883D0 (en) 2005-04-29 2005-06-08 Unilever Plc Polymers for laundry applications
GB0508882D0 (en) * 2005-04-29 2005-06-08 Unilever Plc Polymers for laundry applications
SE529259C2 (sv) 2005-08-31 2007-06-12 Ge Healthcare Bio Sciences Ab Tillverkning av kromarografimatriser, en kromarografimatris, en vätskekromatografikolonn, prcess för att isolera målföreningar och användning av en kromarografimatris för vätskekromatografi
JP2009511656A (ja) 2005-10-28 2009-03-19 ザ プロクター アンド ギャンブル カンパニー 陰イオン修飾カテコール、および汚れ懸濁ポリマー類を含有する組成物
EP1867708B1 (fr) * 2006-06-16 2017-05-03 The Procter and Gamble Company Compositions de lavage
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
ES2568457T3 (es) 2009-03-20 2016-04-29 Henkel Ag & Co. Kgaa Uso de polímeros con grupos carboxilo en combinación con cationes divalentes para la formación de una capa protectora
DE102009001803A1 (de) 2009-03-24 2010-09-30 Henkel Ag & Co. Kgaa Verwendung von Polymeren mit Carboxylgruppen in Kombination mit zweiwertigen Kationen zur Ausbildung einer Schutzschicht
EP2501792A2 (fr) 2009-12-29 2012-09-26 Novozymes A/S Polypeptides amplifiant la detergence
WO2011104339A1 (fr) 2010-02-25 2011-09-01 Novozymes A/S Variants d'un lysozyme et polynucléotides pour les coder
WO2012035103A1 (fr) 2010-09-16 2012-03-22 Novozymes A/S Lysozymes
JP2014508830A (ja) 2011-02-16 2014-04-10 ノボザイムス アクティーゼルスカブ 金属プロテアーゼを含む洗剤組成物
WO2012110563A1 (fr) 2011-02-16 2012-08-23 Novozymes A/S Compositions détersives contenant des métalloprotéases
WO2012110564A1 (fr) 2011-02-16 2012-08-23 Novozymes A/S Composition de détergent comprenant des métalloprotéases m7 ou m35
GB201103974D0 (en) 2011-03-09 2011-04-20 Reckitt Benckiser Nv Composition
JP6126086B2 (ja) 2011-06-24 2017-05-10 ノボザイムス アクティーゼルスカブ プロテアーゼ活性を有するポリペプチドおよびこれをコードするポリヌクレオチド
CN112662734A (zh) 2011-06-30 2021-04-16 诺维信公司 用于筛选α-淀粉酶的方法
MX2014001594A (es) 2011-08-15 2014-04-25 Novozymes As Polipeptidos que tienen actividad de celulasa y polinucleotidos que los codifican.
WO2013041689A1 (fr) 2011-09-22 2013-03-28 Novozymes A/S Polypeptides ayant une activité protéase et polynucléotides codant pour ceux-ci
JP2015500006A (ja) 2011-11-25 2015-01-05 ノボザイムス アクティーゼルスカブ サブチラーゼ変異体およびこれをコードするポリヌクレオチド
BR112014012170A2 (pt) 2011-11-25 2020-06-23 Novozymes A/S polipetídeo isolado, composição, aditivo de ração animal, uso de um polipetídeo, métodos de isolamento de dna de bastérias, e de produção de um poliptídeo, polinucleotídeo isolado, constructo de ácido nucleico ou vetor de expressão, célula hospedeira recombinante, e, planta, parte de planta ou célula de planta
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US9809787B2 (en) 2011-12-29 2017-11-07 Novozymes A/S Detergent compositions comprising lipase
ES2644007T3 (es) 2012-01-26 2017-11-27 Novozymes A/S Uso de polipéptidos con actividad de proteasa en piensos para animales y en detergentes
JP2015509364A (ja) 2012-02-17 2015-03-30 ノボザイムス アクティーゼルスカブ サブチリシン変異体およびそれをコードするポリヌクレオチド
US20150064773A1 (en) 2012-03-07 2015-03-05 Novozymes A/S Detergent Composition and Substitution of Optical Brighteners in Detergent Composition
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EP2861749A1 (fr) 2012-06-19 2015-04-22 Novozymes Bioag A/S Réduction enzymatique de la teneur en hydroperoxydes
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BR112015003724A2 (pt) 2012-08-22 2017-08-08 Novozymes As polipeptídeo isolado, composição, uso de uma composição, polinucleotídeo isolado, constructo de ácido nucleico ou vetor de expressão, célula hospedeira recombinante, e, métodos de produção de um polipeptídeo e de produção de uma proteína.
EP2888360B1 (fr) 2012-08-22 2017-10-25 Novozymes A/S Métalloprotéases dérivées de alicyclobacillus sp.
BR112015003726A2 (pt) 2012-08-22 2019-09-24 Novozymes As composição detergente, uso de uma composição e de um polipeptídeo, e, método para remoção de uma nódoa de uma superfície.
WO2014090940A1 (fr) 2012-12-14 2014-06-19 Novozymes A/S Élimination de souillures issues de la peau
US9551042B2 (en) 2012-12-21 2017-01-24 Novozymes A/S Polypeptides having protease activity and polynucleotides encoding same
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EP2970830B1 (fr) 2013-03-14 2017-12-13 Novozymes A/S Films solubles dans l'eau contenant une protéase et un inhibiteur
EP3461881A1 (fr) 2013-05-03 2019-04-03 Novozymes A/S Microencapsulation d'enzymes détergentes
WO2014183921A1 (fr) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides présentant une activité alpha-amylase
US10538751B2 (en) 2013-06-06 2020-01-21 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2014207224A1 (fr) 2013-06-27 2014-12-31 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
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EP3613853A1 (fr) 2013-07-29 2020-02-26 Novozymes A/S Variants de protéase et polynucléotides les codants
RU2670946C9 (ru) 2013-07-29 2018-11-26 Новозимс А/С Варианты протеазы и кодирующие их полинуклеотиды
WO2015049370A1 (fr) 2013-10-03 2015-04-09 Novozymes A/S Composition détergente et utilisation de celle-ci
EP3083954B1 (fr) 2013-12-20 2018-09-26 Novozymes A/S Polypeptides a activite de protease et polynucleotides les codant
EP3114219A1 (fr) 2014-03-05 2017-01-11 Novozymes A/S Compositions et procédés destinés à améliorer les propriétés de matériaux textiles non-cellulosiques par l'utilisation d'endo-xyloglucane transférase
CN106062271A (zh) 2014-03-05 2016-10-26 诺维信公司 用于改进具有木葡聚糖内糖基转移酶的纤维素纺织材料的性质的组合物和方法
US20170015950A1 (en) 2014-04-01 2017-01-19 Novozymes A/S Polypeptides having alpha amylase activity
WO2015155350A1 (fr) 2014-04-11 2015-10-15 Novozymes A/S Composition de détergent
US20170121695A1 (en) 2014-06-12 2017-05-04 Novozymes A/S Alpha-amylase variants and polynucleotides encoding same
WO2016001319A1 (fr) 2014-07-03 2016-01-07 Novozymes A/S Stabilisation améliorée d'enzyme autre que la protéase
EP3739029A1 (fr) 2014-07-04 2020-11-18 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
WO2016001449A1 (fr) 2014-07-04 2016-01-07 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
US10287562B2 (en) 2014-11-20 2019-05-14 Novoszymes A/S Alicyclobacillus variants and polynucleotides encoding same
US10683491B2 (en) 2014-12-04 2020-06-16 Novozymes A/S Subtilase variants and polynucleotides encoding same
WO2016087619A1 (fr) 2014-12-04 2016-06-09 Novozymes A/S Compositions de nettoyage liquides comprenant des variants de protéase
WO2016096714A1 (fr) 2014-12-15 2016-06-23 Henkel Ag & Co. Kgaa Composition de détergent comprenant des variants de subtilase
WO2016096996A1 (fr) 2014-12-16 2016-06-23 Novozymes A/S Polypeptides ayant une activité n-acétylglucosamine oxydase
US11518987B2 (en) 2014-12-19 2022-12-06 Novozymes A/S Protease variants and polynucleotides encoding same
CN107109388A (zh) 2014-12-19 2017-08-29 诺维信公司 蛋白酶变体以及对其进行编码的多核苷酸
EP3280791A1 (fr) 2015-04-10 2018-02-14 Novozymes A/S Procédé de lavage de linge, utilisation d'adnase et composition détergente
EP3106508B1 (fr) 2015-06-18 2019-11-20 Henkel AG & Co. KGaA Composition détergente comprenant des variantes de subtilase
EP3310912B1 (fr) 2015-06-18 2021-01-27 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
US20180171271A1 (en) 2015-06-30 2018-06-21 Novozymes A/S Laundry detergent composition, method for washing and use of composition
WO2017046260A1 (fr) 2015-09-17 2017-03-23 Novozymes A/S Polypeptides présentant une activité de dégradation de xylanase et polynucléotides codant pour ceux-ci
MX2018002831A (es) 2015-10-07 2018-09-28 Novozymes As Polipeptidos.
EP3362556B1 (fr) 2015-10-14 2024-07-10 Novozymes A/S Variants polypeptidiques
CN108291215A (zh) 2015-10-14 2018-07-17 诺维信公司 具有蛋白酶活性的多肽以及编码它们的多核苷酸
WO2016203064A2 (fr) 2015-10-28 2016-12-22 Novozymes A/S Composition de détergent comprenant des variants de protéase et d'amylase
EP3380608A1 (fr) 2015-11-24 2018-10-03 Novozymes A/S Polypeptides ayant une activité de protéase et polynucléotides codant pour ceux-ci
WO2017097866A1 (fr) 2015-12-07 2017-06-15 Novozymes A/S Polypeptides ayant une activité bêta-glucanase, polynucléotides codant pour celles-ci et utilisations de ceux-ci dans des compositions nettoyantes et détergentes
US20210171927A1 (en) 2016-01-29 2021-06-10 Novozymes A/S Beta-glucanase variants and polynucleotides encoding same
EP3715442A1 (fr) 2016-03-23 2020-09-30 Novozymes A/S Utilisation d'un polypeptide ayant une activité dnase pour le traitement de tissus
CN109312270B (zh) 2016-04-08 2022-01-28 诺维信公司 洗涤剂组合物及其用途
EP3448978B1 (fr) 2016-04-29 2020-03-11 Novozymes A/S Compositions détergentes et leurs utilisations
WO2017210188A1 (fr) 2016-05-31 2017-12-07 Novozymes A/S Compositions stabilisées de peroxyde liquide
WO2017207762A1 (fr) 2016-06-03 2017-12-07 Novozymes A/S Variants de subtilase et polynucléotides codant pour ceux-ci
CN109563495A (zh) 2016-06-30 2019-04-02 诺维信公司 脂肪酶变体及包含表面活性剂和脂肪酶变体的组合物
WO2018002261A1 (fr) 2016-07-01 2018-01-04 Novozymes A/S Compositions détergentes
CN109715794A (zh) 2016-07-05 2019-05-03 诺维信公司 果胶裂解酶变体以及编码它们的多核苷酸
WO2018007573A1 (fr) 2016-07-08 2018-01-11 Novozymes A/S Compositions détergentes contenant de la galactanase
CN109642222A (zh) 2016-07-13 2019-04-16 诺维信公司 食物芽孢杆菌dna酶变体
US11512300B2 (en) 2016-08-24 2022-11-29 Novozymes A/S Xanthan lyase variants and polynucleotides encoding same
CN109563498A (zh) 2016-08-24 2019-04-02 汉高股份有限及两合公司 包含黄原胶裂解酶变体i的洗涤剂组合物
CA3031609A1 (fr) 2016-08-24 2018-03-01 Novozymes A/S Variants d'endoglucanase gh9 et polynucleotides codant pour de tels variants
EP3504313A1 (fr) 2016-08-24 2019-07-03 Henkel AG & Co. KGaA Composition détergente comprenant des variants i d'endoglucanase gh9
CN109996859B (zh) 2016-09-29 2021-11-30 诺维信公司 含孢子的颗粒
EP3532592A1 (fr) 2016-10-25 2019-09-04 Novozymes A/S Compositions détergentes
US11753605B2 (en) 2016-11-01 2023-09-12 Novozymes A/S Multi-core granules
WO2018108865A1 (fr) 2016-12-12 2018-06-21 Novozymes A/S Utilisation de polypeptides
WO2018177938A1 (fr) 2017-03-31 2018-10-04 Novozymes A/S Polypeptides présentant une activité dnase
WO2018177936A1 (fr) 2017-03-31 2018-10-04 Novozymes A/S Polypeptides ayant une activité dnase
US11149233B2 (en) 2017-03-31 2021-10-19 Novozymes A/S Polypeptides having RNase activity
US20200109352A1 (en) 2017-04-04 2020-04-09 Novozymes A/S Polypeptide compositions and uses thereof
US20200109354A1 (en) 2017-04-04 2020-04-09 Novozymes A/S Polypeptides
CN110651029B (zh) 2017-04-04 2022-02-15 诺维信公司 糖基水解酶
ES2728758T3 (es) 2017-04-05 2019-10-28 Henkel Ag & Co Kgaa Composiciones de detergente que comprenden mananasas bacterianas
EP3385362A1 (fr) 2017-04-05 2018-10-10 Henkel AG & Co. KGaA Compositions détergentes comprenant des mannanases fongiques
WO2018185285A1 (fr) 2017-04-06 2018-10-11 Novozymes A/S Compositions de nettoyage et utilisations correspondantes
WO2018184818A1 (fr) 2017-04-06 2018-10-11 Novozymes A/S Compositions de nettoyage et leurs utilisations
US11407964B2 (en) 2017-04-06 2022-08-09 Novozymes A/S Cleaning compositions and uses thereof
US10968416B2 (en) 2017-04-06 2021-04-06 Novozymes A/S Cleaning compositions and uses thereof
EP3607042A1 (fr) 2017-04-06 2020-02-12 Novozymes A/S Compositions de nettoyage et leurs utilisations
CA3058519A1 (fr) 2017-04-06 2018-10-11 Novozymes A/S Compositions de nettoyage comprenant une desoxyribonuclease et une protease
WO2018184873A1 (fr) 2017-04-06 2018-10-11 Novozymes A/S Compositions de détergent et leurs utilisations
WO2018185280A1 (fr) 2017-04-06 2018-10-11 Novozymes A/S Compositions de nettoyage et leurs utilisations
EP3401385A1 (fr) 2017-05-08 2018-11-14 Henkel AG & Co. KGaA Composition détergente comprenant un polypeptide comprenant un domaine de liaison aux glucides
WO2018206535A1 (fr) 2017-05-08 2018-11-15 Novozymes A/S Domaine de liaison aux glucides et polynucléotides codant pour celui-ci
WO2018224544A1 (fr) 2017-06-08 2018-12-13 Novozymes A/S Compositions comprenant des polypeptides ayant une activité cellulase et une activité amylase et leurs utilisations dans des compositions de nettoyage et détergentes
US20200181542A1 (en) 2017-06-30 2020-06-11 Novozymes A/S Enzyme Slurry Composition
WO2019038058A1 (fr) 2017-08-24 2019-02-28 Novozymes A/S Variants d'endoglucanase gh9 et polynucléotides codant pour de tels variants
EP3673060A1 (fr) 2017-08-24 2020-07-01 Henkel AG & Co. KGaA Composition détergente comprenant des variants de xanthane lyase ii
CN111344404A (zh) 2017-08-24 2020-06-26 诺维信公司 黄原胶裂解酶变体以及编码其的多核苷酸
US11624059B2 (en) 2017-08-24 2023-04-11 Henkel Ag & Co. Kgaa Detergent compositions comprising GH9 endoglucanase variants II
US11414814B2 (en) 2017-09-22 2022-08-16 Novozymes A/S Polypeptides
WO2019067390A1 (fr) 2017-09-27 2019-04-04 The Procter & Gamble Company Compositions de détergent contenant des lipases
WO2019068713A1 (fr) 2017-10-02 2019-04-11 Novozymes A/S Polypeptides présentant une activité mannanase et polynucléotides codant pour ces polypeptides
CN111373036A (zh) 2017-10-02 2020-07-03 诺维信公司 具有甘露聚糖酶活性的多肽和编码它们的多核苷酸
WO2019076800A1 (fr) 2017-10-16 2019-04-25 Novozymes A/S Compositions de nettoyage et leurs utilisations
CN111448302A (zh) 2017-10-16 2020-07-24 诺维信公司 低粉化颗粒
WO2019076834A1 (fr) 2017-10-16 2019-04-25 Novozymes A/S Granulés à faible teneur en poussière
WO2019081515A1 (fr) 2017-10-24 2019-05-02 Novozymes A/S Compositions comprenant des polypeptides présentant une activité mannanase
EP3701017A1 (fr) 2017-10-27 2020-09-02 Novozymes A/S Variants de dnase
CN111386340B (zh) 2017-10-27 2024-05-24 宝洁公司 包含多肽变体的洗涤剂组合物
BR112020008737A2 (pt) 2017-11-01 2020-10-13 Novozymes A/S polipeptídeos e composições que compreendam tais polipeptídeos
DE102017125558A1 (de) 2017-11-01 2019-05-02 Henkel Ag & Co. Kgaa Reinigungszusammensetzungen, die dispersine i enthalten
EP3704220A1 (fr) 2017-11-01 2020-09-09 Novozymes A/S Procédés de nettoyage de dispositifs médicaux
DE102017125559A1 (de) 2017-11-01 2019-05-02 Henkel Ag & Co. Kgaa Reinigungszusammensetzungen, die dispersine ii enthalten
CN111479919A (zh) 2017-11-01 2020-07-31 诺维信公司 多肽以及包含此类多肽的组合物
DE102017125560A1 (de) 2017-11-01 2019-05-02 Henkel Ag & Co. Kgaa Reinigungszusammensetzungen, die dispersine iii enthalten
KR20200124258A (ko) 2018-02-23 2020-11-02 헨켈 아게 운트 코. 카게아아 크산탄 리아제 및 엔도글루카나제 변이체를 포함하는 세제 조성물
CN111770788B (zh) 2018-03-13 2023-07-25 诺维信公司 使用氨基糖低聚物进行微囊化
WO2019180111A1 (fr) 2018-03-23 2019-09-26 Novozymes A/S Variants de subtilase et compositions les comprenant
WO2019201793A1 (fr) 2018-04-17 2019-10-24 Novozymes A/S Polypeptides ayant une activité de liaison des hydrates de carbone dans des compositions détergentes et leur utilisation pour réduire les plis de textiles ou de tissus
WO2019201785A1 (fr) 2018-04-19 2019-10-24 Novozymes A/S Variants améliorés de cellulase
US11661592B2 (en) 2018-04-19 2023-05-30 Novozymes A/S Stabilized endoglucanase variants
CN112368363A (zh) 2018-06-28 2021-02-12 诺维信公司 洗涤剂组合物及其用途
EP3814473A1 (fr) 2018-06-29 2021-05-05 Novozymes A/S Compositions détergentes et leurs utilisations
WO2020002255A1 (fr) 2018-06-29 2020-01-02 Novozymes A/S Variants de subtilase et compositions les comprenant
WO2020007863A1 (fr) 2018-07-02 2020-01-09 Novozymes A/S Compositions de nettoyage et leurs utilisations
WO2020007875A1 (fr) 2018-07-03 2020-01-09 Novozymes A/S Compositions de nettoyage et leurs utilisations
WO2020008024A1 (fr) 2018-07-06 2020-01-09 Novozymes A/S Compositions de nettoyage et leurs utilisations
WO2020008043A1 (fr) 2018-07-06 2020-01-09 Novozymes A/S Compositions de nettoyage et leurs utilisations
US20210340466A1 (en) 2018-10-01 2021-11-04 Novozymes A/S Detergent compositions and uses thereof
WO2020070209A1 (fr) 2018-10-02 2020-04-09 Novozymes A/S Composition de nettoyage
WO2020070011A1 (fr) 2018-10-02 2020-04-09 Novozymes A/S Composition de nettoyage
WO2020070014A1 (fr) 2018-10-02 2020-04-09 Novozymes A/S Composition de nettoyage comprenant un tensioactif anionique et un polypeptide ayant une activité rnase
WO2020070249A1 (fr) 2018-10-03 2020-04-09 Novozymes A/S Compositions de nettoyage
US11993762B2 (en) 2018-10-03 2024-05-28 Novozymes A/S Polypeptides having alpha-mannan degrading activity and polynucleotides encoding same
WO2020074498A1 (fr) 2018-10-09 2020-04-16 Novozymes A/S Compositions de nettoyage et leurs utilisations
WO2020074499A1 (fr) 2018-10-09 2020-04-16 Novozymes A/S Compositions de nettoyage et leurs utilisations
EP3864124A1 (fr) 2018-10-11 2021-08-18 Novozymes A/S Compositions de nettoyage et leurs utilisations
EP3647397A1 (fr) 2018-10-31 2020-05-06 Henkel AG & Co. KGaA Compositions de nettoyage contenant des dispersions iv
EP3647398B1 (fr) 2018-10-31 2024-05-15 Henkel AG & Co. KGaA Compositions de nettoyage contenant des dispersines v
US20220056379A1 (en) 2018-12-03 2022-02-24 Novozymes A/S Powder Detergent Compositions
EP3891264A1 (fr) 2018-12-03 2021-10-13 Novozymes A/S Composition détergente en poudre de faible ph
US11959111B2 (en) 2018-12-21 2024-04-16 Novozymes A/S Polypeptides having peptidoglycan degrading activity and polynucleotides encoding same
CN113330101A (zh) 2018-12-21 2021-08-31 诺维信公司 包含金属蛋白酶的洗涤剂袋
EP3702452A1 (fr) 2019-03-01 2020-09-02 Novozymes A/S Compositions détergentes comprenant deux protéases
BR112021018731A2 (pt) 2019-03-21 2021-12-21 Novozymes As Variantes de alfa-amilase e polinucleotídeos codificando as mesmas
US20220169953A1 (en) 2019-04-03 2022-06-02 Novozymes A/S Polypeptides having beta-glucanase activity, polynucleotides encoding same and uses thereof in cleaning and detergent compositions
WO2020207944A1 (fr) 2019-04-10 2020-10-15 Novozymes A/S Variants polypeptidiques
US20220186151A1 (en) 2019-04-12 2022-06-16 Novozymes A/S Stabilized glycoside hydrolase variants
WO2021009067A1 (fr) 2019-07-12 2021-01-21 Novozymes A/S Émulsions enzymatiques pour détergents
US20220325204A1 (en) 2019-08-27 2022-10-13 Novozymes A/S Detergent composition
US20220315866A1 (en) 2019-09-19 2022-10-06 Novozymes A/S Detergent Composition
WO2021064068A1 (fr) 2019-10-03 2021-04-08 Novozymes A/S Polypeptides comprenant au moins deux domaines de liaison aux hydrates de carbone
KR20220119608A (ko) 2019-12-20 2022-08-30 헨켈 아게 운트 코. 카게아아 디스페르신 viii을 포함하는 세정 조성물
WO2021122117A1 (fr) 2019-12-20 2021-06-24 Henkel Ag & Co. Kgaa Composition de nettoyage comprenant une dispersine et une carbohydrase
WO2021122118A1 (fr) 2019-12-20 2021-06-24 Henkel Ag & Co. Kgaa Compositions de nettoyage comprenant des dispersines vi
AU2020405786A1 (en) 2019-12-20 2022-08-11 Henkel Ag & Co. Kgaa Cleaning compositions comprising dispersins IX
CN114929848A (zh) 2019-12-20 2022-08-19 诺维信公司 稳定的液体无硼酶组合物
EP4077656A2 (fr) 2019-12-20 2022-10-26 Novozymes A/S Polypeptides présentant une activité protéolytique et leur utilisation
WO2021130167A1 (fr) 2019-12-23 2021-07-01 Novozymes A/S Compositions enzymatiques et utilisations associées
EP4093842A1 (fr) 2020-01-23 2022-11-30 Novozymes A/S Compositions enzymatiques et leurs utilisations
WO2021152120A1 (fr) 2020-01-31 2021-08-05 Novozymes A/S Variants de mannanase et polynucléotides codant pour ceux-ci
BR112022014946A2 (pt) 2020-01-31 2022-10-04 Novozymes As Variantes de mananase e polinucleotídeos codificando as mesmas
DE102020201317A1 (de) 2020-02-04 2021-08-05 Henkel Ag & Co. Kgaa Chitosanderivate als schmutzablösevermögende Wirkstoffe
EP3892708A1 (fr) 2020-04-06 2021-10-13 Henkel AG & Co. KGaA Compositions de nettoyage comprenant des variantes de dispersine
CN115210371A (zh) 2020-04-08 2022-10-18 诺维信公司 碳水化合物结合模块变体
EP4139431A1 (fr) 2020-04-21 2023-03-01 Novozymes A/S Compositions de nettoyage comprenant des polypeptides ayant une activité de dégradation de fructane
WO2021239818A1 (fr) 2020-05-26 2021-12-02 Novozymes A/S Variants de subtilase et compositions les comprenant
EP3936593A1 (fr) 2020-07-08 2022-01-12 Henkel AG & Co. KGaA Compositions de nettoyage et leurs utilisations
WO2022043321A2 (fr) 2020-08-25 2022-03-03 Novozymes A/S Variants de xyloglucanase de la famille 44
US20230323330A1 (en) 2020-08-28 2023-10-12 Novozymes A/S Polyester degrading protease variants
WO2022074037A2 (fr) 2020-10-07 2022-04-14 Novozymes A/S Variants d'alpha-amylase
EP4232539A2 (fr) 2020-10-20 2023-08-30 Novozymes A/S Utilisation de polypeptides ayant une activité de dnase
EP4032966A1 (fr) 2021-01-22 2022-07-27 Novozymes A/S Composition enzymatique liquide avec piégeur de sulfite
EP4039806A1 (fr) 2021-02-04 2022-08-10 Henkel AG & Co. KGaA Composition détergente comprenant des variants de xanthane lyase et d'endoglucanase à stabilité améliorée
WO2022171780A2 (fr) 2021-02-12 2022-08-18 Novozymes A/S Variants d'alpha-amylase
WO2022171872A1 (fr) 2021-02-12 2022-08-18 Novozymes A/S Détergents biologiques stabilisés
EP4305146A1 (fr) 2021-03-12 2024-01-17 Novozymes A/S Variants polypeptidiques
EP4060036A1 (fr) 2021-03-15 2022-09-21 Novozymes A/S Variantes de polypeptides
WO2022194673A1 (fr) 2021-03-15 2022-09-22 Novozymes A/S Variants de la dnase
EP4359518A1 (fr) 2021-06-23 2024-05-01 Novozymes A/S Polypeptides d'alpha-amylase
WO2023061928A1 (fr) 2021-10-12 2023-04-20 Novozymes A/S Endoglucanase à stabilité améliorée
EP4206309A1 (fr) 2021-12-30 2023-07-05 Novozymes A/S Particules de protéines à blancheur améliorée
WO2023165950A1 (fr) 2022-03-04 2023-09-07 Novozymes A/S Variants de dnase et compositions
WO2023194204A1 (fr) 2022-04-08 2023-10-12 Novozymes A/S Variants et compositions d'hexosaminidase
WO2023247348A1 (fr) 2022-06-21 2023-12-28 Novozymes A/S Variants de mannanase et polynucléotides codant pour ceux-ci
WO2024083819A1 (fr) 2022-10-20 2024-04-25 Novozymes A/S Agents d'élimination de lipides pour détergents
WO2024110541A1 (fr) 2022-11-22 2024-05-30 Novozymes A/S Granulés colorés ayant une stabilité de colorant améliorée
WO2024121070A1 (fr) 2022-12-05 2024-06-13 Novozymes A/S Variants de protéase et polynucléotides codant pour ceux-ci
WO2024131880A2 (fr) 2022-12-23 2024-06-27 Novozymes A/S Composition détergente comprenant une catalase et une amylase

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010267A1 (fr) * 2001-07-20 2003-02-06 Unilever Plc Utilisation de polymeres greffes dans le nettoyage de tissus

Family Cites Families (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB320842A (en) 1928-04-18 1929-10-18 Henry Dreyfus The manufacture and treatment of cellulose derivatives
FR702116A (fr) 1929-08-02 1931-03-30 Kodak Pathe Soc Procédé de fabrication d'esters mixtes de cellulose
SE1061757A (fr) * 1957-11-22
US3303051A (en) 1963-04-05 1967-02-07 United Merchants & Mfg Process of conditioning cellulose acetate with hydroxyethylcellulose
GB1243785A (en) 1967-10-12 1971-08-25 De La Rue Instr Improvements in sheet counting apparatus
US3756966A (en) * 1971-09-28 1973-09-04 Lever Brothers Ltd Compositions sulfosuccinate derivatives of carbohydrates as builders for detergent
US4020015A (en) * 1971-10-12 1977-04-26 Lever Brothers Company Detergent compositions
GB1437950A (en) 1972-08-22 1976-06-03 Unilever Ltd Detergent compositions
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
US4605509A (en) 1973-05-11 1986-08-12 The Procter & Gamble Company Detergent compositions containing sodium aluminosilicate builders
DE2433485A1 (de) 1973-07-16 1975-02-06 Procter & Gamble Zur verwendung in waschmitteln geeignete aluminosilikat-ionenaustauscher
DE2613791A1 (de) * 1975-04-02 1976-10-21 Procter & Gamble Waschmittel
GB1567947A (en) 1976-07-02 1980-05-21 Unilever Ltd Esters of quaternised amino-alcohols for treating fabrics
US4235735A (en) * 1979-07-30 1980-11-25 Milliken Research Corporation Laundry detergent containing cellulose acetate anti-redeposition agent
ATE7044T1 (de) * 1980-12-17 1984-04-15 Unilever Nv Detergenszusammensetzung mit antiwiederablagerungseigenschaften.
GB2123044B (en) 1982-06-10 1986-02-05 Kao Corp Bleaching detergent composition
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
GB8519046D0 (en) * 1985-07-29 1985-09-04 Unilever Plc Detergent compositions
US4686063A (en) 1986-09-12 1987-08-11 The Procter & Gamble Company Fatty peroxyacids or salts thereof having amide moieties in the fatty chain and low levels of exotherm control agents
US4751015A (en) 1987-03-17 1988-06-14 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
US4818426A (en) 1987-03-17 1989-04-04 Lever Brothers Company Quaternary ammonium or phosphonium substituted peroxy carbonic acid precursors and their use in detergent bleach compositions
US4933103A (en) 1987-03-23 1990-06-12 Kao Corporation Bleaching composition
US4915863A (en) 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
IT1233846B (it) 1988-01-20 1992-04-21 Ausimont Spa Perossiacidi immido aromatici
IT1215739B (it) 1988-01-20 1990-02-22 Ausimont Spa Perossiacidi immido aromatici come agenti sbiancanti.
GB8810193D0 (en) 1988-04-29 1988-06-02 Unilever Plc Detergent compositions & process for preparing them
DE3823172C2 (de) 1988-07-08 1998-01-22 Hoechst Ag omega-Phthalimidoperoxihexansäure, Verfahren zu dessen Herstellung und dessen Verwendung
ES2085273T3 (es) 1988-11-02 1996-06-01 Unilever Nv Procedimiento para preparar una composicion detergente granular de alta densidad aparente.
CA2001927C (fr) 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates et detergents
GB8907187D0 (en) 1989-03-30 1989-05-10 Unilever Plc Detergent compositions and process for preparing them
US4988451A (en) 1989-06-14 1991-01-29 Lever Brothers Company, Division Of Conopco, Inc. Stabilization of particles containing quaternary ammonium bleach precursors
GB8922018D0 (en) 1989-09-29 1989-11-15 Unilever Plc Detergent compositions and process for preparing them
US5142034A (en) 1990-04-16 1992-08-25 Eastman Kodak Company Cellulose ester compositions and process for the preparation thereof
ES2100925T3 (es) 1990-05-21 1997-07-01 Unilever Nv Activacion de blanqueador.
GB9108136D0 (en) 1991-04-17 1991-06-05 Unilever Plc Concentrated detergent powder compositions
US5397501A (en) 1993-07-26 1995-03-14 Lever Brothers Company, Division Of Conopco, Inc. Amido peroxycarboxylic acids for bleaching
EP0874802A1 (fr) * 1995-10-27 1998-11-04 Basf Aktiengesellschaft Derives d'acides gras et leur utilisation comme agents tensio-actifs dans des produits de lavage et de nettoyage
DE69723575T2 (de) 1996-12-26 2004-05-13 The Procter & Gamble Company, Cincinnati Waschmittelzusammensetzungen enthaltend zellulosepolymere
AU746433B2 (en) * 1997-09-15 2002-05-02 Procter & Gamble Company, The Laundry detergent compositions with cellulosic based polymers to provide appearance and integrity benefits to fabrics laundered therewith
DE19740558C2 (de) 1997-09-15 2003-01-09 Siemens Ag Verfahren zum Übertragen von "MWI-Dienst"-spezifischen Nachrichten in Telekommunikationsnetzen, insbesondere in hybriden DECT/ISDN-spezifischen Telekommunikationsnetzen
GB9821218D0 (en) 1998-09-30 1998-11-25 Unilever Plc Treatment for fabrics
GB9821217D0 (en) * 1998-09-30 1998-11-25 Unilever Plc Treatment for substrates
GB9900151D0 (en) 1999-01-05 1999-02-24 Unilever Plc Treatment for fabrics
GB9900150D0 (en) * 1999-01-05 1999-02-24 Unilever Plc Treatment for fabrics
JP2002534592A (ja) * 1999-01-13 2002-10-15 ザ、プロクター、エンド、ギャンブル、カンパニー セルロースポリマーを有する洗剤組成物
WO2000065015A2 (fr) * 1999-04-27 2000-11-02 The Procter & Gamble Company Compositions traitante pour surfaces et procede associe

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003010267A1 (fr) * 2001-07-20 2003-02-06 Unilever Plc Utilisation de polymeres greffes dans le nettoyage de tissus

Also Published As

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BR0213709A (pt) 2004-10-26
EP2330178A3 (fr) 2014-05-14
EP1442109A1 (fr) 2004-08-04
WO2003040279A1 (fr) 2003-05-15
EP2330178A2 (fr) 2011-06-08
BR0213709B1 (pt) 2014-11-18
GB0127036D0 (en) 2002-01-02
ES2675289T3 (es) 2018-07-10

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