EP1442109B1 - Polymere für waschanwendungen - Google Patents

Polymere für waschanwendungen 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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Prior art keywords
group
alkyl
cellulose
compositions
use according
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English (en)
French (fr)
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EP1442109A1 (de
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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. Verwendung eines Polymers zur Förderung des Soil-Release während des Waschens eines textilen Gebildes, dadurch gekennzeichnet, dass das Polymer die allgemeine Formel I:
    Figure imgb0019
    aufweist, in welcher jede SU eine Zucker-Einheit in einem Polysaccharid-Gerüst darstellt, wobei das Polysaccharid-Gerüst aus der Gruppe ausgewählt ist, die aus Xyloglucanen, Glucomannanen, Galactomannanen besteht,
    a die Zahl der unsubstituierten Zucker-Einheiten als prozentualer Anteil der Gesamtzahl der Zucker-Einheiten darstellt und in dem Bereich von 0 bis 99,9%, vorzugsweise von 65 bis 99%, bevorzugter von 80 bis 99%, liegt,
    b die Zahl der substituierten Zucker-Einheiten als prozentualer Anteil der Gesamtzahl der Zucker-Einheiten darstellt und in dem Bereich von 0,1 bis 100%, vorzugsweise von 1 bis 35%, bevorzugter von 1 bis 20%, liegt,
    m den Substitutionsgrad je Zucker-Einheit darstellt und von 1 bis 3 beträgt, L eine Ester- oder Ether-Verknüpfung darstellt und
    R1 eine Alkyl-Gruppe darstellt, die eine verzweigte oder unverzweigte gesättigte Kohlenwasserstoff-Gruppe ist, die 1 bis 12 Kohlenstoffatome enthält, substituiert durch eine Gruppe, ausgewählt aus -OH, -CO-OR2, wobei R2 ein Wasserstoffatom oder ein Alkalimetall-, vorzugsweise ein Natrium- oder Kalium-Atom darstellt.
  2. Verwendung nach Anspruch 1, dadurch gekennzeichnet, dass L eine Gruppe -O-CO- oder -O- darstellt.
  3. Verwendung nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Alkyl-Gruppe eine C1-C6-Alkyl-, vorzugsweise eine C1-C4-Alkyl-Gruppe darstellt.
  4. Verwendung nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass R1 eine Hydroxy-C1-C4-Alkyl-, vorzugsweise eine Hydroxymethyl-Gruppe, eine Carboxy-C1-C6-Alkyl-, vorzugsweise eine Carboxy-C1-C4-Alkyl-Gruppe oder eine Sulfo-C2-C4-Alkyl-, vorzugsweise eine Sulfoethyl-Gruppe oder ein Natriumsalz davon darstellt.
  5. Verwendung nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass -L-R1 eine Gruppe darstellt, die aus -O-CH2OH, -O-CH2CH2SO3H, -O-CH2-CO2H und -O-CO-CH2CH2CO2H und Natriumsalzen davon besteht.
  6. Verwendung nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polysaccharid-Gerüst β-1,4-verknüpft ist.
  7. Verwendung nach irgendeinem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Polysaccharid-Gerüst ein zahlenmittleres Molekulargewicht von 10000 bis 1000000 aufweist.
EP02774634.6A 2001-11-09 2002-09-20 Polymere für waschanwendungen Expired - Lifetime EP1442109B1 (de)

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Also Published As

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

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