GB2360794A

GB2360794A - Cellulose derivative rebuild agent for fabrics

Info

Publication number: GB2360794A
Application number: GB0007665A
Authority: GB
Inventors: Andrew Hopkinson
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 2000-03-29
Filing date: 2000-03-29
Publication date: 2001-10-03
Also published as: GB0007665D0

Abstract

A novel fabric rebuild agent (I) for use in laundry treatment has a polymeric backbone comprising cellulose units, and groups R covalently bonded to be pendant on the backbone wherein one or more R groups of the polymer comprise independently a group according to formula (II): wherein each R<SB>1</SB> is independently selected from H, C<SB>1</SB>-C<SB>20</SB> alkyl, C<SB>5</SB>-C<SB>7</SB> cycloalkyl, C<SB>7</SB>-C<SB>20</SB> arylalkyl, C<SB>7</SB>-C<SB>20</SB> alkylaryl, substituted alkyl, hydroxyalkyl, (R<SB>6</SB>)<SB>2</SB>N-alkyl, and (R<SB>6</SB>)<SB>3</SB>N-alkyl, where R<SB>6</SB> is independently selected from H, C<SB>1</SB>-C<SB>20</SB> alkyl, C<SB>5</SB>-C<SB>7</SB> cycloalkyl, C<SB>7</SB>-C<SB>20</SB> arylalkyl, C<SB>7</SB>-C<SB>20</SB> alkylaryl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloaminoalkyl and hydroxyalkyl, the average degree of substitution based on the total of all groups pendant on the saccharide rings of the backbone and capable of undergoing chemical change, upon use in a laundry process, being from 0.3 to 3, preferably from 0.4 to 1, more preferably from 0.5 to 0.75, most preferably from 0.6 to 0.7.

Description

Treatment for Fabrics Technical Field The present invention relates to an ingredient for laundry cleaning or treatment products, for deposition onto fabric during a washing, rinsing or other treatment process. It further extends to compositions containing such an ingredient and methods of fabrics treatment using these compositions. Background of the Invention Repeated washing of garments, particularly those comprising cotton or other cellulosic fibres, causes gradual loss of material from individual fibres and the loss of whole fibres from the fabric. These processes of attrition result in thinning of the fabric, eventually rendering it semi- transparent, more prone to accidental tearing and generally detracting from its original appearance. Hitherto, there has been no way of minimising this kind of damage except by employing less frequent washing and use of less harsh detergent products and/or wash conditions, which obviously tends to less effective cleaning. In laundry cleaning or treatment products, it is essential for some ingredients to be deposited onto and adhere to the fabric for them to deliver their beneficial effects. Typical examples are fabric conditioners or softeners. Nevertheless, the benefits conferred by such conventional materials do not include rebuilding the fabric.

It has now been found possible to include in laundry products, agents which deposit cellulose or cellulose-like materials onto the fabric to at least partially replace the lost material of the fibre. EP-A-0 084 772 discloses a graft polymer dispersion comprising a vinyl-containing organopolysiloxane, an organopolysiloxane with unsubstituted silicon atom and polymerised units of vinyl monomers. Aqueous emulsions of these materials are used as water repellents to be applied to textiles during manufacture, whilst also endowing a softening and smoothing effect. Unlike conventional silicones they are said to offer the advantage of retaining elasticity and "recovery" of the weave. There is also a disclosure of strengthening of textiles during manufacture by application of acrylates, polyacrylates and polymetacrylates. However, there is nothing in this reference to suggest use of a material during a laundry process, for rebuilding the material of the fabric. EP-A-0 025 255 discloses laundry wash or softening agents and shampoo compositions, containing a complex of an arylamine and a fatty acid or phosphate ester. The heat of the wash/rinse water softens the solid particles of this material to enhance its deposition. However, again, there is no suggestion of this agent being able to rebuild cellulose-type fibres. EP-A-0 266 324 discloses fabric conditioners which are amine-anionic surfactant ion pair complexes. Thus, these are not polymeric, nor do they aid fabric rebuild. WO-A-98/00500 discloses detergent compositions comprising a peptide or protein deposition aid having a high affinity for fibres or a surface, and having a benefit agent attached/absorbed to the deposition aid. There is no disclosure of use for these materials as fabric rebuild agents. Moreover, the peptide/protein material is significantly more costly than the polysaccharides used in the present invention. WO-A-98/29528 discloses cellulose ethers in which some substituents are (poly) alkoxylated, analogues of the latter in which the (poly) alkoxylated groups are terminated with a cationic moiety in the form of a quaternary ammonium group, and cellulose ethers in which some substituents are carboxylic acids in the salt form (i.e. the materials are essentially carboxymethylcellulose variants). None of these substituents in any variant is of a kind which would undergo a chemical change to enhance fabric affinity. WO-A-99/14245 discloses laundry detergent compositions containing cellulosic based polymers to provide appearance and integrity benefits to fabrics. These polymers are cellulosic polymers in which the saccharide rings have pendant oxygen atoms to which substituents `R' are bonded, i.e. they are attached to the rings via an ether linkage. The groups `R' can be hydrogen, lower alkyl or alkylene linkages terminated by carboxylic acid, ester or amide groups. Optionally, up to five alkyleneoxy groups may be interspersed between the groups are the respective oxygen atom. At least some of these groups may undergo a chemical change such as hydrolysis, in the wash liquor. However no such change would result in an increased affinity for the fabric. On the contrary, because the "ester" group is configured with the carbonyl group closer to the polysaccharide than the oxygen atom (i.e. esters of carboxyalkyl groups), any hydrolysis will result in free acid substituents which will actually result in an increase in solubility and therefore, a decrease in affinity for the fabric. WO-A-99/14295 discloses structures analogous to those described in WO-A-99/14245 but in one alternative, the substituents `R' together with the oxygen on the saccharide ring, constitute pendant half-esters of certain dicarboxylic acids. A single example of such a material is given. The dicarboxylic acid half-esters would tend to hydrolyse in the wash liquor and thereby increase affinity of the material for a cotton fabric. However, first, this mechanism of action or behaviour is not mentioned. Secondly, the degree of substitution for this variant is specified as being from 0.001 to 0.1. This is so low as to make the enhancement of fabric affinity too low to be worthwhile for this mechanism of action. Thirdly, the structures described and claimed insofar as they have such half ester substituents, must also have substituents of the type which are carboxyalkyl groups or esters thereof, i.e. of the type also described in WO-A- 99/14245. In the latter (ester) case, these would hydrolyse to the free acid form. The degree of substitution of the latter (0.2 to 2) is considerably higher than for the half- ester groups and the resultant increase in solubility would easily negate any enhanced affinity for the fabric by hydrolysis of the half-ester groups. International patent application no. PCT/EP99/07422, published on .................. discloses a laundry treatment composition comprising a water-soluble or water- dispersible rebuild agent for deposition onto a fabric during a treatment process, wherein the rebuild agent undergoes, during the treatment process, a chemical change by which change the affinity of the rebuild agent for the fabrics is increased, the chemical change resulting in the loss or modification of one or more groups covalently bonded to be pendant to a polymeric backbone of the rebuild agent. In one aspect, the pendant covalent group is derived from a monocarboxylic acid bonded via an ester link to the polymeric backbone. In another aspect, the average degree of substitution of groups capable of undergoing the chemical change is in the range 0.3-3.0. The present inventors have now discovered that a polymer which comprises a polymeric backbone comprising cellulose units, having covalently bonded thereto substituents based on keto-esters can also act as fabric rebuild agents which undergo a chemical change during the treatment process which increases their affinity for fabric. Definition of the Invention The present invention provides a laundry treatment composition comprising a water-soluble or water-dispersible rebuild agent for deposition onto a fabric during a treatment process; wherein the rebuild agent is selected from one or more polymeric molecules of formula (I), having a polymeric backbone comprising cellulose units and groups covalently bonded to be pendant on the backbone

wherein at least one or more R groups of the polymer comprise independently a group according to formula (II):

wherein each R1 is independently selected from the group consisting of H, C1-C20 alkyl, CS-C-7 cycloalkyl, arylalkyl, C7-C20 alkylaryl, substituted alkyl, hydroxyalkyl, (R6) 2N-alkyl, and (R6) 3N-alkyl, where R6 is independently selected from the group consisting of H, Cl-C20 alkyl, CS-C7 cycloalkyl, C7-C2o arylalkyl, C7-C20 alkylaryl, aminoalkyl, alkylaminoalkyl, dial kylaminoalkyl, pipe ridinoalkyl, morpholinoalkyl, cycloaminoalkyl and hydroxyalkyl; wherein the rebuild agent undergoes during the treatment process, a chemical change by which change the affinity of the rebuild agent for the fabric is increased, the chemical change occurring in or to the pendant groups, the average degree of substitution based on the total of all groups pendant on the saccharide rings of the backbone and capable of undergoing the chemical change, being from 0.3 to 3, preferably from 0.4 to 1, more preferably from 0.5 to 0.75, most preferably from 0.6 to 0.7. Further, the present invention provides a fabric rebuild agent according to formula (I) set out above. Further, the present invention provides a method of rebuilding a fabric to replace fibre loss due to washing, the process comprising treating the fabric with a composition according to the invention. Throughout this specification, "average degree of substitution" refers to the number of substituted pendant groups per saccharide ring, averaged over all saccharide rings of the rebuild agent. Each saccharide ring prior to substitution has three -OH groups and therefore, an average degree of substitution of 3 means that each of these groups on a11 molecules of the sample, bears a substituent. The exact mechanism by which any of these rebuild agents exert their effect is not fully understood. Whether or not they can repair thinned or damaged fibres is not known. However, they are capable of replacing lost fibre weight with deposited and/or bonded material, usually of cellulosic type. This can provide one or more advantages such as repair or rebuilding of the fabric, strengthening of the textile or giving it enhanced body or smoothness, reducing its transparency, reducing fading of colours, improving the appearance of the fabric or of individual fibres, improved comfort during garment wear, dye transfer inhibition, increased stiffness, anti-wrinkle, effect and ease of ironing. In the case of those rebuild agents having a cellulose backbone and pendant ester groups, without being bound by any particular theory or explanation, the inventors have conjectured that the mechanism of deposition is as follows. Cellulose is substantially insoluble in water. Attachment of the ester groups causes disruption of the hydrogen bonding between rings of the cellulose chain, thus increasing water solubility or dispersibility. In the treatment liquor, it is believed that the ester groups are hydrolysed, causing the affinity for the fabric to increase and the polymer to be deposited on the fabric. Detailed Description of the Invention. The Rebuild Aaent The rebuild agent material of the present invention is water-soluble or water-dispersible in nature and comprises a polymeric backbone having one or more pendant groups which undergo the chemical change to cause an increase in affinity for fabric. The weight average molecular weight (MW) of the rebuild agent (as determined by GPC) may typically be in the range of 500 to 2,000,000 for example 1,000 to 1,500,000. Preferably though, it is from 1,000 to 100,000, more preferably from 5,000 to50,000, especially from10,000 to 40,000. By water-soluble, as used herein, what is meant is that the material forms an isotropic solution on addition to water or another aqueous solution. By water-dispersible, as used herein, what is meant is that the material forms a finely divided suspension on addition to water or another aqueous solution. Preferably though, the term "water-dispersible" means that the material, in water at pH 7 and at 25 C, produces a solution or a dispersion having long-term stability. By an increase in the affinity of the material for the fabric upon a chemical change, what is meant is that at some time during the treatment process, the amount of material that has been deposited is greater when the chemical change is occurring or has occurred, compared to when the chemical change has not occurred and is not occurring, or is occurring more slowly, the comparison being made with a11 conditions being equal except for that change in the conditions which is necessary to affect the rate of chemical change. Deposition includes adsorption, cocrystallisation, entrapment and/or adhesion. The Polymeric Backbone The polymer backbone is a polysaccharide and may be straight or branched. 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 (and therefore are not in themselves counted in the degree of substitution) on a main polymeric backbone. A polysaccharide comprises a plurality of saccharide rings which have pendant hydroxyl groups. The pendant groups can be bonded chemically or by other bonding mechanism, to these hydroxyl groups by any means described hereinbelow. The "average degree of substitution" means the average number of pendant groups per saccharide ring for the totality of polysaccharide molecules in the sample and is determined for a11 saccharide rings whether they form part of a linear backbone or are themselves, pendant side groups in the polysaccharide. Other polymeric backbones suitable as according to the present invention include those described in Hydrocolloid Applications, A. Nussinswitch, Blackie 1997. Pendant Groups which undergo the Chemical Change The chemical change which causes the increased fabric affinity will usually be hydrolysis or perhydrolysis or else it is preferably bond-cleavage, optionally catalysed by an enzyme or another catalyst. However, preferably this change is not merely protonation or deprotonation, i.e. a pH induced effect. It is essential that at least one group R of the polymer comprises a group as defined above. However, there may be additional groups which can undergo the chemical change. The chemical change can occur in or to the additional groups covalently bonded to the polymeric backbone, especially the loss of one or more such groups. Suitable additional groups which can undergo the chemical change are as follows.

wherein each R2 is independently selected from Cl-20 (preferably CI-6) alkyl, CZ_2o (preferably C2_6) alkenyl (e.g. vinyl) and CS_7 aryl (e.g. phenyl) any of which is optionally substituted by one or more substituents independently selected from CI-4 alkyl, Cl-12 (preferably C1_9) alkoxy, hydroxyl, keto, vinyl and phenyl groups; each R3 is independently selected from hydrogen and groups R2 as hereinbefore defined; RQ is a bond or is selected from C1-4 alkylene, C2_4 alkenylene and C5_7 arylene (e.g. phenylene) groups, the carbon atoms in any of these being optionally substituted by one or more substituents independently selected from Cl-12 (preferably Cl_ 4) alkoxy, vinyl, hydroxyl, halo and amine groups; each RS is independently selected from hydrogen, counter cations such as alkali metal (preferably Na) or 2Ca or img, and groups R2 as hereinbefore defined; and groups R which together with the oxygen atom forming the linkage to the respective saccharide ring forms an ester or herni-ester group of a tricarboxylic- or higher polycarboxylic- or other complex acid such as citric acid, an amino acid, a synthetic amino acid analogue or a protein. For the avoidance of doubt, as already mentioned, in formula (I) some of the R groups may optionally have one or more structures, for example as hereinbefore described. For example, one or more R groups may simply be hydrogen or an alkyl group. Some preferred R groups may be independently selected from one or more of acetate, propanoate, trifluroacetate, 2-(2- hydroxy-1-oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate, cinnamate, formate, salicylate, carbamate, methylcarbamate, benzoate, gluconate, methanesulphonate and toluene sulphonate groups and hemiester groups of fumaric, malonic, itaconic, oxalic, malefic, succinic, tartaric, glutamic, aspartic and malic acids. Other Pendant Groups As well as the groups which undergo the chemical change, pendant groups of other types may optionally be present, i.e. groups which do not undergo a chemical change to enhance fabric affinity. Within that class of other groups is the subclass of groups for enhancing the solubility of the rebuild agent (e.g. groups which are, or contain one or more free carboxylic acid/salt and/or sulphonic acid/salt and/or sulphate groups). Examples of solubility enhancing substituents include carboxyl, sulphonyl, hydroxyl, (poly) ethyl eneoxy-and/or (poly)propyleneoxy-containing groups, as well as amine groups. The other pendant groups preferably constitute from0% to 650, more preferably from0% to 100 (e.g. from0% to 50) of the total number of pendant groups. The minimum number of other pendant groups may, for example be 0.10 or to of the total. The water-solubilising groups could comprise from0% to 1000 of those other groups but preferably from0% to 200, more preferably from0% to10%, still more preferably from Oo to 50 of the total number of other pendant groups. Synthetic Routes Those rebuild agents according to the present invention which are not commercially available may be prepared by a number of different synthetic routes, for example:- (1) polymerisation of suitable monomers, for example, enzymatic polymerisation of saccharides, e.g. per S. Shoda, & S. Kobayashi, Makromol. Symp. 1995, 99, 179-184 or oligosaccharide synthesis by orthogonal glycosylation e.g. per H. Paulsen, Angew. Chem. Int. Ed. Engl. 1995, 34, 1432- 1434.; (2) derivatisation of a polymeric backbone (either naturally occurring, especially polysaccharides, especially beta-1,4- linked polysaccharides, especially cellulose, mannan, glucomannan, galactomannan, xyloglucan; or synthetic polymers) up to the required degree of substitution with functional groups which improve the solubility of the polymer using a reagent (especially diketenes, acid halides, especially carboxylic acid halides, anhydrides, carboxylic acid anhydrides, carboxylic acids, carbonates or esters) in a solvent which either dissolves the backbone, swells the backbone, or does not swell the backbone but dissolves or swells the product; (3) hydrolysis of polymer derivatives (especially esters) down to the required degree of substitution; or (4) a combination of any two or more of routes (1)-(3). Routes particularly suitable for incorporating the ketomonoester substitutents according to the invention are reactions between a polymeric backbone and diketene, alkyl acetoacetate or 2,2,6-trimethyl-4H-1,3-dioxin-4-one acetoacetate in N,N-dimethylacetamide/ CICL or 1-methyl- pyrolidinone as solvent (as described in K. J. Edgar et al, Macro Molecules, 28(12) (1995), pp. 4122-4128, or WO 92/06304). Some particular routes for introducing other hydrolysable pendant groups into the polysaccharide chain are as follows. The degree and pattern of substitution from routes (1) or (2) may be subsequently altered by partial removal of functional groups by hydrolysis or solvolysis or other cleavage. Relative amounts of reactants and reaction times can also be used to control the degree of substitution. In addition, or alternatively, the degree of polymerisation of the backbone may be reduced before, during, or after the derivatisation with functional groups. The degree of polymerisation of the backbone may be increased by further polymerisation or by cross linking agents before, during, or after the derivatisation step.

Cellulose esters of hydroxyacids can be obtained using the acid anhydride, typically in acetic acid solution at 20- 30 C. When the product has dissolved the liquid is poured into water. Glycollic and lactic esters can be made in this way. Cellulose glycollate may also be obtained from cellulose chloracetate (B.P. 320,842) by treating100 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 (F. P. 702,116). The ester is heated at about 100 with the acid which, preferably, should be a solvent for the ester. By this means 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. As an example cellulose acetate (10 g) in dioxan (75 ml) containing oxalic acid (10 g) is heated at 100 for 2 hours under reflux. Multiple 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). With solid acids 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. Thus: 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 i00 for 18 hours. The product is soluble in water and is precipitated and washed with ether-acetone. M.p. 230-250 . Compositions The rebuild agent may be incorporated into compositions containing only a diluent and/or also comprising another active ingredient. The compound is typically included in said compositions at levels of from0.005% to 25% by weight, preferably 0.01% to 100, most preferably0.025% to 2.50. The component (s) of the composition should be such that when in use, e.g. when dissolved or dispersed in the wash or rinse liquor, deposition of the rebuild agent can occur. Most, if not all, conventional laundry wash and/or rinse compositions already fulfil this requirement. However, to assist such deposition, one may include at least one water- soluble additive capable of inducing or assisting the said deposition of the rebuild agent. The optional water soluble additive(s) is/are selected e.g. from those which, in the washing or rinsing solution, have an anion capable of decomposing and a cation capable of forming a soluble salt with the anion originating from the substituent or substituents. In the case of rebuild agents which are water-dispersible cellulose esters, the said deposition additives can be in particular water-soluble, alkaline, de-esterifying additives, for example the carbonates, hydrogen. carbonates, oxalates, tartrates, etc. of alkali metals, in: particular sodium. The water-soluble additive, capable of inducing, in the washing or rinsing medium, the deposition rebuild agent, is present in the said composition in an amount at least sufficient to induce chemical change in all groups provided for this prupose. In the case of a water-dispersible esterified cellulose, the alkaline de-esterifying additive is present in the said composition in an amount at least sufficient to de-esterify the said water-soluble esterified cellulose. This amount is preferably at least 5 times, preferably at least 10 times the stoichiometric amount necessary for complete de-esterification of the ester. It is generally less than100 times the necessary stoichiometric amount. The other active ingredient (if present) 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. The 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 (especially aqueous) liquid. In particular the compositions may be used in laundry compositions, especially in liquid or powder laundry composition, for example for use in a wash and/or rinse and/or drying process. When the composition is a fabric softening composition, it may be in the form of a tumble dryer article, for example a sheet of absorbent material containing the composition, which is designed to be added to a tumble dryer whilst drying clothes. The 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. Many suitable surface-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

The preferred detergent -active compounds that can be used are soaps and synthetic non-soap anionic and non-ionic compounds. The compositions of the invention may contain linear al kylbenzene sulphonate, particularly linear alkylbenzene sulphonates having an alkyl chain length of C$-C15. It is preferred if the level of linear alkylbenzene sulphonate is from 0 wto to 30 wt%, more preferably 1 wt% to 25 wt%, most preferably from 2 wt`-'; to15 wt%. The compositions of the invention may additionally or alternatively contain one or more other anionic surfactants in total amounts corresponding to percentages quoted above for alkyl benzene sulphonates. Suitable anionic surfactants are well-known to those skilled in the art. These include primary and secondary alkyl sulphates, particularly CB-C15 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates. Sodium salts are generally preferred. The compositions of the invention may contain non-ionic surfactant. Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, especially the C8-C20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide). It is preferred if the level of total non-ionic surfactant is from 0 wto to 30 wt o, preferably from 1 wto to 25 wt o, most preferably from 2 wto to 15 wto. Another class of suitable surfactants comprises certain mono- alkyl cationic surfactants useful in main-wash laundry compositions. Cationic surfactants that may be used include quaternary ammonium salts of the general formula RlR2R3R4N+ X_ wherein the R groups are long or short hydrocarbon chains, typically alkyl, hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion (for example, compounds in which R1 is a C8-C22 alkyl group, preferably a C$-Clo or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4, which may be the same or different, are methyl or hydroxyethyl groups); and cationic esters (for example, choline esters). The choice of surface-active compound (surfactant), and the amount present, will depend on the intended use of the detergent composition. In fabric washing compositions, different 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 wto, for example, in a composition for washing fabrics by hand. In compositions for machine washing of fabrics, an amount of from 5 to 40 wto is generally appropriate. Typically the compositions will comprise at least 2 wt% surfactant e.g. 2 600, preferably 15-40% most preferably 25-35%. Detergent compositions suitable for use in most automatic fabric washing machines generally contain anionic non-soap surfactant, or non-ionic surfactant, or combinations of the two in any suitable ratio, optionally together with soap. Any conventional fabric conditioning agent may be used in the compositions of the present invention. The conditioning agents may be cationic or non-ionic. If the fabric conditioning compound is to be employed in a main wash detergent composition the compound will typically be non-ionic. If used in the rinse phase, they will typically be cationic. They may for example be used in amounts from 0.5% to 35%, preferably from 1 % to30% more preferably from 3% to 25% by weight of the composition. Preferably the fabric conditioning agent has two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to C16. Most preferably at least 50% of the long chain alkyl or alkenyl groups have a chain length of C18 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 LP to La transition temperature greater than 25 C, preferably greater than 35 C, most preferably greater than 45 C. This L(3 to La 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 o in deminerailised water at 20 C. Preferably the fabric softening compounds have a solubility less than 1 x 10-4 wt o, most preferably less than 1 x10-8 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 C2o 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 C14. Preferably, 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.

As used in the context of the quarternary ammonium cationic fabric softening agents, the term `ester group', includes an ester group which is a linking group in the molecule.

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.

Also preferred are 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. 12 to 20 carbon atoms, such as coco-alkyl, tallowalkyl, hydrogenated tallowalkyl or substituted higher alkyl, and 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. Preferably the quaternary ammonium material is a compound having two C12-C22 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 C20- More preferably, 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 C19. Even more preferably each chain has an average chain length equal to or greater than C16. Most preferably at least 500 of each long chain alkyl or alkenyl group has a chain length of C18. It is preferred if the long chain alkyl or alkenyl groups are predominantly linear. The most preferred type of ester-linked quaternary ammonium material that can be used in compositions according to the invention is represented by the formula (A) :

wherein R1, n, R2 and X- are as defined above. It is advantageous for environmental reasons if 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. Preferably these materials comprise small amounts of the corresponding monoester as described in US-A-4 137 180 for example 1-hardened tallow-oyloxy-2-hydroxy-3- trimethylammonium propane chloride. Another class of preferred ester-linked quaternary ammonium materials for use in compositions according to the invention can be represented by the formula:

wherein each R1 group is independently selected from C1_9 alkyl, hydroxyal kyl or C2_9 alkenyl groups; and wherein each R2 group is independently selected fromCB-28 alkyl or alkenyl groups; X- is any suitable counter-ion, i.e. a halide, acetate or lower alkosulphate ion, such as chloride or methosulphate.

n is an integer from 1-5 or is 0 It is especially preferred that each R1 group is methyl and each n is 2. Of the compounds of formula (B), 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 R1, R2 and X 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.

The 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 o, preferably from 10 to 60 wt o .

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 crystal line /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 w Jth L this L 'n-vention. I

The 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 wto. The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na20. A1203. 0.8-6 Si02 These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 Si0z 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. However, according to a preferred embodiment of the invention, 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. Especially preferred is 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.

Especially preferred organic builders are citrates, suitably used in amounts of :from 5 to 30 wt o, preferably from 10 to 25 wt o; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt o, preferably from 1 to 10 wt%. Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.

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. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. 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

noanoyloxybenzene sulphonate (SNOBS). 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. examples of such 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 phtalimido peroxy caproic acid (PAP). Such peracids are suitably present at 0.1 - 120, preferably 0.5 - 100. A bleach stabiliser (transistor metal sequestrant) 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). The compositions according to the invention may also contain one or more enzyme(s). Suitable enzymes include the proteases, amylases, cellulases, oxidases, peroxidases and lipases usable for incorporation in detergent compositions. Preferred proteolytic enzymes (proteases) 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.

Examples of suitable proteolytic enzymes are the subtilisins 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.

Particularly suitable is a 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). The preparation of these and analogous enzymes is described in GB 1 243 785. 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 wto. However, any suitable physical form of enzyme may be used. The 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 wto, preferably from 2 to 40 wto. However, 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. One preferred powder structurant is fatty acid soap, suitably present in an amount of from 1 to 5 wt o . Other materials that may be present in detergent compositions of the invention include sodium silicate; antiredeposition agents such as cellulosic polymers; inorganic salts such as sodium sulphate; lat=her control agents or lather boosters as appropriate; proteolytic and lipolytic enzymes; dyes; coloured speckles; perfumes; foam controllers; fluorescers and decoupling polymers. This list is not intended to be exhaustive. It is often advantageous if soil release or soil suspendng polymers are present, for example in amounts in the order of 0.01% to 100, preferably in the order of0.1% to 5o and in particular in the order of 0.2% to3% by weight, such as - cellulose derivatives such as cellulose hydroxyethers, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, h ydroxybutyl methyl cell _'-,_ilose; - polyvinyl esters grafted onto polya-@kylene backbones, such as polyvinyl acetates grafted onto polyoxyethylene backbones (EP-A-219 048); - polyvinyl alcohols; - polyester copolymers based on ethylene terephthalate and/or propylene terephthalate units and polyethyleneoxy terephthalate units, with a molar ratio (number of units) of ethylene terephthalate and/or propylene terephthalate / (number of units) polyethyleneoxy terephthalate in the order of 1/10 to 10/1, the polyethyleneoxy terephthalate units having polyethyleneoxy units with a molecular weight in the order of 300 to 10,000, with a molecular weight of the copolyester in the order of 1000 to 100,000; polyester copolymers based on ethylene terephthalate and/or propylene terephthalate units and polyethyleneoxy and/or polypropyleneoxy units, with a molar ratio (number of units) of ethylene terephthalate and/or propylene terephthalate / (number of units) polyethyleneoxy and/or polypropyleneoxy in the order of 1/10 to 10/1, the polyethyleneoxy and/or polypropyleneoxy units having a molecular weight in the order of 250 to 10,000, with a molecular weight of the copolyester in the order of 1000 to 100,000 (US-A-3 959 230, US-A-3 962 152, US-A-3 893 929, US-A-4 116 896, US-A-4 702 857, US-A-4 770 666, EP-A- 253 567, EP-A-201 124) ; copolymers of ethylene or propylene terephthalate / polyethyleneoxy terephthalate comprising sulphoisophthaloyl units in their chain (US-A-4 711 730, US-A-4 702 857, US-A-4 713 194); terephthalic copolyester oligomers having polyalkyleneoxyalkyl sulphonate/sulphoaroyl terminal groups and optionally containing sulphoisophthaloyl units in their chain (US-A-4 721 580, US-A-S 415 807, US-A-4 877 896, US-A-5 182 043, US-A-5 599 782, US-A-4 764 289, EP-A- 311 342, W092/04433, W097/42293) ; sulphonated terephthalic copolyesters with a molecular weight less than 20,000, obtained e.g. from a diester of terephthalic acid, isophthalic acid, a diester of sulphoisophthalic acid and a diol, in particular ethylene glycol (W095/32997); polyurethane polyesters, obtained by reaction of a polyester with a molecular weight of 300 to 4000, obtained from a terephthalic acid diester, possibly a sulphoisophthalic acid diester and a diol, on a prepolymer with isocyanate terminal groups, obtained from a polyethyleneoxy glycol with a molecular weight of 600 to 4000 and a diisocyanate (US-A-4 201 824); - sulphonated polyester oligomers obtained by sulphonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2-propylene diol, having 1 to 4 sulphonate groups (US-A-4 968 451); The detergent composition when diluted in the wash liquor (during a typical wash cycle) will typically give a pH of the wash liquor from 7 to10.5 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 7ia the slurry. The skilled detergent formulator will have no difficulty in deciding which ingredients should be included in the slurry and which should not. Particulate detergent compositions of the invention preferably have a bulk density of at least 400 g/1, more preferably at least 500 g/1. 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. Any suitable method may be used to produce the compounds of the present invention. Treatment Process Treatment of the fabric with the rebuild agent can be made b y any suitable method such as washing, soaking or rinsing of the substrate. Typically 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 fabric with an aqueous medium comprising the composition of the present invention. The present invention will now be explained in more detail by way of the following non-limiting examples. Examples Example 1: Cellulose Monoacetate This was prepared by the methods of WO 91/16359 and is referred to in the examples as "the polymer". Example 2: Spray-Drled Powder

Component -% w/w Na PAS 11.5 Dobanol 25-7 6.3 Soap 2.0 Zeolite 24.1 SCMC 0.6 Na Citrate 10.6 Na Carbonate 23.0 Polymer of the invention 0.3 Silicone Oil 0.5 Dequest 2066 0.4 Sokalan CPS 0.9 Savinase 16L 0.7 Lipolase 0.1 Perfume 0.4 Water/salts to 100 Example 3 :Detergent Granulate Prepared by Non-Spray Drying Method The following composition was prepared by the two-stage mechanical granulation method described in EP-A- 367 339.

Component % w/w NaPAS 13.5 Dobanol 25-7 2.5 STPP 45.3 Na Carbonate 4.0 Polymer of the invention 0.28 Na Silicate 10.1 Minors 1.5 Water balance Example 4: Isotropic Laundry Liquid

Component % w/w Na-citrate (37. 5%) 10.7 Propyleneglycol 7.5 Ethylene Glycol 4.5 Borax 3.0 Savinase 16L 0.3 Lipolase 0.1 Polymer of the invention 0.25 Monoethanolamine 0.5 Cocofatty acid 1.7 NaOH (500) 2.2

LAS 10.3 Dobanol 25-7 6.3 LES 7.6 Minors 1.3 (adjust pH to 7 with NaOH) Water up to 100 Example 5: Structurf;d Laundry Liquid

Component % w/w LAS 1_6.5 Dobanol 25-7 9 Oleic acid (Priolene 6907) 4.5 Zeolite 15 KOH, neutralisation of acids and pH to 8.5 Citric acid 8.2 deflocculating polymer 1 Protease 0.38 Lipolase 0.2 Polymer of the inven-ion 0.15 Minors 0.4 Water to 100o

ri (#) l0 O O lo O O CO Vr M Ol O O O O O O O O O N m O O # O rn L- O O l- O O @ l0 di N O O O O O O O O O ri Lll O W ri O O O O O O O O O O O\ M O H M O O O O Co O O O O O N O O O O O O O O O t H -1 O N O O O O O O 0 O O Ol N O O N CO cr O O O O Ln CO O O OD O O O M O O O p O O1 r1 O 0 Lll N L- O O O O M O O m O O O 00 O O 1-4 r-1 O O N O O O M M M O O O M N 01 O O 0 O C> N O O O 00 r-1 O O di N M O O O r1 @ll O O O N O Ill 00 O O < -i 3 O M M d# O CO 10 O O O O M M O O O O N O O O . . O o t- O O O lz:vM O O p o r @o N o O O O @ o O 0) 1-1 00 C) O (D CO M M O V1 O') O O O O CD 0 O O O O N O O N (Y) In O N O O N M O O O In O O O M N O O O O O O O1 M ('r1 O 01 01 O O O O 01 O O N `1 O m O O 00 O W O Ln O O O ('M N O O O O In O\ O N O O N M O C O r-i co 00 r- CD O O r1 O 1- O L(1 di O O O O di 10 O O O r1 O1 O p O Ln O r--i O N M O O O O O O O O N t ) O O (d v v v U U .I, O l@ r" r" r' r6 (d rd @-I #4 `d 0 .@ .L? in 4.a .--. .@ 0 v r-i O O O a] rd M -ri 1.1 :# W W W #:J S-I r-i rd ul 0) t- M 0 4-) ..@ v @ v v v v v v v Q4 > r-i v 4-) 1J 1) 1J > o\0 Gi N rd (d to r-1 v rd M -ri to v r-i H < -i 0 v .r, F-i v F-: -W 0 00 N 4-> >., @., >., 0 U r0 0 4-) rd rd ..A @- v O ..R co X X 5C 5-: rrd-1 -- # @i W -i #-i 0 0 0 rd r-i # U 0 @i ..1~ 0 ro (1) >#i (d .C," .i='. ..L; @i o1 R$ -H #Q (d 04 Vr ,Q U ri r1 `...c,' v 'b 1J 1) J-) J, #A r-i S-I U r-I N @-i #--I --J 4-i 0 4-) -H v v v -r-1 (1) 0 -r-1 rd -ri #j r;C v (1) r# 0 .i: (d t11 U U G@" r-I .Q (Q U ,Q Ul 04 Q.r rd Qy 0 !d r-1 r1 r-1 v 0 Q) Q' U @I `-' 0 O 0 E E E E E E 1l E rd 01 U@ Q) .. p r--1 (d #J >1 .iz: .11. .11. #j ?r -r-1 ;# #l #:j ;# :# -r1 #5 Q) (d v .J_) -r-1 1-1 0 0 0 -r-1 04 ,Q -r1 -r1 -r1 -r1 -r1 (34 r--I -r-1 J-) C-) 0 v O rd -H rd O (o r-U-i r-U-i rUi O # 0 O O O O O H QO) O O # -r-i (0 0 O U z r1 to to 4-i rd it rd to Q, m u) u) to u) to to N CO 0 E-a E 3 #a4 E-a Raw Material Specification

Component Specification LAS Linear Alkyl Benzene Sulphonic-acid, Marlon AS3, ex Huls Na-LAS LAS-acid neutralised with NaOH Dobanol 25-7 C12-15 ethoxylated alcohol, 7E0, ex Shell LES Lauryl ether Sulphate, Dobanol 25-S3, ex Shell Zeolite Wessalith P, ex Degussa STPP Sodium -'ri PolyPhosphate, Thermphos NW, ex Hoechst Dequest 2066 Metal chelating agent, ex Monsanto Silicone oil Antifoam, DB 100, ex Dow Corning Tinopal CBS-X Fluorescer, ex Ciba-Geigy Lipolase Type ex Novo Savinase 16L Protease, ex Novo Sokalan CP5 Acrylic/Meleic Builder Polymer ex BASF Deflocculating Polymer Polymer A-11 disclosed in EP-A- 346 995 SCMC Sodium Carboxymethyl Cellulose Minors antiredeposition polymers, transition-metal scavangers/bleach stabilisers, fluorescers, antifoams, dye-transfer-inhibition polymers, enzymes, and perfume.

Claims

CLAIMS: 1. A laundry treatment composition comprising a water- soluble or water-dispersible rebuild agent for deposition onto a fabric during a treatment process; wherein the rebuild agent is selected from one or more polymeric molecules of formula (I), having a polymeric backbone comprising cellulose units, and groups R covalently bonded to be pendant on the backbone

wherein one or more R groups of the polymer comprise independently a group according to formula (II):

wherein each R1 is independently selected from the group consisting of H, C1-C2o alkyl, CS-C-7 cycloalkyl, C7-C20 arylalkyl, alkylaryl, substituted alkyl, hydroxyalkyl, (R6) 2N-alkyl, and (R6) 3N-alkyl, where R6

is independently selected from the group consisting of H, C1-C20 alkyl, CS-C7 cycloalkyl, C7-C20 arylalkyl, C7_ C20 alkylaryl, aminoalkyl, alkylaminoalkyl, dialkylaminoalkyl, piperidinoalkyl, morpholinoalkyl, cycloaminoalkyl and hydroxyalkyl;;

wherein the rebuild agent undergoes during the treatment process, a chemical change by which change the affinity of the rebuild agent for the fabric is increased, the chemical change occurring in or to the pendant groups, the average degree of substitution based on the total of all groups pendant on the saccharide rings of the backbone and capable of undergoing the chemical change, being from 0.3 to 3, preferably from 0.4 to 1, more preferably from 0.5 to 0.75, most preferably from 0.6 to 0.7.
2. A composition according to claim :L, wherein the chemical change is -ysis, for example hydrolysis or perhydrolysis, or bond-cleavage, optionally catalysed by an enzyme or another catalyst.
3. A composition according to either claim 1 or claim 2, wherein the chemical change is not protonation or deprotonation.
4. A composition according to any of claims 1 to 3, wherein at least one or more of the groups R of the polymer are independently selected from groups of formulae:-

wherein each R2 is independently selected from Cl-20 (preferably C__6.) alkyl, C2_20 (preferably C2_6) alkenyl (e.g. vinyl) and C7_7 aryl (e.g. phenyl) any of which is optionally substituted by one or more substituents independently selected from C1_4 alkyl, C1_,2 (preferably C1_4) alkoxy, hydroxyl, vinyl and phenyl groups; each R3 is independently selected from hydrogen and groups R2 as hereinbefore defined; Rq is a bond or is selected from C1_4 alkylene, C2_4 alkenylene and CS_7 arylene (e.g. phenylene) groups, the carbon atoms in any of these being optionally substituted by one or more substituents independently selected from lz (preferably C1_4) alkoxy, vinyl, hydroxyl, halo and amine groups; each RS is independently selected from hydrogen, counter cations such as alkali metal (preferably Na) or 1 -2 Ca or-Mg, and groups R2 as hereinbefore defined; and

groups R which together with the oxygen atom forming the linkage to the respective saccharide ring forms an ester or hemi-ester group of a tricarboxylic- or higher polycarboxylic- or other complex acid such as citric acid, an amino acid, a synthetic amino acid analogue or a protein.
5. A composition according to any of claims 1-4, wherein at least some of the groups which undergo the chemical change are selected from one or more independently selected methane sulphonate and toluene sulphonate groups and hemiester groups of fumaric, malonic, itaconic, oxalic, maleic, succinic, tartaric, glutamic, aspartic and malic acids.
6. A composition according to any preceding claim, wherein the groups which undergo the chemical change are independently selected from one or more of acetate, propanoate, trifluoroacetate, 2-(2-hydroxy-l oxopropoxy) propanoate, lactate, glycolate, pyruvate, crotonate, isovalerate, cinnamate, formate, salicylate, carbamate, methylcarbamate, benzoate and gluconate groups.
7. A composition according to any preceding claim, wherein up to 650, preferably up to10% of the total number of pendant are groups other than those which undergo the chemical change.
8. A composition according to claim 7, wherein up to 200, preferably up to 100, more preferably up to 5% of the total number of the other groups are water-solubilising groups.
9. A composition according to any preceding claim, which further comprises a surfactant.
10. A composition according to any preceding claim, comprising from 0.005% to 250, preferably from 0.01% to 10%,. more preferably from0.025% to 2.5% by weight of the rebuild agent.
i1. A novel rebuild agent of formula(I) as defined in

claim 1.
12. A method of rebuilding a fabric to replace fibre loss due to washing, the process comprising treating the fabric with a composition according to any of claims 1 10.