GB2378960A

GB2378960A - Fabric care composition

Info

Publication number: GB2378960A
Application number: GB0120429A
Authority: GB
Inventors: Anthony Nicholas Jarvis; Adelle Louise Killey
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 2001-08-22
Filing date: 2001-08-22
Publication date: 2003-02-26
Also published as: GB0120429D0

Abstract

A fabric care composition comprises a fluorocarbon stain-blocking agent and a cationic cross-linking polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, wherein the cationic cross-linking polymeric material comprises one or more poly(oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups. Use of the composition improves the surface colour definition and stain repellency of a fabric after multiple washings and imparts pill and/or fuzz resistance.

Description

FABRIC CARE COMPOSITION Technical Field This invention relates to fabric care compositions and to methods of treating fabric using the compositions or the cationic cross-linking polymeric materials and fluorocarbon stain-blocking agents they contain. More particularly, it relates to fabric care compositions which reduce the appearance of wear or ageing of fabrics without affecting stain removal.

Background and Prior Art The laundry process generally has several benefits for fabric, the most common being to remove dirt and stains from the fabric during the wash cycle and to soften the fabric during the rinse cycle. However, there are numerous disadvantages associated with repeated use of conventional laundry treatment compositions and/or the actual laundry process ; one of these being a harsh treatment of fabric in the laundry process.

Fabrics can be damaged in several ways because of repeated laundering and/or wear. Fabric pilling and loss of fabric surface appearance e. g. fuzzing, fibrillation, pilling, shrinkage (or stretching or bagging), loss of colour from the fabric or running of colour on the fabric (usually termed dye transfer) are some of the common problems associated with repeated laundering. These problems may occur merely from repeated hand washing as well as from

machine washing process. Furthermore, problems relating to damage of fabric over time through normal use, such as loss of shape and increased likelihood of wrinkling are also significant.

Laundry detergent compositions containing cationic polyamide-polyamine fabric treatment agents are described in WO 98/29530. The compositions are claimed to impart improved overall appearance to fabrics laundered using the detergent compositions, in terms of surface appearance properties such as pill/fuzz reduction and anti-fading.

Laundry compositions containing cationic polyamide-polyamine treatment agents of similar types are taught in WO 97/42287.

Laundry compositions containing cationic polyamide-polyamine fabric treatment agents can exhibit increased dye pick-up (ie, increased dye transfer) and poor stain removal properties compared to other conventional laundry compositions.

US 5571286 (Connell et al) discloses certain polymers and prepolymers derived from polyoxyalkyleneamines and their use in a process for shrink-proofing wool. The treated wool may also have a softer handle than untreated wool. This document does not mention the treatment of cellulosic fabrics or the problems of loss of fabric surface appearance that they can experience following laundering. Furthermore, it deals entirely with treatment of wool on an industrial scale and does not mention the application of the compositions to fabric in the context of laundering processes.

WO 01/27232 discloses a fabric care composition comprising a cationic cross-linking polymeric material capable of self cross-linking and/or of reacting with cellulose, together with one or more textile compatible carriers. The cationic cross-linking polymeric material comprises one or more poly (oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups. The compositions may be used to treat fabric as part of a laundering process and to improve the surface colour definition and hence the appearance of wear.

There exists a problem with the use of cationic crosslinking polymeric compounds as described above in treating fabrics to reduce the appearance of wear. The cationic nature of the cross-linking polymeric compounds results in an increased tendency for hydrophobic or anionic substances, such as soils and stains, to adhere to fabrics which have been treated with the cationic cross-linking polymeric compounds. This is most noticeable on pale coloured or white fabrics.

The effects of the cationic cross-linking polymeric materials in preventing the appearance of wear are most noticeable on dark shaded dyed or printed fabrics rather than white or pastel fabrics. One way to avoid the problem is for the user to only employ the cationic cross-linking polymeric materials on deeply coloured fabrics by separating out their wash loads and using different laundry compositions for the paler fabrics. However, it is inconvenient for the users of laundry compositions to separate their wash loads. It is also inconvenient for the

user to have to store and use different sets of laundry compositions for different loads. It is also the case that many fabrics are striped or patterned with white or pale and brightly coloured regions in the same garment.

The use of fluorocarbon polymers as soil release agents in fabric laundry treatment compositions is disclosed in US 6075003 The present invention is based on the finding that by combining certain cationic cross-linking polymeric materials, including those described in US 5571286, with certain fluorocarbon stain-blocking agents in a fabric conditioning composition, said composition can impart improved surface appearance to dark or brightly coloured dyed or printed cellulosic fabrics (or blends thereof) while considerably reducing the tendency of soil and stains to adhere to light coloured fabrics. Surprisingly, the presence of the fluorocarbon stain-blocking agent does not prevent the functioning of the cationic cross-linking polymeric materials, even though no precautions are taken as to the order of deposition of the cationic cross-linking polymeric materials and the fluorocarbon stain-blocking agents onto the fabrics.

Definition of the Invention According to the present invention, there is provided a fabric care composition comprising a fluorocarbon stainblocking agent and a cationic cross-linking polymeric material which is capable of self cross-linking and/or of

reacting with cellulose together with one or more textile compatible carriers, in which when the textile compatible carrier is water a further additive suitable for use in laundry compositions is present, wherein the cationic crosslinking polymeric material comprises one or more poly (oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.

The fluorocarbon stain-blocking agent and the cationic cross-linking polymeric material are present at amounts in the composition such that the composition is effective in improving the surface colour definition and soiling resistance of a fabric after multiple washings.

The invention also provides a method of treating fabric, as part of a laundering process, which comprises applying to the fabric a fabric care composition of the invention or applying the combination of fluorocarbon stain-blocking agent and cationic cross-linking polymeric material which is a component of the fabric care composition of the invention.

Further provided by the invention in another aspect is the use of a fabric care composition of the invention or the combination of fluorocarbon stain-blocking agent and cationic cross-linking polymeric material which is a component of the fabric care composition of the invention, to improve the surface colour definition and soiling resistance of a fabric after multiple washings.

In another aspect, the invention provides the use of a fabric care composition of the invention or the combination of a fluorocarbon stain-blocking agent and a cationic crosslinking polymeric material which is a component of the fabric care composition of the invention to impart pill and/or fuzz resistance combined with soiling resistance to fabric during laundering. In addition, the invention can impart other beneficial properties to the fabric, such as reduced creasing and/or wrinkling combined with improved soiling resistance of the fabric during laundering.

Detailed Description of the Invention The compositions of the present invention comprise a fluorocarbon stain-blocking agent and a cationic crosslinking polymeric material which is capable of self crosslinking and/or of reacting with cellulose together with one or more textile compatible carriers, wherein the cationic cross-linking polymeric material comprises one or more poly (oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups.

The compositions of the invention have the surprising advantage of providing the combination of imparting wear resistance to fabrics, and thereby causing improved surface colour definition of the fabric after laundering, particularly after multiple washings, while simultaneously improving the soiling resistance of the fabric. It is surprising that the cationic cross-linking polymeric material can still function in the presence of the

fluorocarbon stain-blocking agent in spite of no requirements to ensure that the cationic cross-linking polymeric material is deposited onto the fabric first.

Furthermore, the combination of fluorocarbon stain-blocking agent and cationic cross-linking polymeric materials contained in the compositions need not cause unacceptable dye transfer and/or stain removal problems.

Fluorocarbon Stain-blocking Agent A suitable fluorocarbon stain-blocking agents is a polymer or copolymer from monomer units according to formula (I); Formula (I) CH2=C (R) CO. O (CH2) nRf; wherein R is H or CH3, n is 1 or 2, and Rf is a fluorinated or perfluorinated alkyl residue, preferably C2-C18, more

preferably C6-C12. Particularly preferred are polymers or copolymers from monomers which are lH, lH-perfluoroalkanol esters or 1H, lH, 2H, 2H-perfluoroalkanol esters.

It is further preferred if the fluorocarbon polymer is present as a cationic emulsion. An example of a suitable commercially available material is Zonyl 6991 (trademark) (available from Du Pont). This is supplied as a cationic emulsion comprising an acrylate polymer, having as a monomer unit the above formula, in which R = H, and n = 2.

It is advantageous in some instances if the cationic emulsion of fluoropolymer further comprises a short chain carboxylic acid.

It is also preferable if the cationic emulsion of fluoropolymer further comprises a paraffin wax.

As described above it is preferable that if after treatment of laundry with the fabric conditioner of the invention the laundry is heat-treated to cure the fluorocarbon polymer.

This can be done either by tumble drying the laundry or by ironing. If ironing is used it is preferred if the iron is hot (greater than 150 C).

The fluorocarbon stain-blocking agent is preferably present in sufficient quantity to give an amount of 0.02% to 1% by weight on the fabric, more preferably 0.05% to 0.07% by weight on fabric, based on the weight of the fabric. The amount of the fluorocarbon stain-blocking agent in the composition required to achieve the above percentages of fluorocarbon stain-blocking agent by weight on fabric will typically be in the range 0.1% to 4% by weight, preferably 0.1% to 1.5% by weight based on the weight of composition.

When the textile compatible carrier of the composition is a cationic fabric softening compound, the fluorocarbon stainblocking agent is preferably present in the product in a weight ratio of 1 part fluorocarbon stain blocking agent to 3 parts cationic fabric softening compound.

Cationic cross-linking polymeric material The cationic cross-linking polymeric material which can be used in the present invention can be any of the polymers or prepolymers derived from polyoxyalkyleneamines that are described in US 5571286, the contents of which are incorporated herein by reference. Methods for preparing the cationic cross-linking polymeric materials are described in US 5571286. Hence the cationic cross-linking polymeric material can be, for example, the reaction product of a diamine or triamine polyoxyalkylene polymer having a polymerisation degree of from 4 to 50 or a mixture thereof with epichlorohydrin in a ratio of epichlorohydrin to amino nitrogen of from 1: 1 to 3: 1.

The amino groups in the cationic cross-linking polymeric material of the invention may be wholly or partly in the form of derivatives of amino groups. Derivatives include, for example, adducts formed by alkylation or hydroxyalkylation at the nitrogen atom or by the formation of an amide group at the nitrogen atom. The derivatives may be formed by the reaction of the amino groups with a bifunctional bridging agent or with a cross-linking agent.

Preferably, the cationic cross-linking polymeric material is obtainable by the reaction of a polymer of formula B (R) n, wherein n is from 1 to 20, B is a backbone group to which each R is covalently bonded and R is a group comprising a poly (oxyalkylene) chain, which chain comprises an amino end group, the polymer being optionally reacted with a bridging compound, with a cross-linking agent. It will thus be

appreciated that the cationic cross-linking polymeric material of the invention is a relatively complex mixture comprising a number of different compounds, some or all of which may be cross-linked.

The poly (oxyalkylene) chain which forms a part of the R group may be, for example, a poly (oxyethylene), poly (oxybutylene) or poly (oxyprop-l, 2-ylene) chain. The length of the chain can vary from 2 to 100 repeat units.

Conveniently, n is 2 or 3. It will be appreciated that n may not be a whole number where the cross-linking polymeric material of the invention comprises a mixture of different polymers of formula B (R) n.

In some of the cationic cross-linking polymeric materials

which may be used in the invention, B is

- 0-CH2 (CH) m-CH2-0-0- (ie, B is the residue of glycerol when I M is 1) and m is equal to n-2.

0 I

However, B can also represent other values such as, for example, the residue of other triols or the residue of a di-, tetra-, penta-or hexa-hydroxy compound. Alternatively, B can represent the residue of a di-, tri-or poly-amine.

Preferably, at least one R group has the formula- (CH2CH (R') (CH2) aO) p-A-NHR'', wherein: R'is H or CH3; a is 0, 1 or 2; p is an integer from 5 to 30; A is an alkylene

group; and Reis H or alkyl. More preferably, p is from 10 to 25.

The term"alkyl", as used herein, includes Cl to C6 alkyl, optionally substituted on the alkyl chain, which may be branched or unbranched and, for C3 to C6 alkyl, may be cyclic. The term"alkylene"is defined similarly but refers to a divalent radical.

It will be appreciated that the term"end group"refers to the group at or near to the end of the poly (oxyalkylene) chain, which end, when the polymer is of formula B (R) n, is at the other end of the polymer chain from the end which is attached to B.

Suitable polymers of formula B (R) n include those having the following structure:

wherein R'is as defined herein before, p, q and r are integers which may be the same or different and may be from 5 to 30 and A is branched or unbranched lower alkylene.

Other suitable polymers of formula B (R) n, in which n is equal to 2, include those having the following formula: H2N- (CH2) b- (0 (CH2) 4) d-O (CH2) cO- ( (CH2) 40) d2- (CH2) b-NH2 wherein: b is an integer from 1 to 6, preferably 3; c is an integer from 1 to 6, preferably 4; and d and d2 are the same or different and are integers from 10 to 15.

The cross-linking agent which is used to form the crosslinking polymeric material of the invention by reaction with the polymer, or the polymer after prior reaction with the bridging compound, preferably comprises an epihalohydrin.

Epichlorohydrin is a suitable epihalohydrin.

Preferably the molar ratio of cross-linking agent to polymer of formula B (R) n is from 0.5 : 1 to 4: 1. Other amounts of cross-linking agent may be present in the cationic crosslinking polymeric material of the invention.

Suitable bridging compounds comprise two epoxide or carboxylic acid groups. The epoxide or carboxylic acid groups may be linked by a linker comprising alkylene, arylene, poly (oxyalkylene) or siloxane groups or combinations thereof. Examples of bridging compounds therefore include benzene-1, 4-dicarboxylic acid, hexane-1, 6dicarboxylic acid and poly (oxyethylene) compounds terminated at both ends of the molecule by an epoxide group. Other suitable bridging compounds are disclosed in US 5571286.

The composition of the invention can contain the cationic cross-linking polymeric material, optionally together with

other cross-linking polymeric materials. The compositions may further comprise a silicone which is capable of reacting with the cationic cross-linking polymeric material.

Suitable reactive silicones include those having amino or hydroxyl groups which are well-known to those skilled in the art.

Cationic cross-linking polymeric materials which are suitable for use in the present invention are available from Precision Processes Textiles (Ambergate, Derbyshire, UK) under the trade marks POLYMER AM and POLYMER MRSM. The cationic cross-linking polymeric materials of the invention are preferably in the form of aqueous solutions.

Polymer AM is a polymer having the following structure: POLYMER AM

Polymer MRSM has the same structures as polymer AM but has silicone added to the polymer mixture.

The cationic cross-linking polymeric material is preferably present in the product in a sufficient quantity to give an amount of 0.0005% to 5% by weight on the fabric based on the weight of the fabric, more preferably 0.001% to 2% by weight on fabric. The amount of the cationic cross-linking polymeric material in the composition required to achieve the above percentages by weight on fabric will typically be in the range 0.01% to 35% by weight, preferably 0.05 to 10% by weight, most preferably 1% to 5% by weight based on the total weight of the composition.

The compositions of the invention, when applied to a fabric, can impart benefits to the fabric when uncured. However, they may be cured by a domestic curing step including ironing and/or domestic tumble drying, preferably tumble drying. The curing is preferably carried out at a temperature in the range of from 50 to 100 C, more preferably from 80 to 100 C.

Textile Compatible Carrier The compositions of the invention may comprise a textile compatible carrier. In the context of the present invention, the term"textile compatible carrier"is a component, which can assist in the interaction of the first component with the fabric. The carrier can also provide benefits in addition to those provided by the first component e. g. softening, cleaning etc.

The nature of the textile compatible carrier will be dictated to a large extent by the stage at which the

composition of the invention is used in a laundering process, the compositions being capable of being used, in principle, at any stage of the process. For example, where the compositions are for use as main wash detergent compositions, the one or more textile compatible carriers comprise a detergent active compound. Where the compositions are for use in the rinsing step of a laundering process, the one or more textile compatible carriers may comprise a fabric softening and/or conditioning compound or, where the compositions are for use as rinse adjuncts, the textile compatible carrier may be water. However when the textile compatible carrier is solely water perfume must be present.

Laundering Process In the method of the invention, the composition of the invention may be used at any stage of the laundering process.

The laundering methods (or processes) of the present invention include the large scale and small scale (eg domestic) cleaning of fabrics. Preferably, the processes are domestic.

The fabrics which may be treated in the present invention include those which comprise cellulosic fibres, preferably from 1% to 100% by weight of cellulosic fibres (more preferably 5% to 100% cellulosic fibres, most preferably 40% to 100%). The fabric may be in the form of a garment, in which case the method of the invention may represent a method

of laundering a garment. When the fabric contains less than 100% cellulosic fibres, the balance comprises other fibres or blends of fibres suitable for use in garments such as polyester, for example. Preferably, the cellulosic fibres are of cotton or regenerated cellulose such as viscose.

The laundering processes of the present invention include the large scale and small scale (eg domestic) cleaning of fabrics. Preferably, the processes are domestic.

In the invention, the combination of fluorocarbon stainblocking agent and cationic cross-linking polymeric material or the composition of the invention may be used at any stage of the laundering process. Preferably, the composition or the combination of fluorocarbon stain-blocking agent and cationic cross-linking polymeric material is used to treat the fabric in the rinse cycle of a laundering process. The rinse cycle preferably follows the treatment of the fabric with a detergent composition.

Detergent Compositions Surfactants Surfactants may be chosen from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds, and mixtures thereof.

Many suitable detergent active compounds are available and are fully described in the literature, for example, in

"Surfactant Science and Technology, 2nd edition By Dave Myers, John Wiley and Sons Inc 1992.

The preferred textile-compatible carriers that can be used are soaps and synthetic non-soap anionic and nonionic compounds.

Anionic surfactants are well known to those skilled in the art and include higher fatty acid carboxylate salts or soap.

Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow. Non-soap anionic surfactants include those containing sulphonates or sulphate ester groups. and include: alkylbenzene sulphonates, particularly linear alkylbenzene sulphonates having an alkyl chain length of C8C22; primary and secondary alkylsulphates, particularly C8C22 primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccinates; alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, alkyl toluene sulphonates, paraffin sulfonates and fatty acid ester sulphonates, branched primary alkyl sulfates. Other anionic surfactants include: mono or alkyl phosphates, phosphate esters, isethionates such as the acyl isethionates, N-acyl taurates and alkyl polyethoxy carboxylates. Sodium salts are generally preferred. Further suitable anionic surfactants are described in"Surfactants Science Series volume 7 (parts 1 and 2) ed. Linfield 1976, volume 10 ed.

Gloxhuber 1980, volume 43 eds. Gloxhuber and Kunstler 1992 and volume 56 ed. Stache 1995, Marcel Dekker Inc, New York."

Nonionic surfactants that may be used include alcohol ethoxylates, especially the C8-C22 alcohols ethoxylated with 3 to 80 moles of ethylene oxide per mole of alcohol, preferably an average of 5 to 20 moles, 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. Analogous polypropylene and polybutylene oxide condensates may also be used. Nonalkoxylated nonionic surfactants include alkylpolyglycosides and the equivalent glucoside, glycerol monoethers, and polyhydroxy fatty acid amides (glucamides) and alkylpolysaccharides. Further suitable nonionic surfactants are described in "Surfactants Science Series volume 1 ed.

Schick 1987, volume 19 ed. Cross 1987, volume 23 ed. Schick 1987 and volume 72 ed. Van Os 1997, Marcel Dekker Inc, New York".

Cationic surfactants that may be used include cationic esters (choline esters), pyridinium salts, and quaternary

ammonium salts of the general formula RRRRN X* wherein the R groups are independently of one another hydrocarbyl chains of Cl-C22 length (typically alkyl, hydroxyalkyl or ethoxylated alkyl groups). For example, R1 is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R2 is a methyl group, and R3 and R4 are methyl or hydroxyethyl groups. X-is a solubilising anion, preferably chloride.

Further suitable cationic surfactants are described in "Surfactants Science Series volume 34 ed. Richmond 1990, volume 37 ed. Rubingh 1991 and volume 53 eds. Cross and Singer 1994, Marcel Dekker Inc. New York."

Amphoteric/zwitterionic surfactants may also be used, for example amine oxides, betaines or sulphobetaines. Further non-limiting examples of amphoteric and zwitterionic surfactants that can be used are described in"Surfactant Science Series Volume 12", by Bluestein and Hilton. Dekker Inc. New York 1982.

Further surfactants that could be used in the present invention are described in"Surfactant Science Series" volume 74, ed. Holmberg, Marcel Dekker Inc, New York 1999.

The total amount of surfactant present will also depend on the intended end use and may be as low as 0. 5 wt%, for example, in a machine dishwashing composition, or 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.

Builder 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%, preferably from 10 to 60 wt%. The quantity of builder is in the range of from 15 to 50% by weight for granular compositions and 1 to 10% by weight for liquid compositions.

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.

Preferred builders are crystalline aluminosilicate, preferably an alkali metal aluminosilicate, more preferably a sodium aluminosilicate.

The aluminosilicate may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50%. Aluminosilicates are materials having the general formula:

where M is a monovalent cation, preferably sodium. 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 to 3.5 Si02 units in the formula above. They 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 GB1429143 (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-, diand trisuccinates, carboxymethyloxysuccinates, 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%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.

Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.

Bleaches Bleaching systems may be present in the fabric treatment compositions. Preferred bleaching systems are based on peroxygen bleaches such as alkali metal peroxides, organic peroxide bleaching compounds, especially preferred are perborate or percarbonate based systems.

The sodium percarbonate may have a protective coating against destabilisation by moisture. Sodium percarbonate having a protective coating comprising sodium metaborate and sodium silicate is disclosed in GB 2 123 044 (Kao).

The peroxy bleach compound, for example sodium percarbonate, is suitably present in an amount of from 5 to 35 wt %, preferably from 10 to 25 wt %.

The peroxy bleach compound, for example sodium percarbonate, 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 1 to 8 wt %, preferably from 2 to 5 wt %.

Preferred bleach precursors are peroxycarboxylic acid precursors, more especially peracetic acid precursors, pernoanoic acid precursors and peroxybenzoic acid precursors.

Especially preferred bleach precursors 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 imidoperoxycarboxylic class of peracids described in EP 325 288A, EP 349 940A, DE 3 823 172A and EP 325 289A. A particularly preferred example is phthalimido peroxy caproic acid (PAP). Such peracids are suitably present at levels of from 0.1 to 12%, preferably from 0.5 to 10%.

A bleach stabiliser (heavy metal sequestrant) may also be present. Suitable bleach stabilisers include ethylenediamine tetraacetate (EDTA), the aminopolyphosphonates such as Dequest (Trade Mark), for example, ethylenediamine tetramethylen phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate (DETPMP), and non-phosphate stabilisers such as EDDS (ethylene diamine disuccinate).

Also suitable are iron based bleaching catalysts described in EP0918840, EP0923635, US5853428, US5876625, US6099586, W09803625 and W09803626.

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).

Soil Release Polymers The compositions may also contain soil release polymers, for example sulphonated and unsulphonated PET/POET polymers, both end-capped and non-end-capped, and polyethylene glycol/polyvinyl alcohol graft copolymers such as Sokolan (Trade Mark) HP22.

Enzymes A highly preferred optional ingredient are enzymes, known as 'detersive enzymes'. These can be of any suitable origin such as vegetable, animal, bacterial, fungal and yeast origin.'Detersive enzyme'as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases.

The enzyme-containing compositions herein may also optionally comprise an enzyme stabilising system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e. g. , by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

Fabric Softening and/or Conditioner Compositions If the composition of the present invention is in the form of a fabric conditioner composition, the textile-compatible carrier will be a fabric softening and/or conditioning compound (hereinafter referred to as"fabric softening compound"), which may be a cationic or nonionic compound.

The softening and/or conditioning compounds may be water insoluble quaternary ammonium compounds. The compounds may be present in amounts of up to 8% by weight (based on the total amount of the composition) in which case the compositions are considered dilute, or at levels from 8% to about 50% by weight, in which case the compositions are considered concentrates.

Compositions suitable for delivery during the rinse cycle may also be delivered to the fabric in the tumble dryer if

used in a suitable form. Thus, another product form is a composition (for example, a paste) suitable for coating onto, and delivery from, a substrate e. g. a flexible sheet or sponge or a suitable dispenser during a tumble dryer cycle.

Suitable cationic fabric softening compounds are substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl long chain having an average chain length greater than or equal to C20 or, more preferably, compounds comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to C14. Preferably the fabric softening compounds have 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 CIS or above. It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear.

Quaternary ammonium compounds having two long-chain aliphatic groups, for example, distearyldimethyl ammonium chloride and di (hardened tallow alkyl) dimethyl ammonium chloride, are widely used in commercially available rinse conditioner compositions. Other examples of these cationic compounds are to be found in"Surfactants Science Series" volume 34 ed. Richmond 1990, volume 37 ed. Rubingh 1991 and volume 53 eds. Cross and Singer 1994, Marcel Dekker Inc. New York.

Any of the conventional types of such compounds may be used in the compositions of the present invention.

The fabric softening compounds are preferably compounds that provide excellent softening, and are characterised by a chain melting L to La transition temperature greater than 252C, preferably greater than 352C, most preferably greater than 45QC. This L to La transition can be measured by (DSC) Differential Scanning Calorimetery as defined in "Handbook of Lipid Bilayers", D Marsh, CRC Press, Boca Raton, Florida, 1990 (pages 137 and 337).

Substantially water-insoluble fabric softening compounds are defined as fabric softening compounds having a solubility of less than 1 x 10-3 wt % in demineralised water at 20oC.

Preferably the fabric softening compounds have a solubility

- 4 -8 of less than 1 x 10 wt%, more preferably less than 1 x 10 to 1 x 10 wt%.

Especially preferred are cationic fabric softening compounds that are water-insoluble quaternary ammonium materials having two C12-22 alkyl or alkenyl groups connected to the molecule via at least one ester link, preferably two ester links. An especially preferred ester-linked quaternary ammonium material can be represented by the formula II:

wherein each R1 group is independently selected from Cl-4 alkyl or hydroxyalkyl groups or C2-4 alkenyl groups; each R2 group is independently selected from C8-28 alkyl or alkenyl groups; and wherein R3 is a linear or branched alkyl group of 1 to 5 carbon atoms or alkenyl group of 2 to 5 carbon atoms, T is

and p is 0 or is an integer from 1 to 5.

Di (tallowoxyloxyethyl) dimethyl ammonium chloride and/or its hardened tallow analogue is especially preferred of the compounds of formula (II).

A second preferred type of quaternary ammonium material can be represented by the formula (III):

wherein Rl, p and R2 are as defined above.

A third preferred type of quaternary ammonium material are those derived from triethanolamine (hereinafter referred to

as'TEA quats') as described in for example US 3915867 and represented by formula (IV).

(TOCH2CH2) 3N+ (R2) (IV) wherein T is H or (R1-CO-) where R1 group is independently selected from C8-28 alkyl or alkenyl groups and R2 is Cl-4 alkyl or hydroxyalkyl groups or C2-4 alkenyl groups. For example N-methyl-N, N, N-triethanolamine ditallowester or di- hardened-tallowester quaternary ammonium chloride or methosulphate. Examples of commercially available TEA quats include Rewoquat WE18 and Rewoquat WE20, both partially unsaturated (ex. WITCO), Tetranyl AOT-1, fully saturated (ex. KAO) and Stepantex VP 85, fully saturated (ex. Stepan).

It is advantageous if the quaternary ammonium material is biologically biodegradable.

Preferred materials of this class such as 1, 2-bis (hardened tallowoyloxy)-3-trimethylammonium propane chloride and their methods of preparation are, for example, described in US 4 137 180 (Lever Brothers Co). Preferably these materials comprise small amounts of the corresponding monoester as described in US 4 137 180, for example, 1hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.

Other useful cationic softening agents are alkyl pyridinium salts and substituted imidazoline species. Also useful are primary, secondary and tertiary amines and the condensation products of fatty acids with alkylpolyamines.

The compositions may alternatively or additionally contain water-soluble cationic fabric softeners, as described in GB 2 039 556B (Unilever).

The compositions may comprise a cationic fabric softening compound and an oil, for example as disclosed in EP-A-0829531.

The compositions may alternatively or additionally contain nonionic fabric softening agents such as lanolin and derivatives thereof.

Lecithins and other phospholipids are also suitable softening compounds.

Nonionic softeners include L phase forming sugar esters (as described in M Hato et al Langmuir 12,1659, 1666, (1996)) and related materials such as glycerol monostearate or sorbitan esters. ). Particularly preferred are softening agents such as liquid or soft solid derivatives of a cyclic polyol (CPE) or of a reduced saccharide (RSE) resulting from 35 to 100% of the hydroxyl groups in the cyclic polyol or reduced saccharide being esterified or etherified, the derivative (CPE or RSE) having at least 2 or more of ester or ether groups independently attached to a C8-C22 alkyl or alkenyl chain or mixtures thereof, and containing at least 35% tri or higher esters. Often these materials are used in conjunction with cationic materials to assist deposition (see, for example, GB 2 202 and WO 01/07546.

Silicones are used in a similar way as a co-softener with a cationic softener in rinse treatments (see, for example, GB

1 549 180). Further examples of nonionic softening agents are taught in WO 98/16538.

In fabric softening compositions nonionic stabilising agent may be present. Suitable nonionic stabilising agents may be present such as linear C8 to C22 alcohols alkoxylated with 10 to 20 moles of alkylene oxide, Clo to C20 alcohols, or mixtures thereof. Other stabilising agents include the deflocculating polymers as described in EP 0415698A2 and EP 0458599 Bl.

Advantageously the nonionic stabilising agent is a linear C8 to C22 alcohol alkoxylated with 10 to 20 moles of alkylene oxide. Preferably, the level of nonionic stabiliser is within the range from 0.1 to 10% by weight, more preferably from 0.5 to 5% by weight, most preferably from 1 to 4% by weight. The mole ratio of the quaternary ammonium compound and/or other cationic softening agent to the nonionic stabilising agent is suitably within the range from 40: 1 to about 1: 1, preferably within the range from 18: 1 to about 3: 1.

The composition can also contain fatty acids, for example C8 to C24 alkyl or alkenyl monocarboxylic acids or polymers thereof. Preferably saturated fatty acids are used, in particular, hardened tallow C16 to C18 fatty acids.

Preferably the fatty acid is non-saponified, more preferably the fatty acid is free, for example oleic acid, lauric acid or tallow fatty acid. The level of fatty acid material is preferably more than 0.1% by weight, more preferably more

than 0.2% by weight. Concentrated compositions may comprise from 0.5 to 20% by weight of fatty acid, more preferably 1% to 10% by weight. The weight ratio of quaternary ammonium material or other cationic softening agent to fatty acid material is preferably from 10: 1 to 1: 10.

The fabric conditioning compositions may include silicones, such as predominately linear polydialkylsiloxanes, e. g. polydimethylsiloxanes or aminosilicones containing aminefunctionalised side chains; soil release polymers such as block copolymers of polyethylene oxide and terephthalate; amphoteric surfactants; smectite type inorganic clays; zwitterionic quaternary ammonium compounds; and nonionic surfactants.

The fabric conditioning compositions may also include an agent, which produces a pearlescent appearance, e. g. an organic pearlising compound such as ethylene glycol distearate, or inorganic pearlising pigments such as microfine mica or titanium dioxide (Ti02) coated mica.

The fabric conditioning compositions may be in the form of emulsions or emulsion precursors thereof.

Other optional ingredients include emulsifiers, electrolytes (for example, sodium chloride or calcium chloride) preferably in the range from 0.01 to 5% by weight, pH buffering agents, and perfumes (preferably from 0.1 to 5% by weight).

Further Optional Ingredients Further optional ingredients that can be included in the present invention, regardless of its form, include nonaqueous solvents, perfume carriers, fluorescers, colorants, hydrotropes, antifoaming agents, antiredeposition agents, further enzymes, optical brightening agents, opacifiers, dye transfer inhibiting agents, anti-shrinking agents, antiwrinkle agents, anti-pilling agents, anti-fuzzing agents, anti-bobbling agents, fabric wear prevention agents, fabric abrasion prevention agents, malodour prevention agents, fabric friction imparting agents, anti-spotting agents, germicides, fungicides, anti-oxidants, UV absorbers (sunscreens), heavy metal sequestrants, chlorine and other bleach scavengers, dye fixatives, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids.

This list is not meant to be exhaustive.

The compositions of the invention preferably comprise a perfume, such as of the type which is conventionally used in fabric care compositions. The compositions may be packaged and labelled for use in a domestic laundering process.

Product Form The composition of the invention may be in the form of a liquid (either a free liquid or a liquid encapsulated in a water-soluble film), solid (e. g. granules, powder, hollow or solid tablets or spheres), a gel or paste, foam, structured foam, mousse or aerosol. The invention can be used as a soaking product, a rinse treatment (e. g. conditioner or

finisher) or a mainwash product (detergent or adjunct). The composition may also be applied to a substrate e. g. a flexible sheet or sponge or used in a dispenser which can then be used in the wash cycle, rinse cycle or during the dryer cycle. The composition can also be directly applied to garments or fabrics using either a spray, stick, rollerball applicator or a wipe.

The invention will now be described by way of example only and with reference to the following non-limiting examples.

EXAMPLES POLYMER AM (Trade Mark) is a cationic cross-linking polymeric material according to the invention and was obtained from Precision Processes Textiles of Ambergate, Derbyshire, UK as a 10 wt% aqueous solution of the polymer.

Zonyl 8868 (Trade Mark) is a fluorinated polymer ex Du Pont (Trade Mark) supplied as 25% by weight of polymer in a cationic emulsion.

HEQ is Hamburg Ester Quaternary, a cationic surfactant used in fabric conditioner formulations is 1, 2-bis (hardened tallowoyloxy)-3-trimethylammonium propane chloride comprising small amounts of the corresponding monoester 1hardened tallowoyloxy-2-hydroxy-3-trimethylammonium propane chloride.

Example A Preparation of a comparative fabric conditioner composition with fluorocarbon stain-blocking agent was carried out as follows.

15.9 g of molten HEQ were added to a warm (approximately 50 2C) mixture of 442.4 g of water and 41.7g of Zonyl 8868 (containing 25% by weight of fluorinated polymer). The solution was stirred throughout the addition of the HEQ and stirring continued until the mixture cooled to ambient temperature (approximately 20 2C).

Application of fabric conditioner compositions to fabric Mixed 1kg (measured as dry fabric) wash loads of fabrics were prepared comprising: Red and black pigment printed 100% cotton woven fabric purchased from Abakhan Fabrics, Birkenhead (3 pieces of 50cm x 50cm), Tencel (tu) (100% synthetic cellulosic) fabric supplied by Acordis, Tencel Innovation Studio, Sponden, Derby (3 pieces of 50cm x 50cm), 100% cotton interlock (undyed) (4 pieces of 50cm x 50cm), 100% cotton interlock (blue) (2 pieces of 50cm x 50cm), 50 : 50 polyester: cotton sheeting (2 pieces of 50cm x 50cm), one Hanes (Trade Mark) teeshirt, 100% cotton, supplied by Westlairds, Birkenhead, 100% cotton sheeting (woven) (to 1kg).

Washing was performed using a Miele Novotronic W916 (Trade Mark) front loading automatic washing machine, 40 C cotton cycle set to short wash. Persil Performance powder (tam) (ex.

Lever Faberg Europe, May 2001) was used as detergent (40g).

After washing the wash loads were tumble dried in a Miele Novotronic T430 (Trade Mark) moisture sensitive tumble drier on extra dry setting (drying time-45 minutes).

In total each load was subjected to three wash-dry cycles.

For each set of experiments, one of the following formulations was added during the final rinse of each wash cycle.

1) Comparative Example A (55g) 2) Comparative Example B: 30g of Polymer AM solution (containing 10wt% polymer AM).

3) Example 1 according to the invention: Example A (55g) mixed with 30ml of polymer AM solution just prior to addition to the machine.

After three wash-dry cycles the fabrics were rested at 20 C for 24 hours at 65% Relative Humidity prior to testing.

Colour Measurement The colours of the Tencel and striped cotton fabrics were measured as new and after treatment and resting using a Datacolor International Spectraflash SF600 reflectance spectrophotometer linked to a computer. The viewing

conditions were: 10 degree observer, D65 illumination, specular included, Ultra Violet excluded. Each fabric sample had its colour measured eight times in different orientations. The average CIELAB values were obtained and the colour difference (delta E) between the new fabric and the fabric after treatment with the examples was calculated and is shown in table 1.

Table 1

Example Tencel Red woven cotton Black woven cotton A 3. 6 9. 5 4. 3 B 2. 8 6. 0 1. 3 1 3. 0 5. 9 1. 4 For the fabric to maintain a new appearance, it is desirable that the change in colour following repeated washings should be as small as possible. Thus the best results are for the smallest values of delta E. It can be seen from the results in table 1 for the composition according to the invention are similar in magnitude to those for the comparative example B and considerably better than for comparative example A. This shows that, surprisingly, the incorporation of the fluorocarbon stain-blocking agent into the composition does not prevent the functioning of the cationic cross-linking polymeric material.

Soil Repellency Approximately lOxlOcm squares of the treated fabrics were ironed with a hot iron and rested for at least 24 hours at

20 2C and 65% relative humidity prior to testing. Each square was cut into quarters. Using an accurate balance (to at least. 001 gm), the cut cloths were weighed individually (-0. 5g each) and put onto a non-absorbent surface. With an accurate pipette either olive oil (0.05ml, ex. Aldrich) or aqueous propan-2-ol solution (0.05ml, 30% weight/volume) was dropped onto the centre of a square and left for 5 seconds.

The excess liquid was wiped from the surface of the cloth with a paper tissue. Another paper tissue, 4 layers thick, was then placed on top of the cloth and a lkg weight put on top of it for 5 seconds. The weight and tissue were then removed and the cloth re-weighed. The percentage of the stain remaining on the fabric was then calculated and hence the percentage of the stain repelled by the fabric. Three repeat samples were taken for each treatment.

The results for each example are shown in table 2.

Table 2 Soil repellency expressed as percentages

Example Oil Propan-2-ol & Water A 65 88 B 10 17 1 90 92 It can be seen from table 2 that the composition according to the invention provides improved soil repellency over the comparative examples.

Claims

CLAIMS 1. Fabric care composition comprising a fluorocarbon stain- blocking agent characterised in that it further comprises a cationic cross-linking polymeric material which is capable of self cross-linking and/or of reacting with cellulose together with one or more textile compatible carriers, wherein the cationic cross- linking polymeric material comprises one or more poly (oxyalkylene) groups having an end group which comprises one or more amino groups or derivatives of said amino groups, wherein, when the textile compatible carrier is water, a further additive suitable for use in laundry compositions is present.
2. Composition as claimed in Claim 1, wherein the cationic cross-linking polymeric material is obtainable by the reaction of a polymer of formula B (R) n, wherein n is from 1 to 20, B is a backbone group to which each R is covalently bonded and R is a group comprising a poly (oxyalkylene) chain, which chain comprises an amino end group, the polymer being optionally reacted with a bridging compound, with a cross-linking agent.
3. Composition as claimed in Claim 2, wherein n is 2 or 3.
4. Composition as claimed in Claim 2 or Claim 3, wherein B

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5. Composition as claimed in any one of Claims 2 to 4, wherein at least one R group has the formula- (CH2CH (R') (CH2) aO) p-A-NHR'', wherein: R'is H or CH3 ; a is 0,1 or 2 ; p is an integer from 5 to 30; A is an alkylene group ; and R''is H or alkyl.
6. Composition as claimed in any one of Claims 2 to 5, wherein p is from 10 to 25.
7. Composition as claimed in any one of Claims 2 to 6, wherein the polymer of formula B (R) n is

wherein p, q and r are integers which may be the same or different and may be from 5 to 30 and A is branched or unbranched lower alkylene.
8. Composition as claimed in any one of Claims 2 to 6, wherein the polymer of formula B (R) n is

wherein: b is an integer from 1 to 6; c is an integer from 1 to 6; and d and d2 are the same or different and are integers from 10 to 15.

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9. Composition as claimed in Claim 8, wherein b is 3 and/or c is 4.
10. Composition as claimed in any one of Claims 2 to 9, wherein the cross-linking agent comprises an epihalohydrin.
11. Composition as claimed in any one of Claims 2 to 10 wherein the molar ratio of cross-linking agent to polymer of formula B (R) n is from 0.5 : 1 to 4: 1.
12. Composition as claimed in any one of Claims 2 to 11, wherein the bridging compound comprises two epoxide or carboxylic acid groups.
13. Composition as claimed in Claim 11, wherein the epoxide or carboxylic acid groups are linked by a linker comprising alkylene, arylene, poly (oxyalkylene) or siloxane groups or combinations thereof.
14. Composition as claimed in any preceding claim further comprising a silicone which is capable of reacting with the cationic cross-linking polymeric material.
15. Composition as claimed in any preceding claim wherein the fluorocarbon stain-blocking agent is a polymer or copolymer from monomer units according to formula (I):

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wherein R is H or CH3, n is 1 or 2, and Rf is a fluorinated or perfluorinated alkyl residue.
16. Composition as claimed in any preceding claim wherein the fluorocarbon stain-blocking agent is present as a cationic emulsion.
17. Composition as claimed in any preceding claim wherein the one or more textile compatible carriers comprise a detergent active compound.
18. Composition as claimed in any preceding claim, wherein the one or more textile compatible carriers comprise a fabric softening and/or conditioning compound.
19. Composition as claimed in any preceding claim, further comprising a perfume.
20. A method of treating fabric, as part of a laundering process, which comprises applying to the fabric a fabric care composition according to any one of claims 1 to 19.
21. A method of treating fabric, as part of a laundering process, which comprises applying to the fabric a fluorocarbon stain-blocking agent and a cationic cross- linking polymeric material as defined in any one of Claims 1 to 16.
22. A method as claimed in Claim 20 or Claim 21 wherein the composition is applied to the fabric during a wash cycle.

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23. A method as claimed in Claim 20 or Claim 21, wherein the composition is applied to the fabric during a rinse cycle.
24. Use of a fabric care composition according to any one of Claims 1 to 19 to improve the surface colour definition and stain repellency of a fabric after multiple washings.
25. Use of a fabric care composition according to any one of Claims 1 to 19 to impart pill and/or fuzz resistance and stain repellency to fabric during laundering.
26. Use as claimed in Claim 24 or Claim 25, wherein the fabric comprises cellulosic fibres.