WO2014060235A2

WO2014060235A2 - Laundry compositions

Info

Publication number: WO2014060235A2
Application number: PCT/EP2013/070846
Authority: WO
Inventors: Martin Charles Crossman; Craig Jonathon FAIRGRIEVE; Ezat Khoshdel
Original assignee: Unilever Plc; Unilever N.V.; Conopco, Inc., D/B/A Unilever
Priority date: 2012-10-17
Filing date: 2013-10-07
Publication date: 2014-04-24
Also published as: AR093030A1; ZA201502548B; CN104704101A; EP2909295A2; ES2601135T3; BR112015008051B1; EP2909295B1; CN104704101B; WO2014060235A3; BR112015008051A2

Abstract

The present invention relates to a laundry detergent composition comprising (a) nonionic surfactant, (b) anionic surfactant, (c) alkyl ether carboxylic acid or carboxylate salt thereof, and, (d) a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine; and to its use to soften fabrics.

Description

LAUNDRY COMPOSITIONS

FIELD OF THE INVENTION

This invention relates to a laundry composition. More particularly, the invention is directed to a softening in the wash laundry composition.

BACKGROUND OF THE INVENTION

Textile fabrics, including clothes, have traditionally been cleaned with laundry detergents. After cleaning, fabrics can often feel harsh. To prevent the

drawbacks of fabrics feeling harsh after cleaning and especially experienced after multiple wash and wear cycles, technologies have been developed to increase the softness of fabrics, including rinse-added conditioner compositions and softening systems added to the detergent composition. These formulations are sometimes classed as softening in the wash laundry detergents.

There is a need to improve softening in the wash laundry detergents.

Alkyi ether carboxylates are known as anionic surfactants for laundry formulations. We have found that a formulation comprising an alkyi ether carboxylic acid or alkyi ether carboxylate salt along with a polyglucosamine or a copolymer of

glucosamine and N-acetylglucosamine, provides excellent softening in the wash.

SUMMARY OF THE INVENTION

In a first aspect, the invention is directed to a laundry detergent composition comprising:-

(a) from 1 to 40 wt.% nonionic surfactant;

(b) from 1 to 40 wt.% anionic surfactant;

(c) from 1 to 15 wt.% of an alkyi ether carboxylic acid or carboxylate salt thereof; and, (d) from 0.1 to 10 wt.% of a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine.

Preferably the alkyl ether carboxylic acid or salt thereof, and the polyglucosamine or copolymer of glucosamine and N-acetylglucosamine are included in the form of an emulsion.

Preferably the emulsion is an aqueous emulsion. The emulsion may optionally include an emulsifier.

Preferred compositions according to the invention comprise:-

(a) from 1 to 40 wt.% nonionic surfactant;

(b) from 1 to 40 wt.% anionic surfactant; and,

(c) an aqueous emulsion comprising by weight of total composition :- (i) 1 to 15 wt.% of an alkyl ether carboxylic acid or carboxylate salt thereof; and,

(ii) 0.1 to 10 wt.% of a polyglucosamine or a copolymer of

glucosamine and N-acetylglucosamine.

Preferably the polyglucosamine or copolymer of glucosamine and N- acetylglucosamine is chitosan.

Preferably the polyglucosamine or copolymer of glucosamine and N- acetylglucosamine is neutralised by an organic acid.

Preferably the polyglucosamine or copolymer of glucosamine and N- acetylglucosamine is present at a level of from 0.5 to 7.5 wt.%, more

from 1 to 5 wt.%, most preferably at a level of from 1 to 2.5 wt.%. Preferably the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, more preferably at a level of from 2 to 7.5 wt.%.

Preferred alkyl ether carboxylic acid or carboxylate salt are depicted by formula 1 :

Formula 1

wherein R denotes a saturated or unsaturated C6-C22 alkyl chain; R¹ and R² are either both hydrogen; or R¹ is hydrogen and R² is CH₃; or R¹ is CH₃ and R² is hydrogen; R³ is hydrogen, or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium; and, n is a number from 2 to 20, preferably 3 to 12, more preferably 3 to 10, which denotes the number of repeat units.

Preferred alkyl ether carboxylic acids or carboxylate salts thereof have a C₈-Ci₈ alkyl chain with between 2 to 20, more preferably between 3 to 12, even more preferably between 3 to 10 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof. By this is meant that the molecule of formula 1 may contain mixtures of polyethylene glycol (also known as ethylene oxide) and polypropylene glycol (also known as propylene oxide) repeat units Preferably a cationic polymer is present at a level of from 0.1 to 2.5 wt.%.

Preferably the nonionic surfactant comprises an alcohol ethoxylate.

Preferably the detergent composition is a liquid laundry detergent composition. If the composition is a liquid, then preferably it has a pH of from 6.2 to 9, more preferably from pH 6.5 to 8.5, for example from pH 6.5 to 8.

Preferably the ratio by weight of the alkyl ether carboxylic acid or carboxylate salt thereof to the polyglucosamine or a copolymer of glucosamine and N- acetylglucosamine is from 1 .5:1 to 100:1 .

In a second aspect, the invention provides a method of softening fabrics, comprising the steps:- (a) providing a laundry composition according to the first aspect;

(b) contacting one or more textile articles with the composition at one or more points during the main wash of a laundering process; and,

(c) allowing the textile articles to dry or mechanically tumble-drying them. In a third aspect, the invention provides the use of an aqueous emulsion comprising an alkyl ether carboxylic acid or carboxylate salt thereof, and a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine as described herein to provide softness to fabrics. DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "comprising" means including, made up of, composed of, consisting and/or consisting essentially of.

All percentages quoted are wt.% based on total amount in the laundry composition unless otherwise stated.

The invention is directed to laundry compositions containing alkyl ether carboxylic acid or carboxylate salt thereof, a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine, a nonionic surfactant, and an anionic surfactant. The composition displays improved softening in the wash. Form of the Invention

The invention can take any of a number of forms that are laundry compositions. Examples include powders, granules, bars, gels and liquids. Preferably the composition is in the form of a liquid laundry product. Preferably they are main wash products. It can take the form of a laundry composition for the main wash, which may be dilutable or non-dilutable. The laundry composition may for example be an isotropic liquid, or a surfactant-structured liquid. Particularly preferred forms of this invention include combination detergent/softener products to provide "softening in the wash".

Preferably the detergent composition is a liquid laundry detergent composition. Preferably the liquid composition has a pH of from 6.2 to 9, more preferably from pH 6.5 to 8.5, for example from pH 6.5 to 8.

Preferably the ratio by weight of the alkyl ether carboxylic acid or carboxylate salt thereof to the polyglucosamine or a copolymer of glucosamine and N- acetylglucosamine is from 1 .5:1 to 100:1 . Polyglucosamine

The composition comprises a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine.

The polyglucosamine may be derived from plant or animal feedstocks and is prepared by deacetylating chitin, e.g. between 50-100% deacetylation. The polyglucosamine may therefore be a copolymer of glucosamine and N- acetylglucosamine. For the purposes of this invention, where reference to polyglucosamine is made, it encompasses both polyglucosamine (e.g. where a chitin feedstock is 100% deacetylated) and a copolymer of glucosamine and N- acetylglucosamine (e.g. where a chitin feedstock is only partially deacetylated). The polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine is present at a level of from 0.1 to 10 wt.%. Preferably the polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine is present at a level of from 0.1 to 7.5 wt.%, more preferably at a level of from 0.1 to 5 wt.%, most preferably at a level of from 0.2 to 2.5 wt.%.

Alternatively the polyglucosamine or a copolymer of glucosamine and N- acetylglucosamine may be present at a level of from 0.5 to 7.5 wt.%, preferably at a level of from 1 to 5 wt.%, more preferably at a level of from 1 to 2.5 wt.%.

The preferred polyglucosamine or a copolymer of glucosamine and N- acetylglucosamine is chitosan. The chitosan can be low, medium or high molecular weight and polydispersity.

The polyglucosamine or copolymer of glucosamine and N-acetylglucosamine, preferably chitosan, may be neutralised (wholly or partially) by an organic acid. Alkyl Ether Carboxylic Acid

The composition comprises 1 to 15 wt.% alkyl ether carboxylic acid or carboxylate salt thereof.

The alkyl ether carboxylic acid/carboxylate (AEC) is usually derived from a fatty alcohol which is alkoxylated, usually with ethylene glycol and/or propylene glycol, a carboxylic acid is then introduced to the material to form the alkyl ether carboxylic acid.

Preferably the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, more preferably at a level of from 2 to 7.5 wt.%. Preferred alkyl ether carboxylic acid or carboxylate salt are depicted by formula 1 :

Formula 1

wherein R denotes a saturated or unsaturated C₆-C₂2 alkyl chain; R¹ and R² are either both hydrogen (in which case the repeat unit is ethylene glycol known as (EO) for short); or R¹ is hydrogen and R² is CH₃; or R¹ is CH₃ and R² is hydrogen (in which case the repeat unit is propylene glycol, known as (PO) for short); R³ is hydrogen (in which case it is an alkyl ether carboxylic acid), or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium (in which case it is an alkyl ether carboxylate salt); and, n is a number from 2 to 20, preferably 3 to 12, more preferably 3 to 10, which denotes the number of repeat units.

Preferred alkyl ether carboxylic acids or carboxylate salts thereof have a C₈-Ci₈ alkyl chain with between 2 to 20, more preferably between 3 to 12, even more preferably between 3 to 10 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof. By this is meant that the molecule of formula 1 may contain mixtures of polyethylene glycol (also known as ethylene oxide) and polypropylene glycol (also known as propylene oxide) repeat units.

When in the form of an alkyl ether carboxylate salt, a preferred salt is sodium. Examples of suitable materials are oleyl alkyl ether (8EO) carboxylic acid, oleyl alkyl ether (10EO) carboxylic acid or laureth-5 carboxylic acid (5EO), and the sodium salts thereof. Emulsions

The polyglucosamine and alkyl ether carboxylic acid or carboxylate salt thereof are most preferably delivered in the composition in the form of an emulsion.

Delivery of a complex of these two actives in the form of an emulsion even more so improves the softening in the wash for fabrics that are treated.

Preferably the emulsion is an aqueous emulsion.

In an example emulsion, the alkyl ether carboxylic acid or carboxylate salt thereof is dissolved in water and protonated with mole equivalent acid (e.g. HCI), the polyglucosamine is added, and the mixture is allowed to stir for 24 hours. The alkyl ether carboxylate/polyglucosamine emulsion is then filtered (for example through cheesecloth) to remove any undissolved reactants, and dialysed to remove any remaining free acid, resulting in the desired aqueous emulsion comprising the polyglucosamine and the alkyl ether carboxylic acid/carboxylate salt.

An optional emulsifier may be included to aid formation of the emulsion, though it is not required.

Surfactants

The detergent composition comprises nonionic surfactant and anionic surfactant. The nonionic surfactant component preferably comprises alcohol ethoxylate.

The alcohol ethoxylates are formed from the reaction of primary or secondary alcohols with ethylene oxide. Typically an aliphatic Cs to Cie primary or secondary linear or branched alcohol is reacted with ethylene oxide in the required molar amount to produce the alcohol ethoxylate. Preferred alcohol ethoxylates have from 2 to 40, preferably from 3 to 30, more preferably from 5 to 20 ethylene oxide units attached to the aliphatic chain.

The surfactants may be chosen from the surfactants described in "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .

Preferably the surfactants used are saturated.

Suitable nonionic detergent compounds which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are C6 to C22 alkyl phenol- ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C₈ to C-|₈ primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

Suitable anionic detergent compounds which may be used can be water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher C₈ to Ci₈ alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C-m to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The anionic surfactant may also include soaps of C6-C22 fatty acids. The preferred anionic detergent compounds are sodium Cn to Ci5 alkyl benzene sulphonates and sodium C12 to C-is alkyl sulphates. Salts of sulphonates included as hydrotrobes can additionally be considered as anionic surfactants as defined herein. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl

monoglycosides. The nonionic detergent is present in amounts of from 1 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.

The anionic surfactant is present in amounts of from 1 to 40 wt.%, preferably from 5 to 35 wt.%, more preferably from 6 to 20 wt.%.

The total amount of surfactant present in the composition is preferably at least 5 wt.%, more preferably at least 10 wt.%, More preferably the total amount of surfactant is from 15 to 65 wt.%, preferably from 10 to 50 wt.%. Other surfactants such as cationic surfactants, and amphoteric/zwitterionic surfactants such as betaines may also be present in addition to the

aforementioned nonionic and anionic surfactants.

Optional Ingredients

Cationic Polymer

The composition may additionally comprise a cationic polymer.

This term refers to polymers having an overall positive charge. Preferably the cationic polymer is selected from the group consisting of: cationic polysaccharide polymers, and cationic non-saccharide polymers having cationic protonated amine or quaternary ammonium functionalities that are homo or copolymers derived from monomers containing an amino or quaternary nitrogen functional group polymerised from at least one of the following monomer classes: acrylate, methacrylate, acrylamide, methacrylamide; allyls (including diallyl and methallyl); ethylene imine; and/or vinyl monomer classes, and mixtures thereof.

More preferably the cationic polymer is selected from the group consisting of cationic cellulose polymers, cationic guar polymers, cationic diallyl quaternary ammonium-containing polymers and homo or copolymers of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or tert-butylaminoethyl

(meth)acrylate in their quaternary or protonated amine form, and mixtures thereof. Most preferably the cationic polymer is a cationic polysaccharide polymer.

More preferably the cationic polysaccharide polymer is a cationic guar or cationic cellulose polymer. Most preferably the cationic polymer is a cationic cellulose polymer, for example, quaternised hydroxy ethyl cellulose.

The composition may include a single cationic polymer or a mixture of cationic polymers from the same or different classes, i.e. the composition may contain a cationic polysaccharide polymer and a cationic non-polysaccharide polymer. Cationic Polysaccharide Polymer

The term "cationic polysaccharide polymer" refers to polymers having a

polysaccharide backbone and an overall positive charge. Polysaccharides are polymers made up from monosaccharide monomers joined together by glycosidic bonds. The cationic polysaccha de-based polymers present in the compositions of the invention have a modified polysaccharide backbone, modified in that additional chemical groups have been reacted with some of the free hydroxyl groups of the polysaccharide backbone to give an overall positive charge to the modified cellulosic monomer unit.

A preferred class of cationic polysaccharide polymers suitable for this invention are those that have a polysaccharide backbone modified to incorporate a quaternary ammonium salt. Preferably the quaternary ammonium salt is linked to the polysaccharide backbone by a hydroxyethyl or hydroxypropyl group.

Preferably the charged nitrogen of the quaternary ammonium salt has one or more alkyl group substituents.

Preferred cationic polysaccharide-based polymers have a guar based, or cellulosic based backbone. Cellulose based cationic polymers are most preferred. Guar is a galactomannan having a β-1 ,4 linked mannose backbone with

branchpoints to a-1 ,6 linked galactose units.

Suitable cationic guar gum derivatives, such as guar hydroxypropyltrimonium chloride, specific examples of which include the Jaguar series commercially available from Rhone-Poulenc Incorporated and the N-Hance series commercially available from Aqualon Division of Hercules, Inc.

An example of a preferred guar based cationic polymer is guar 2-hydroxy-3- (trimethylammonium) propyl ether salt.

Cellulose is a polysaccharide with glucose as its monomer, specifically it is a straight chain polymer of D-glucopyranose units linked via β-1 ,4 glycosidic bonds and is a linear, non-branched polymer. Example cationic cellulose polymers are salts of hydroxyethyl cellulose reacted with trimethyl ammonium substituted epoxide, referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 10 and is commercially available from the Amerchol Corporation, a subsidiary of The Dow Chemical Company, marketed as the Polymer LR, JR, and KG series of polymers. Other suitable types of cationic celluloses include the polymeric quaternary ammonium salts of hydroxyethyl cellulose reacted with lauryl dimethyl ammonium- substituted epoxide referred to in the field under the International Nomenclature for Cosmetic Ingredients as Polyquatemium 24. These materials are available from Amerchol Corporation marketed as Polymer LM-200.

Typical examples of preferred cationic cellulosic polymers include

cocodimethylammonium hydroxypropyl oxyethyl cellulose,

lauryldimethylammonium hydroxypropyl oxyethyl cellulose,

stearyldimethylammonium hydroxypropyl oxyethyl cellulose, and

stearyldimethylammonium hydroxyethyl cellulose; cellulose 2-hydroxyethyl 2- hydroxy 3-(trimethyl ammonio) propyl ether salt, polyquaternium-4,

polyquaternium-10, polyquaternium-24 and polyquaternium-67 or mixtures thereof.

More preferably the cationic cellulosic polymer is a quaternised hydroxy ether cellulose cationic polymer. These are commonly known as polyquaternium-10. Suitable commercial cationic cellulosic polymer products for use according to the present invention are marketed by the Amerchol Corporation under the trade name UCARE.

Other Cationic Polymer Classes

Non-polysaccharide based cationic polymers may also be used. Suitable cationic non-saccharide polymers include those having cationic protonated amine or quaternary ammonium functionalities that are homo or copolymers derived from monomers containing an amino or quaternary nitrogen functional group

polymerised from at least one of the following monomer classes: acrylate, methacrylate, acrylamide, methacrylamide; allyls (including diallyl and methallyl); ethylene imine; and/or vinyl monomer classes, and mixtures thereof.

Preferred cationic non-saccharide polymers include cationic diallyl quaternary ammonium-containing polymers and homo or copolymers of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate or tert-butylaminoethyl

(meth)acrylate in their quaternary or protonated amine form, and mixtures thereof.

Other suitable cationic polymers for use in the compositions include copolymers of 1 -vinyl-2-pyrrolidone and 1 -vinyl-3-methylimidazolium salt (known as

Polyquatemium-16); copolymers of 1 -vinyl-2-pyrrolidone and dimethylaminoethyl methacrylate (known as Polyquaternium-1 1 ); cationic diallyl quaternary

ammonium-containing polymers, including, for example, dimethyldiallylammonium chloride homopolymer, copolymers of acrylamide and dimethyldiallylammonium chloride (known as Polyquatemium 6 and Polyquatemium 7 respectively);

amphoteric copolymers of acrylic acid including copolymers of acrylic acid and dimethyldiallylammonium chloride (known as Polyquatemium 22), terpolymers of acrylic acid with dimethyldiallylammonium chloride and acrylamide (known as Polyquatemium 39), and terpolymers of acrylic acid with methacrylamidopropyl trimethylammonium chloride and methylacrylate (known as Polyquatemium 47). Preferred cationic substituted monomers are the cationic substituted

dialkylaminoallcyl acrylamides, dialkylaminoallcyl methacrylamides, and

combinations thereof.

The counterion of the cationic polymer is freely chosen from the halides: chloride, bromide, and iodide; or from hydroxide, phosphate, sulphate, hydrosulphate, ethyl sulphate, methyl sulphate, formate, and acetate. The cationic polymer is present at a level of from 0.1 to 2.5 wt.%, preferably from 0.1 to 2 wt.%, more preferably from 0.2 to 1 wt.%.

Many of the aforementioned cationic polymers can be synthesised in, and are commercially available in, a number of different molecular weights. Preferably the molecular weight of the cationic polymer is from 10,000 to 2,000,000 Daltons, more preferably from 10,000 to 500,000 Daltons.

The detergent composition may optionally comprise one or more of the following optional ingredients, shading dye, enzyme, antiredeposition polymer, dye transfer inhibiting polymer, builder, sequestrant, sunscreen and/or soil release polymer.

Builders and sequestrants

The detergent compositions may also optionally contain relatively low levels of organic detergent builder or sequestrant material. Examples include the alkali metal, citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene

polycarboxylic acids, ethylene diamine tetra-acetic acid, diethylenetriamine- pentaacetic acid, alkyl- or alkenylsuccinic acid, nitrilotriacetic acid, and citric acid. Other examples are DEQUEST™, organic phosphonate type sequestering agents sold by Monsanto and alkanehydroxy phosphonates.

Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and their salts, such as those sold by BASF under the name SOKALAN™. Another suitable builder is sodium carbonate.

If utilized, the builder materials may comprise from about 0.5% to 20 wt%, preferably from 1 wt% to 10 wt%, of the composition. The preferred builder level is less than 10 wt% and preferably less than 5 wt% of the composition.

Preferably the laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e., contains less than 1 wt.% of phosphate.

Shading Dye

Shading dyes deposit to fabric during the wash or rinse step of the washing process providing a visible hue to the fabric. Shading of white garments may be done with any colour depending on consumer preference. Blue and Violet are particularly preferred shades and consequently preferred dyes or mixtures of dyes are ones that give a blue or violet shade on white fabrics. The shading dyes used are preferably blue or violet. The shading dye chromophore is preferably selected from the group comprising: mono-azo, bis-azo, triphenylmethane, triphenodioxazine, phthalocyanin, naptholactam, azine and anthraquinone. Most preferably mono-azo, bis-azo, azine and anthraquinone. Most preferably the dye bears at least one sulfonate group.

Preferred shading dyes are selected from direct dyes, acid dyes, hydrophobic dyes, cationic dyes and reactive dyes. If included, the shading dye is present is present in the composition in range from 0.0001 to 0.01 wt %.

Fluorescent Agent

The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt.%, more preferably 0.01 to 0.1 wt.%. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2-(4-styryl-3-sulfophenyl)-2H-napthol[1 ,2- d]trazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl-N-2 hydroxyethyl) amino 1 ,3,5- triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6- morpholino-1 ,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'- bis(2-sulfoslyryl)biphenyl.

Perfume

Preferably the composition comprises a perfume. The perfume is preferably in the range from 0.001 to 3 wt.%, most preferably 0.1 to 1 wt.%. Many suitable examples of perfumes are provided in the CTFA (Cosmetic, Toiletry and

Fragrance Association) 1992 International Buyers Guide, published by CFTA Publications and OPD 1993 Chemicals Buyers Directory 80th Annual Edition, published by Schnell Publishing Co.

It is commonplace for a plurality of perfume components to be present in a formulation. In the compositions of the present invention it is envisaged that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.

In perfume mixtures preferably 15 to 25 wt.% are top notes. Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80 [1955]). Preferred top-notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol. It is preferred that the laundry treatment composition does not contain a peroxygen bleach, e.g., sodium percarbonate, sodium perborate, and peracid. Polymers

The composition may comprise one or more polymers. Polymers can assist in the cleaning process by helping to retail soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.

The composition may comprise one or more polymers. Examples are

carboxymethylcellulose, hydroxyethyl cellulose, hydroxpropyl cellulose, poly(ethylene glycol), polyvinyl alcohol), ethoxylated polyamines,

polycarboxylates such as polyacrylates, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.

Dye transfer inhibitors

Modern detergent compositions typically employ polymers as so-called 'dye- transfer inhibitors'. These prevent migration of dyes, especially during long soak times. Generally, such dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, manganese pthalocyanine, peroxidases, and mixtures thereof, and are usually present at a level of from 0.01 to 10 wt.% based on total amount in the laundry composition.

Anti-redeposition polymers

Anti-redeposition polymers are designed to suspend or disperse soil. Typically antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, Acrylic acid based homo or copolymers available under the trade mark ACUSOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF.

Soil Release Polymers

Examples of suitable soil release polymers include graft copolymers of polyvinyl ester), e.g., Ci -C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones. Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany). Further suitable soil release polymers of a different type include the commercially available material ZELCON 5126 (from DuPont) and MILEASE T (from ICI). If present, the soil release polymer may be included at a level of from from 0.01 to 10 wt.% based on total amount in the laundry composition. Further examples of soil release polymers are terephthalic acid / glycol copolymers sold under the tradenames Texcare, Repel-o-tex, Gerol, Marloquest, Cirrasol.

Hydrotrope

The detergent composition, especially when a liquid composition may optionally include a hydrotrope, which can prevent liquid crystal formation. The addition of the hydrotrope thus aids the clarity/transparency of the composition. Suitable hydrotropes include but are not limited to propylene glycol, ethanol, urea, salts of benzene sulphonate, toluene sulphonate, xylene sulphonate or cumene sulphonate. Suitable salts include but are not limited to sodium, potassium, ammonium, monoethanolamine, triethanolamine. Salts of sulphonates can also be considered as anionic surfactants as defined herein. Preferably, the hydrotrope is selected from the group consisting of propylene glycol, xylene sulfonate, ethanol, and urea to provide optimum performance. The amount of the hydrotrope is generally in the range of from 0 to 30%, preferably from 0.5 to 30%, more preferably from 0.5 to 30%, most preferably from 1 to 15%. Enzvmes

Enzymes can also be present in the formulation. Preferred enzymes include protease, lipase, pectate lyase, amylase, cutinase, cellulase, mannanase. If present the enzymes may be stabilized with a known enzyme stabilizer for example boric acid.

Examples

Preparation of the alkyl ether carboxylic carboxylate/chitosan emulsion

1 1 .19g of Emulsogen Col 100 (an Oleic alcohol polyethylene glycol ether (10EO) carboxylic acid available from Clariant) was dissolved in deionised water (500ml) and protonated with mole equivalent HCI. Chitosan LMW (2.5g) was then added, and the mixture was allowed to stir for 24hrs. The resulting product was filtered through cheesecloth to remove any undissolved reactants, and then dialysed to remove free acid.

This resulted in an aqueous emulsion comprising chitosan and the alkyl ether carboxylic carboxylate.

Softening performance

The softening performance of the emulsion was tested, by itself and in a laundry detergent (Formulation A) against various controls (water and the laundry detergent formulation itself).

Four formulations were tested :- 1 . Water

2. Formulation A (dosed at 1 .25g per wash)

3. Emulsion of chitosan/alkyl ether carboxylate (dosed at 5g per wash)

4. Formulation A (dosed at 1 .25g per wash) + emulsion (dosed at 5g per wash)

The experiment involved dosing 500ml of water in a 1 litre bottle along with 4 pieces of terry towel. Liquor to cloth weight ratio was 10:1 . The amounts of formulation were also added, and the bottle was agitated for 30 minutes on a rotary stirrer at room temperature to replicate a washing machine. The wash liquor was removed, and each set of terry towels were rinsed twice, for 10 minutes using 500ml of water, again on the rotary stirrer at room temperature. The terry towels were line dried.

The treated terry towels were assessed by 10 panellists who ranked them 1 -4 terms of softness (4 = most soft). The total rankings were averaged to give a softness score.

It is clear form the softness results that the emulsion provided vastly improved softening over the water control. It is also clear that the emulsion also vastly improved the softening of the laundry detergent composition.

Claims

C LAI MS

1 . A laundry detergent composition comprising:-

(a) from 1 to 40 wt.% nonionic surfactant;

(b) from 1 to 40 wt.% anionic surfactant; and,

(c) from 1 to 15 wt.% of an alkyl ether carboxylic acid or carboxylate salt thereof; and,

(d) from 0.1 to 10 wt.% of a polyglucosamine or a copolymer of

glucosamine and N-acetylglucosamine.

2. A composition according to claim 1 , wherein the alkyl ether carboxylic acid or salt thereof, and the polyglucosamine or copolymer of glucosamine and N-acetylglucosamine are included in the form of an emulsion, preferably an aqueous emulsion, and optionally including an emulsifier.

3. A composition according to claim 1 or claim 2, comprising:-

(a) from 1 to 40 wt.% nonionic surfactant;

(b) from 1 to 40 wt.% anionic surfactant; and,

(c) an aqueous emulsion comprising by weight of total composition :-

(i) 1 to 15 wt.% of an alkyl ether carboxylic acid or carboxylate salt thereof; and,

(ii) 0.1 to 10 wt.% of a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine.

4. A composition according to any preceding claim, wherein the

polyglucosamine or copolymer of glucosamine and N-acetylglucosamine is chitosan.

A composition according to any preceding claim, wherein the polyglucosamine or copolymer of glucosamine and N-acetylglucosamine is neutralised by an organic acid.

A composition according to any preceding claim, wherein the

polyglucosamine or copolymer of glucosamine and N-acetylglucosamine is present at a level of from 0.1 to 7.5 wt.%, preferably at a level of from 0.1 to 5 wt.%, more preferably at a level of 0.2 to 2.5 wt.%.

A composition according to any preceding claim, wherein the alkyl ether carboxylic acid or carboxylate salt thereof is present at a level of from 1 to 10 wt.%, preferably at a level of from 2 to 7.5 wt.%.

A composition according to any preceding claim, wherein the alkyl ether carboxylic acid or carboxylate salt is depicted by:

wherein R denotes a saturated or unsaturated C6-C22 alkyl chain; R¹ and R² are either both hydrogen; or R¹ is hydrogen and R² is CH₃; or R¹ is CH₃ and R² is hydrogen; R³ is hydrogen, or a solubilising cation such as sodium, potassium, ammonium or substituted ammonium; and, n is a number from 2 to 20, preferably 3 to 12, denoting the number of repeat units.

9. A composition according to any preceding claim, wherein the alkyl ether carboxylic acid or carboxylate salt has a Cs-C-is alkyl chain with between 2- 12 glycol repeat units, wherein the glycol repeat units are selected from ethylene glycol, propylene glycol or mixtures thereof.

10. A composition according to any preceding claim, additionally comprising from 0.1 to 1 wt.% of a cationic polymer.

1 1 . A composition according to any preceding claim, which is a liquid

composition.

12. A composition according to claim 1 1 , having a pH of from 6.2 to 9,

preferably from pH 6.5 to 8.5, most preferably from pH 6.5 to 8.

A composition according to any preceding claim, wherein the ratio by weight of the alkyl ether carboxylic acid or carboxylate salt thereof to the polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine is from 1 .5:1 to 100:1 .

A method of softening fabrics, comprising the steps:-

(a) providing a laundry composition according to any preceding claim;

(c) allowing the textile articles to dry or mechanically tumble-drying

them.

Use of an aqueous emulsion according to any one of claims 2 to 13, comprising an alkyl ether carboxylic acid or carboxylate salt thereof, and a polyglucosamine or a copolymer of glucosamine and N-acetylglucosamine to provide softness to fabrics.