The present invention relates to laundry liquid compositions with improved hygiene benefits.

US 7 723 281 (Herdt et al) discloses an enzyme stabilisation system and methods for using such in cleaning applications.

EP 1 627 033 (Greenbridge Environmental) discloses anti-viral and anti-bacterial compositions comprising amines.

US 5 929 022 (Velasquez) discloses laundry detergent compositions comprising amine detersives.

Despite the prior art there remains a need for stable laundry liquid compositions which provide cleaning as well as hygiene benefits and are fragranced.

Accordingly, the present invention provides a liquid fabric cleaning composition comprising an alkylamine, and a fragrance, wherein the composition comprises less than 0.25% wt. aldehyde and ketone component, wherein the alkylamine is defined by formula

(I):

(I) RI-N(R ₂ )R ₃

wherein Ri is linear or branched C6-18 alkyl group,

wherein R ₂ is an aminoalkyl group of formula -(CH ₂ ) _m -NH _2,

wherein R ₃ is hydrogen, an aminoalkyl group having the formula -(CH ₂ ) _n -NH ₂ or a carboxyalkyl group having the formula -(CH2) _p -COOH, and

with m and n independently being integers from 2 to 6 and p being an integer from 1 to 5.

We have surprisingly found that fragranced formulations comprising alkylamines can be stable if the level of aldehyde and ketone is kept to less than 0.25% wt. of the

composition. Typically, aldehydes and ketones are included in fragrance components and so fragrances are considered generally incompatible with compositions containing alkylamine actives. Preferably the aldehyde and ketone level in the composition is less than 0.2% wt., more preferably less than 0.1% wt. and most preferably less than 0.05% wt. By‘aldehyde and ketone’ level is meant the total amount of all components that have at least one aldehyde group or at least one ketone group.

Preferably, the pH of the composition is from 7 to 10.5, and preferably 7.5 to 10.5.

Preferably, the composition comprises anionic surfactant. However, where the pH of the composition is from 7 to 8.5, it is preferred that the anionic surfactant is present at less than 4% wt. of the composition. More preferably, in such circumstances the anionic surfactant is present at from 0 to 2% and most preferably from 0 to 0.5% wt. of the composition. Preferably, where the composition has a pH of from 7 to 8.5 the composition comprises less than 0.5% wt. linear alkyl benzonate, preferably less than 0.2% linear alkyl benzonate.

Preferably, the liquid fabric treatment composition comprises non-ionic surfactant.

Preferably, the non-ionic surfactant is present at from 10 to 25% by weight of the composition.

Preferably, the alkylamine is present at from 0.3 to 4.0%, preferably from 1.0 to 3.7% wt. by weight of the composition.

Preferably, the alkylamine is defined by formula (I):

(I) RI-N(R ₂ )R ₃

wherein Ri is linear or branched C6-18 alkyl group, wherein R ₂ is an aminoalkyl group of formula -(CH ₂ ) _m -NH _2,

wherein R ₃ is hydrogen, an aminoalkyl group having the formula -(CH ₂ ) _n -NH ₂ or a carboxyalkyl group having the formula -(CH2) _p -COOH, and

with m and n independently being integers from 2 to 6 and p being an integer from 1 to 5. Preferably, R1 is a linear or branched C10-14, preferably C12 alkyl group. Preferably, m is 3.

Preferably, R3 has the formula -(CH2) _n -NH2 and n is from 2-4, preferably 3.

Liquid laundry detergents

The term“laundry detergent” in the context of this invention denotes formulated compositions intended for and capable of wetting and cleaning domestic laundry such as clothing, linens and other household textiles. The term“linen” is often used to describe certain types of laundry items including bed sheets, pillow cases, towels, tablecloths, table napkins and uniforms. Textiles can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.

Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycle of automatic washing machines, as well as liquid fine wash and liquid colour care detergents such as those suitable for washing delicate garments (e.g. those made of silk or wool) either by hand or in the wash cycle of automatic washing machines.

The term“liquid” in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above. Accordingly, the term“liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes. The viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec ¹ . This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. Pourable liquid detergent compositions generally have a viscosity of from 200 to 1 ,500 mPa.s, preferably from 200 to 500 mPa.s.

Liquid detergent compositions which are pourable gels generally have a viscosity of from 1 ,500 mPa.s to 6,000 mPa.s, preferably from 1 ,500 mPa.s to 2,000 mPa.s.

A composition according to the invention may suitably have an aqueous continuous phase. By“aqueous continuous phase” is meant a continuous phase which has water as its basis. Compositions with an aqueous continuous phase will generally comprise from 15 to 95%, preferably from 20 to 90%, more preferably from 25 to 85% water (by weight based on the total weight of the composition).

A composition according to the invention may also have a low water content, for example when the composition is intended for packaging in polymeric film soluble in the wash water. Low water content compositions will generally comprise no more than 20%, and preferably no more than 10%, such as from 5 to 10% water (by weight based on the total weight of the composition).

A composition of the invention with an aqueous continuous phase preferably has a pH in the range of 5 to 10.5, more preferably 6 to 10.5, when measured on dilution of the composition to 1 % using demineralised water.

A composition of the invention suitably comprises from 3 to 60%, preferably from 5 to 40%, and more preferably from 6 to 30% (by weight based on the total weight of the composition) of one or more detersive surfactants selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof.

The term“detersive surfactant” in the context of this invention denotes a surfactant which provides a detersive (i.e. cleaning) effect to laundry treated as part of a domestic laundering process.

Non-soap anionic surfactants for use in the invention are typically salts of organic sulfates and sulfonates 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 such materials include alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha- olefin sulfonates and mixtures thereof. The alkyl radicals preferably contain from 10 to 18 carbon atoms and may be unsaturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. The counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed. A preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the“para” position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, with the predominant materials having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1-phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.

Also suitable are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.

Some alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulphates with an alkyl chain length of from 10 to 18.

Mixtures of any of the above described materials may also be used. Apart from in lower pH compositions as explained above, preferred mixture of non-soap anionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably Cn to C15 linear alkyl benzene sulfonate) and sodium lauryl ether sulfate (preferably C10 to C18 alkyl sulfate ethoxylated with an average of 1 to 3 EO).

In a composition of the invention the total level of non-soap anionic surfactant may suitably range from 5 to 15% (by weight based on the total weight of the composition).

Nonionic surfactants for use in the invention are typically polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include Ce to C22 alkyl phenol ethoxylates with an average of from 5 to 25 moles of ethylene oxide per mole of alkyl phenol; and aliphatic alcohol ethoxylates such as Cs to C18 primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.

A preferred class of nonionic surfactant for use in the invention includes aliphatic Cs to C18, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.

Mixtures of any of the above described materials may also be used.

In a composition of the invention the total level of nonionic surfactant will suitably range from 1 to 10% (by weight based on the total weight of the composition).

A mixture of non-soap anionic and nonionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably Cn to C15 linear alkyl benzene sulfonate), sodium lauryl ether sulfate (preferably C10 to C-is alkyl sulfate ethoxylated with an average of 1 to 3 EO) and ethoxylated aliphatic alcohol (preferably C12 to C15 primary linear alcohol ethoxylate with an average of from 5 to 10 moles of ethylene oxide per mole of alcohol).

The weight ratio of total non-soap anionic surfactant to total nonionic surfactant in a composition of the invention suitably ranges from about 3:1 to about 1 :1.

NON-AQUEOUS CARRIERS

A composition of the invention may incorporate non-aqueous carriers such as

hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n- or i-propanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol);

polyethylene glycols having a weight average molecular weight (M _w ) ranging from about 200 to 600; C1 to C3 alkanolamines such as mono-, di- and triethanolamines; and alkyl aryl sulfonates having up to 3 carbon atoms in the lower alkyl group (such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulfonates).

Mixtures of any of the above described materials may also be used.

Non-aqueous carriers, when included, may be present in an amount ranging from 0.1 to 20%, preferably from 1 to 15%, and more preferably from 3 to 12% (by weight based on the total weight of the composition).

COSURFACTANTS

A composition of the invention may contain one or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) in addition to the non-soap anionic and/or nonionic detersive surfactants described above.

Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof. Cationic surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, 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. Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

Mixtures of any of the above described materials may also be used. POLYAMINES

The ethoxylated polyamines (EPEI) are generally linear or branched poly (>2) amines. The amines may be primary, secondary or tertiary. A single or a number of amine functions are reacted with one or more alkylene oxide groups to form a polyalkylene oxide side chain. The alkylene oxide can be a homopolymer (for example ethylene oxide) or a random or block copolymer. The terminal group of the alkylene oxide side chain can be further reacted to give an anionic character to the molecule (for example to give carboxylic acid or sulphonic acid functionality).

The composition comprises from about 0.01 % to about 5% polyamine. Preferably, the polyamine is a soil release agent comprising a polyamine backbone corresponding to the formula:

having a modified polyamine formula V(n+1 )WmYnZ, or a polyamine backbone corresponding to the formula: Rlrrr [l^-R!rH^RJk-NH having a modified polyamine formula V(nk+1 )WmYnY'kZ,

wherein k is less than or equal to n,

Preferably, the polyamine backbone prior to modification has a molecular weight greater than about 200 daltons.

Preferably, i) V units are terminal units having the formula: ii) W units are backbone units having the formula iii) Y units are branching units having the formula: and iv) Z units are terminal units having the formula:

Preferably, backbone linking R units are selected from the group consisting of C2-C12 alkylene, -(R10)xR3 (OR1 )x-, -(CH ₂ CH(0R2)CH ₂ 0)z(R10)yR1 (0CH ₂ CH(0R2)CH ₂ )w-, - CH ₂ CH(OR2)CH ₂ - and mixtures thereof, provided that when R comprises C1-C12 alkylene R also comprises at least one - (R10)xR3(0R1 )x-, -(CH ₂ CH(0R2)CH ₂ 0)z(R10)yR1- (OCH ₂ CH(OR2)CH ₂ )w-, or - CH ₂ CH(OR2)CH ₂ -unit;

Preferably, R1 is C2-C6 alkylene and mixtures thereof;

Preferably, R2 is hydrogen, (R10)XB, and mixtures thereof; Preferably, R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -C(O)-, -C(0)NHR5NHC(0)-, C(0)(R4)rC(0)-, - CH ₂ CH(0H)CH ₂ 0(R10)yR10-CH2CH(0H)CH2-, and mixtures thereof;

Preferably, R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof;

Preferably, R5 is C2-C12 alkylene or C6 C12 arylene;

Preferably, E units are selected from the group consisting of (CH ₂ )p-C0 ₂ M, -(CH ₂ )qSC>3M, -CH(CH ₂ C0 ₂ M)C0 ₂ M, (CH ₂ )pPC>3M, -(R10)xB, and mixtures thereof,

Preferably, B is hydrogen, -(CH ₂ )qS0 ₃ M, -(CH ₂ )pC0 ₂ M, -(CH ₂ )q CH(S0 ₃ M)CH ₂ S0 ₃ M, - (CH ₂ )qCH(S0 ₂ M)CH ₂ S0 ₃ M, - (CH2)pP0 ₃ M, -PO ₃ M, and mixtures thereof,

Preferably, M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance;

Preferably X is a water soluble anion;

Preferably k has the value from 0 to about 20;

Preferably m has the value from 4 to about 400;

Preferably n has the value from 0 to about 200;

Preferably p has the value from 1 to 6,

Preferably q has the value from 0 to 6;

Preferably r has the value 0 or 1 ;

Preferably w has the value 0 or 1 ;

Preferably x has the value from 1 to 100;

Preferably y has the value from 0 to 100; and

Preferably z has the value 0 or 1.

BUILDERS

A composition of the invention may contain one or more builders. Builders enhance or maintain the cleaning efficiency of the surfactant, primarily by reducing water hardness. This is done either by sequestration or chelation (holding hardness minerals in solution), by precipitation (forming an insoluble substance), or by ion exchange (trading electrically charged particles).

Builders for use in the invention can be of the organic or inorganic type, or a mixture thereof.

Suitable inorganic builders include hydroxides, carbonates, sesquicarbonates, bicarbonates, silicates, zeolites, and mixtures thereof. Specific examples of such materials include sodium and potassium hydroxide, sodium and potassium carbonate, sodium and potassium bicarbonate, sodium sesquicarbonate, sodium silicate and mixtures thereof.

Suitable organic builders include polycarboxylates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or alkanolammonium salts are preferred. Specific examples of such materials include sodium and potassium citrates, sodium and potassium tartrates, the sodium and potassium salts of tartaric acid monosuccinate, the sodium and potassium salts of tartaric acid disuccinate, sodium and potassium ethylenediaminetetraacetates, sodium and potassium N(2-hydroxyethyl)- ethylenediamine triacetates, sodium and potassium nitrilotriacetates and sodium and potassium N-(2-hydroxyethyl)-nitrilodiacetates. Polymeric polycarboxylates may also be used, such as polymers of unsaturated monocarboxylic acids (e.g. acrylic, methacrylic, vinylacetic, and crotonic acids) and/or unsaturated dicarboxylic acids (e.g. maleic, fumaric, itaconic, mesaconic and citraconic acids and their anhydrides). Specific examples of such materials include polyacrylic acid, polymaleic acid, and copolymers of acrylic and maleic acid. The polymers may be in acid, salt or partially neutralised form and may suitably have a molecular weight (Mw) ranging from about 1 ,000 to 100,000, preferably from about 2,000 to about 85,000, and more preferably from about 2,500 to about 75,000.

Mixtures of any of the above described materials may also be used. Preferred builders for use in the invention may be selected from polycarboxylates (e.g. citrates) in acid and/or salt form and mixtures thereof. Builder, when included, may be present in an amount ranging from about 0.1 to about 20%, preferably from about 0.5 to about 15%, more preferably from about 1 to about 10% (by weight based on the total weight of the composition).

TRANSITION METAL ION CHELATING AGENTS

A composition of the invention may contain one or more chelating agents for transition metal ions such as iron, copper and manganese. Such chelating agents may help to improve the stability of the composition and protect for example against transition metal catalyzed decomposition of certain ingredients.

Suitable transition metal ion chelating agents include phosphonates, in acid and/or salt form. When utilized in salt form, alkali metal (e.g. sodium and potassium) or

alkanolammonium salts are preferred. Specific examples of such materials include aminotris(methylene phosphonic acid) (ATMP), 1-hydroxyethylidene diphosphonic acid (HEDP) and diethylenetriamine penta(methylene phosphonic acid (DTPMP) and their respective sodium or potassium salts. HEDP is preferred. Mixtures of any of the above described materials may also be used.

Transition metal ion chelating agents, when included, may be present in an amount ranging from about 0.1 to about 10%, preferably from about 0.5 to about 3% (by weight based on the total weight of the composition).

FATTY ACID

A composition of the invention will preferably contain one or more fatty acids and / or salts thereof.

Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow). The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.

Mixtures of any of the above described materials may also be used.

Fatty acids and/or their salts, when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).

For formula accounting purposes, in the formulation, fatty acids and/or their salts (as defined above) are not included in the level of surfactant or in the level of builder.

POLYMERIC CLEANING BOOSTERS

To further improve the environmental profile of liquid laundry detergents it may be preferred in some cases to reduce the volume of laundry detergent dosed per wash-load and to add various highly weight efficient ingredients to the composition to boost cleaning performance. In addition to the soil release polymers of the invention described above, a composition of the invention will preferably contain one or more additional polymeric cleaning boosters such as anti-redeposition polymers.

Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil. Suitable soil release polymers for use in the invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. Preferred alkoxylated polyethyleneimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M _w ). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated

polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone. Mixtures of any of the above described materials may also be used.

When included, a composition of the invention will preferably comprise from 0.25 to 8%, more preferably from 0.5 to 6% (by weight based on the total weight of the composition) of one or more anti-redeposition polymers such as, for example, the alkoxylated polyethyleneimines which are described above.

SOIL RELEASE POLYMERS

Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing. The adsorption of a SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.

SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped. The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (M _w ) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.

SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate. Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, Ci-C4 alkylcelluloses and C ₄ hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example C1-C6 vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (I):

in which R ¹ and R ² independently of one another are X-(OC2H4) _n -(OC3H6) _{m ;}

in which X is C1-4 alkyl and preferably methyl;

n is a number from 12 to 120, preferably from 40 to 50;

m is a number from 1 to 10, preferably from 1 to 7; and

a is a number from 4 to 9.

Because they are averages, m, n and a are not necessarily whole numbers for the polymer in bulk.

Mixtures of any of the above described materials may also be used.

The overall level of SRP, when included, may range from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the composition).

Suitable soil release polymers are described in greater detail in U. S. Patent Nos.

5,574,179; 4,956,447; 4,861 ,512; 4,702,857, WO 2007/079850 and WO2016/005271. If employed, soil release polymers will typically be incorporated into the liquid laundry detergent compositions herein in concentrations ranging from 0.01 percent to 10 percent, more preferably from 0.1 percent to 5 percent, by weight of the composition.

POLYMERIC THICKENERS

A composition of the invention may comprise one or more polymeric thickeners. Suitable polymeric thickeners for use in the invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of a monomer mixture including at least one acidic vinyl monomer, such as (meth)acrylic acid (i.e. methacrylic acid and/or acrylic acid); and at least one associative monomer. The term“associative monomer” in the context of this invention denotes a monomer having an ethylenically unsaturated section (for addition

polymerization with the other monomers in the mixture) and a hydrophobic section. A preferred type of associative monomer includes a polyoxyalkylene section between the ethylenically unsaturated section and the hydrophobic section. Preferred HASE copolymers for use in the invention include linear or crosslinked copolymers that are prepared by the addition polymerization of (meth)acrylic acid with (i) at least one associative monomer selected from linear or branched C8-C40 alkyl (preferably linear C12- C22 alkyl) polyethoxylated (meth)acrylates; and (ii) at least one further monomer selected from C1-C4 alkyl (meth) acrylates, polyacidic vinyl monomers (such as maleic acid, maleic anhydride and/or salts thereof) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally comprises about 5 to about 100, preferably about 10 to about 80, and more preferably about 15 to about 60 oxyethylene repeating units.

Mixtures of any of the above described materials may also be used.

When included, a composition of the invention will preferably comprise from 0.1 to 5% (by weight based on the total weight of the composition) of one or more polymeric thickeners such as, for example, the HASE copolymers which are described above. FLUORESCENT AGENTS

It may be advantageous to include fluorescer in the compositions. 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 0.5 wt %.

Preferred classes of fluorescer are: Di-sty ryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra, Tinopal 5BMGX, and Blankophor (T rade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN.

Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]triazole, 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.

SHADING DYES

Shading dye can be used to improve the performance of the compositions. Preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.

Suitable and preferred classes of dyes are discussed below.

Direct Dyes:

Direct dyes (otherwise known as substantive dyes) are the class of water soluble dyes which have an affinity for fibres and are taken up directly. Direct violet and direct blue dyes are preferred.

Preferably bis-azo or tris-azo dyes are used.

Most preferably, the direct dye is a direct violet of the following structures: wherein: ring D and E may be independently naphthyl or phenyl as shown;

Ri is selected from: hydrogen and Ci-C4-alkyl, preferably hydrogen;

R ₂ is selected from: hydrogen, Ci-C ₄ -alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl;

R ₃ and R ₄ are independently selected from: hydrogen and Ci-C ₄ -alkyl, preferably hydrogen or methyl;

X and Y are independently selected from: hydrogen, Ci-C ₄ -alkyl and Ci-C ₄ -alkoxy;

preferably the dye has X= methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2. Preferred dyes are direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99. Bis-azo copper containing dyes for example direct violet 66 may be used. The benzidene based dyes are less preferred. Preferably the direct dye is present at 0.000001 to 1 wt% more preferably 0.00001 wt% to 0.0010 wt% of the composition.

In another embodiment the direct dye may be covalently linked to the photo-bleach, for example as described in W02006/024612.

Acid dyes:

Cotton substantive acid dyes give benefits to cotton containing garments. Preferred dyes and mixes of dyes are blue or violet. Preferred acid dyes are:

(i) azine dyes, wherein the dye is of the following core structure:

wherein R _a , R _t> , R _c and R _d are selected from: H, a branched or linear C1 to C7-alkyl chain, benzyl a phenyl, and a naphthyl; the dye is substituted with at least one SO ₃ or -COO group;

the B ring does not carry a negatively charged group or salt thereof; and the A ring may further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F, and NO2.

Preferred azine dyes are: acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98.

Other preferred non-azine acid dyes are acid violet 17, acid black 1 and acid blue 29. Preferably the acid dye is present at 0.0005 wt% to 0.01 wt% of the formulation. Hydrophobic dyes:

The composition may comprise one or more hydrophobic dyes selected from

benzodifuranes, methine, triphenylmethanes, napthalimides, pyrazole, napthoquinone, anthraquinone and mono-azo or di-azo dye chromophores. Hydrophobic dyes are dyes which do not contain any charged water solubilising group. Hydrophobic dyes may be selected from the groups of disperse and solvent dyes. Blue and violet anthraquinone and mono-azo dye are preferred.

Preferred dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77.

Preferably the hydrophobic dye is present at 0.0001 wt% to 0.005 wt% of the formulation. Basic dyes:

Basic dyes are organic dyes which carry a net positive charge. They deposit onto cotton. They are of particular utility for used in composition that contain predominantly cationic surfactants. Dyes may be selected from the basic violet and basic blue dyes listed in the Colour Index International.

Preferred examples include triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141.

Reactive dyes:

Reactive dyes are dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond. They deposit onto cotton.

Preferably the reactive group is hydrolysed or reactive group of the dyes has been reacted with an organic species for example a polymer, so as to the link the dye to this species. Dyes may be selected from the reactive violet and reactive blue dyes listed in the Colour Index International. Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96.

Dye conjugates:

Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces. Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in W02006/055787.

Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1 , acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.

Shading dye can be used in the absence of fluorescer, but it is especially preferred to use a shading dye in combination with a fluorescer, for example in order to reduce yellowing due to chemical changes in adsorbed fluorescer.

EXTERNAL STRUCTURANTS

Compositions of the invention may have their rheology further modified by use of one or more external structurants which form a structuring network within the composition. Examples of such materials include hydrogenated castor oil, microfibrous cellulose and citrus pulp fibre. The presence of an external structurant may provide shear thinning rheology and may also enable materials such as encapsulates and visual cues to be suspended stably in the liquid.

ENZYMES

A composition of the invention may comprise an effective amount of one or more enzyme selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present with

corresponding enzyme stabilizers. FRAGRANCES

Examples of fragrant components include aromatic, aliphatic and araliphatic

hydrocarbons having molecular weights from about 90 to about 250; aromatic, aliphatic and araliphatic esters having molecular weights from about 130 to about 250; aromatic, aliphatic and araliphatic nitriles having molecular weights from about 90 to about 250; aromatic, aliphatic and araliphatic alcohols having molecular weights from about 90 to about 240; aromatic, aliphatic and araliphatic ketones having molecular weights from about 150 to about 270; aromatic, aliphatic and araliphatic lactones having molecular weights from about 130 to about 290; aromatic, aliphatic and araliphatic ethers having molecular weights from about 150 to about 270; and condensation products of aldehydes and amines having molecular weights from about 180 to about 320.

Specific examples of fragrant components for use in the invention include: i) hydrocarbons, such as, for example, D-limonene, 3-carene, a-pinene, b-pinene, a- terpinene, g-terpinene, p-cymene, bisabolene, camphene, caryophyllene, cedrene, farnesene, longifolene, myrcene, ocimene, valencene, (E,Z)-1 ,3,5-undecatriene, styrene, and diphenylmethane; ii) aliphatic and araliphatic alcohols, such as, for example, benzyl alcohol, 1- phenylethyl alcohol, 2-phenylethyl alcohol, 3-phenylpropanol, 2-phenylpropanol, 2- phenoxyethanol, 2,2-dimethyl-3-phenylpropanol, 2,2-dimethyl-3-(3- methylphenyl)propanol, 1 ,1-dimethyl-2-phenylethyl alcohol, 1 ,1 -dimethyl-3- phenylpropanol, 1 -ethyl-1 -methyl-3-phenylpropanol, 2-methyl-5-phenylpentanol, 3- methyl-5-phenylpentanol, 3-phenyl-2-propen-1-ol, 4-methoxybenzyl alcohol, 1-(4- isopropylphenyl)ethanol, hexanol, octanol, 3-octanol, 2,6-dimethylheptanol, 2- methyl-2-heptanol, 2-methyl-2-octanol, (E)-2-hexenol, (E)- and (Z)-3-hexenol, 1- octen-3-ol, a mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3, 5,6,6- tetramethyl-4-methyleneheptan-2-ol, (E,Z)-2,6-nonadienol, 3,7-dimethyl-7- methoxyoctan-2-ol, 9-decenol, 10-undecenol, and 4-methyl-3-decen-5-ol; iii) cyclic and cycloaliphatic alcohols, such as, for example, 4-tert-butylcyclohexanol, 3,3,5-trimethylcyclohexanol, 3-isocamphylcyclohexanol, 2,6,9-trimethyl-Z2,Z5,E9- cyclododecatrien-1-ol, 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol, alpha, 3,3- trimethylcyclo-hexylmethanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol,

2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)-2-buten-1-o l, 2-ethyl-4-(2,2,3-trimethyl-

3-cyclopent-1-yl)-2-buten-1-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-

2-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol, 3,3-dimethyl-5- (2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol, 1-(2,2,6-trimethylcyclohexyl)pentan-

3-ol, and 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol; iv) aliphatic ketones and oximes thereof, such as, for example, 2-heptanone, 2- octanone, 3-octanone, 2-nonanone, 5-methyl-3-heptanone, 5-methyl-3-heptanone oxime, and 2,4,4,7-tetramethyl-6-octen-3-one; v) aliphatic sulfur-containing compounds, such as, for example, 3-methylthiohexanol, 3-methylthiohexyl acetate, 3-mercaptohexanol, 3-mercaptohexyl acetate, 3- mercaptohexyl butyrate, 3-acetylthiohexyl acetate, and 1-menthene-8-thiol; vi) aliphatic nitriles, such as, for example, 2-nonenenitrile, 2-tridecenenitrile, 2,12- tridecenenitrile, 3,7-dimethyl-2,6-octadienenitrile, and 3,7-dimethyl-6-octenenitrile; vii) aliphatic carboxylic acids and esters thereof, such as, for example, (E)- and (Z)-3- hexenylformate, ethyl acetoacetate, isoamyl acetate, hexyl acetate, 3,5,5- trimethylhexyl acetate, 3-methyl-2-butenyl acetate, (E)-2-hexenyl acetate, (E)- and (Z)-3-hexenyl acetate, octyl acetate, 3-octyl acetate, 1-octen-3-yl acetate, ethyl butyrate, butyl butyrate, isoamyl butyrate, hexylbutyrate, (E)- and (Z)-3-hexenyl isobutyrate, hexyl crotonate, ethylisovalerate, ethyl-2-methyl pentanoate, ethyl hexanoate, allyl hexanoate, ethyl heptanoate, allyl heptanoate, ethyl octanoate, ethyl-(E,Z)-2,4-decadienoate, methyl-2-octinate, methyl-2-noninate, allyl-2-isoamyl oxyacetate, and methyl-3, 7-dimethyl-2,6-octadienoate; viii) acyclic terpene alcohols, such as, for example, citronellol; geraniol; nerol; linalool; lavandulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7- octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-

5.7-octadien-2-ol; 2,6-dimethyl-3,5-octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol;

3.7-dimethyl-1 ,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; as well as formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates thereof; ix) cyclic terpene alcohols, such as, for example, menthol, isopulegol, alpha-terpineol, terpinen-4-ol, menthan-8-ol, menthan-1-ol, menthan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambrinol, vetiverol, guaiol, and the formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates and 3-methyl-2-butenoates of alpha-terpineol, terpinen-4-ol, methan-8-ol, methan-1-ol, methan-7-ol, borneol, isoborneol, linalool oxide, nopol, cedrol, ambrinol, vetiverol, and guaiol; x) cyclic and cycloaliphatic ethers, such as, for example, cineole, cedryl methyl ether, cyclododecyl methyl ether, (ethoxymethoxy)cyclododecane; alpha-cedrene epoxide, 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan, 3a-ethyl-6,6,9a- trimethyldodecahydronaphtho[2,1-b]furan, 1 ,5,9-trimethyl-13-oxabicyclo[10.1.0]- trideca-4, 8-diene, rose oxide and 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1- methylpropyl)-1 ,3-dioxane; xi) cyclic ketones, such as, for example, 4-tert-butylcyclohexanone, 2,2,5-trimethyl-5- pentylcyclopentanone, 2-heptylcyclopentanone, 2-pentylcyclopentanone, 2- hydroxy-3-methyl-2-cyclopenten-1-one, 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1- one, 3-methyl-2-pentyl-2-cyclopenten-1-one, 3-methyl-4-cyclopentadecenone, 3- methyl-5-cyclopentadecenone, 3-methylcyclopentadecanone, 4-(1 -eth oxy vinyl )- 3,3,5,5-tetramethylcyclohexanone, 4-tert-pentylcyclohexanone, 5-cyclohexadecen-

1 -one, 6,7-dihydro-1 , 1 ,2,3,3-pentamethyl-4(5H)-indanone, 5-cyclohexadecen-1 - one, 8-cyclohexadecen-1-one, 9-cycloheptadecen-1-one and cyclopentadecanone; xii) esters of cyclic alcohols, such as, for example, 2-tert-butylcyclohexyl acetate, 4-tert- butylcyclohexyl acetate, 2-tert-pentylcyclohexyl acetate, 4-tert-pentylcyclohexyl acetate, decahydro-2-naphthyl acetate, 3-pentyltetrahydro-2H-pyran-4-yl acetate, decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate, 4,7-methano-3a,4,5,6,7,7a- hexahydro-5 or 6-indenyl acetate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6- indenyl propionate, 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl-isobutyrate and 4,7-methanooctahydro-5 or 6-indenyl acetate; xii) esters of cycloaliphatic carboxylic acids, such as, for example, allyl 3-cyclohexyl- propionate, allyl cyclohexyl oxyacetate, methyl dihydrojasmonate, methyl jasmonate, methyl 2-hexyl-3-oxocyclopentanecarboxylate, ethyl 2-ethyl-6,6- dimethyl-2-cyclohexenecarboxylate, ethyl 2,3,6,6-tetramethyl-2- cyclohexenecarboxylate and ethyl 2-methyl-1 ,3-dioxolane-2-acetate; xiv) esters of araliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate, benzyl propionate, benzyl isobutyrate, benzyl isovalerate, 2- phenylethyl acetate, 2-phenylethyl propionate, 2-phenylethyl isobutyrate, 2- phenylethyl isovalerate, 1-phenylethyl acetate, otrichloromethylbenzyl acetate, a,a- dimethylphenylethyl acetate, a,a-dimethylphenylethyl butyrate, cinnamyl acetate, 2- phenoxyethyl isobutyrate and 4-methoxybenzyl acetate; xv) araliphatic ethers and their acetals, such as, for example, 2-phenylethyl methyl ether, 2-phenylethyl isoamyl ether, 2-phenyethyl cyclohexyl ether, 2-phenylethyl-1- ethoxyethyl ether, phenylacetaldehyde dimethyl acetal, phenylacetaldehyde diethyl acetal, 2-phenylpropionaldehyde dimethyl acetal, phenylacetaldehyde glycerol acetal, 2,4,6-trimethyl-4-phenyl-1 ,3-dioxane, 4,4a,5,9b-tetrahydroindeno[1 ,2-d]-m- dioxin and 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1 ,2-d]-m-dioxin; xvi) aromatic and araliphatic carboxylic acids and esters thereof, such as, for example, benzoic acid, phenylacetic acid, methyl benzoate, ethyl benzoate, hexyl benzoate, benzyl benzoate, methyl phenylacetate, ethyl phenylacetate, geranyl phenylacetate, phenylethyl phenylacetate, methyl cinnamate, ethyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, cinnamyl cinnamate, allyl phenoxyacetate, methyl salicylate, isoamyl salicylate, hexyl salicylate, cyclohexyl salicylate, cis-3-hexenyl salicylate, benzyl salicylate, phenylethyl salicylate, methyl 2,4-dihydroxy-3,6- dimethylbenzoate, ethyl 3-phenylglycidate and ethyl 3-methyl-3-phenylglycidate; xvii) nitrogen-containing aromatic compounds, such as, for example, 2,4,6-trinitro-1 ,3- dimethyl-5-tert-butylbenzene, 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone, cinnamonitrile, 5-phenyl-3-methyl-2-pentenonitrile, 5-phenyl-3-methylpentanonitrile, methyl anthranilate, methyl-N-methylanthranilate, Schiff's bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert.- butylphenyl)propanal or 2,4-dimethyl-3-cyclohexene carbaldehyde, 6- isopropylquinoline, 6-isobutylquinoline, 6-sec-butylquinoline, indole, skatole, 2- methoxy-3-isopropylpyrazine and 2-isobutyl-3-methoxypyrazine; xviii) phenols, phenyl ethers and phenyl esters, such as, for example, estragole,

anethole, eugenol, eugenyl methyl ether, isoeugenol, isoeugenol methyl ether, thymol, carvacrol, diphenyl ether, beta-naphthyl methyl ether, beta-naphthyl ethyl ether, beta-naphthyl isobutyl ether, 1 ,4-dimethoxybenzene, eugenyl acetate, 2- methoxy-4-methylphenol, 2-ethoxy- 5-(1-propenyl)phenol and p-cresyl

phenylacetate; xix) heterocyclic compounds, such as, for example, 2,5-dimethyl-4-hydroxy-2H-furan-3- one, 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one, 3-hydroxy-2-methyl-4H-pyran-4- one, 2-ethyl-3-hydroxy-4H-pyran-4-one; xx) lactones, such as, for example, 1 ,4-octanolide, 3-methyl-1 ,4-octanolide, 1 ,4- nonanolide, 1 ,4-decanolide, 8-decen-1 ,4-olide, 1 ,4-undecanolide, 1 ,4-dodecanolide, 1 ,5-decanolide, 1 ,5-dodecanolide, 1 ,15-pentadecanolide, cis- and trans-1 '- pentadecen-1 ,15-olide, cis- and trans-12-pentadecen-1 ,15-olide, 1 ,16- hexadecanolide, 9-hexadecen-1 ,16-olide, 10-oxa-1 ,16-hexadecanolide, 11-oxa-

1 ,16-hexadecanolide, 12-oxa-1 ,16-hexadecanolide, ethylene-1 , 12-dodecanedioate, ethylene-1 , 13-tridecanedioate, coumarin, 2,3-dihydrocoumarin, and

octahydrocoumarin.

Naturally occurring exudates such as essential oils extracted from plants may also be used as fragrant components in the invention. Essential oils are usually extracted by processes of steam distillation, solid-phase extraction, cold pressing, solvent extraction, supercritical fluid extraction, hydrodistillation or simultaneous distillation-extraction.

Essential oils may be derived from several different parts of the plant, including for example leaves, flowers, roots, buds, twigs, rhizomes, heartwood, bark, resin, seeds and fruits. The major plant families from which essential oils are extracted include Asteraceae, Myrtaceae, Lauraceae, Lamiaceae, Myrtaceae, Rutaceae and Zingiberaceae. The oil is "essential" in the sense that it carries a distinctive scent, or essence, of the plant. Essential oils are understood by those skilled in the art to be complex mixtures which generally consist of several tens or hundreds of constituents. Most of these constituents possess an isoprenoid skeleton with 10 atoms of carbon (monoterpenes), 15 atoms of carbon (sesquiterpenes) or 20 atoms of carbon (diterpenes). Lesser quantities of other constituents can also be found, such as alcohols, esters and phenols. However, an individual essential oil is usually considered as a single ingredient in the context of practical fragrance formulation. Therefore, an individual essential oil may be considered as a single fragrant component for the purposes of this invention.

Specific examples of essential oils for use as fragrant components in the invention include cedarwood oil, juniper oil, cumin oil, cinnamon bark oil, camphor oil, rosewood oil, ginger oil, basil oil, eucalyptus oil, lemongrass oil, peppermint oil, rosemary oil, spearmint oil, tea tree oil, frankincense oil, chamomile oil, clove oil, jasmine oil, lavender oil, rose oil, ylang-ylang oil, bergamot oil, grapefruit oil, lemon oil, lime oil, orange oil, fir needle oil, galbanum oil, geranium oil, grapefruit oil, pine needle oil, caraway oil, labdanum oil, lovage oil, marjoram oil, mandarin oil, clary sage oil, nutmeg oil, myrtle oil, clove oil, neroli oil, patchouli oil, sandalwood oil, thyme oil, verbena oil, vetiver oil and wintergreen oil.

The number of different fragrant components contained in the fragrance formulation (f1 ) will generally be at least 4, preferably at least 6, more preferably at least 8 and most preferably at least 10, such as from 10 to 200 and more preferably from 10 to 100.

Typically, no single fragrant component will comprise more than 70% by weight of the total weight of fragrance formulation (f1 ). Preferably no single fragrant component will comprise more than 60% by weight of the total weight of fragrance formulation (f1 ) and more preferably no single fragrant component will comprise more than 50% by weight of the total weight of fragrance formulation (f 1 ).

The term“fragrance formulation” in the context of this invention denotes the fragrant components as defined above, plus any optional excipients. Excipients may be included within fragrance formulations for various purposes, for example as solvents for insoluble or poorly-soluble components, as diluents for the more potent components or to control the vapour pressure and evaporation characteristics of the fragrance formulation.

Excipients may have many of the characteristics of fragrant components but they do not have strong odours in themselves. Accordingly, excipients may be distinguished from fragrant components because they can be added to fragrance formulations in high proportions such as 30% or even 50% by weight of the total weight of the fragrance formulation without significantly changing the odour quality of the fragrance formulation. Some examples of suitable excipients include ethanol, isopropanol, diethylene glycol monoethyl ether, dipropylene glycol, diethyl phthalate and triethyl citrate. Mixtures of any of the above described materials may also be suitable.

A suitable fragrance formulation (f1 ) for use in the invention comprises a blend of at least 10 fragrant components selected from hydrocarbons; aliphatic and araliphatic alcohols; aliphatic carboxylic acids and esters thereof; acyclic terpene alcohol; cyclic and cycloaliphatic ethers; esters of cyclic alcohols; esters of araliphatic alcohols and aliphatic carboxylic acids; araliphatic ethers and their acetals; aromatic and araliphatic ketones and aromatic and araliphatic carboxylic acids and esters thereof; as are further described and exemplified above.

The content of fragrant components preferably ranges from 50 to 100%, more preferably from 60 to 100% and most preferably from 75 to 100% by weight based on the total weight of fragrance formulation (f1 ); with one or more excipients (as described above) making up the balance of the fragrance formulation (f1 ) as necessary.

Fragrance formulation (f1 ) is in the form of free droplets dispersed in the composition.

The term“free droplets” in the context of this invention denotes droplets which are not entrapped within discrete polymeric microparticles.

In a typical liquid laundry detergent composition according to the invention the level of fragrance formulation (f1 ) will generally range from 0.1 to 0.75%, and preferably ranges from 0.3 to 0.6% (by weight based on the total weight of the composition).

MICROCAPSULES

One type of microparticle suitable for use in the invention is a microcapsule.

Microencapsulation may be defined as the process of surrounding or enveloping one substance within another substance on a very small scale, yielding capsules ranging from less than one micron to several hundred microns in size. The material that is encapsulated may be called the core, the active ingredient or agent, fill, payload, nucleus, or internal phase. The material encapsulating the core may be referred to as the coating, membrane, shell, or wall material.

Microcapsules typically have at least one generally spherical continuous shell

surrounding the core. The shell may contain pores, vacancies or interstitial openings depending on the materials and encapsulation techniques employed. Multiple shells may be made of the same or different encapsulating materials, and may be arranged in strata of varying thicknesses around the core. Alternatively, the microcapsules may be asymmetrically and variably shaped with a quantity of smaller droplets of core material embedded throughout the microcapsule.

The shell may have a barrier function protecting the core material from the environment external to the microcapsule, but it may also act as a means of modulating the release of core materials such as fragrance. Thus, a shell may be water soluble or water swellable and fragrance release may be actuated in response to exposure of the microcapsules to a moist environment. Similarly, if a shell is temperature sensitive, a microcapsule might release fragrance in response to elevated temperatures. Microcapsules may also release fragrance in response to shear forces applied to the surface of the microcapsules.

A preferred type of polymeric microparticle suitable for use in the invention is a polymeric core-shell microcapsule in which at least one generally spherical continuous shell of polymeric material surrounds a core containing the fragrance formulation (f2). The shell will typically comprise at most 20% by weight based on the total weight of the

microcapsule. The fragrance formulation (f2) will typically comprise from about 10 to about 60% and preferably from about 20 to about 40% by weight based on the total weight of the microcapsule. The amount of fragrance (f2) may be measured by taking a slurry of the microcapsules, extracting into ethanol and measuring by liquid

chromatography.

Polymeric core-shell microcapsules for use in the invention may be prepared using methods known to those skilled in the art such as coacervation, interfacial polymerization, and polycondensation. The process of coacervation typically involves encapsulation of a generally water- insoluble core material by the precipitation of colloidal material(s) onto the surface of droplets of the material. Coacervation may be simple e.g. using one colloid such as gelatin, or complex where two or possibly more colloids of opposite charge, such as gelatin and gum arabic or gelatin and carboxymethyl cellulose, are used under carefully controlled conditions of pH, temperature and concentration.

Interfacial polymerisation typically proceeds with the formation of a fine dispersion of oil droplets (the oil droplets containing the core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsule and the dimensions of the dispersed droplets directly determine the size of the subsequent microcapsules.

Microcapsule shell-forming materials (monomers or oligomers) are contained in both the dispersed phase (oil droplets) and the aqueous continuous phase and they react together at the phase interface to build a polymeric wall around the oil droplets thereby to encapsulate the droplets and form core-shell microcapsules. An example of a core-shell microcapsule produced by this method is a polyurea microcapsule with a shell formed by reaction of diisocyanates or polyisocyanates with diamines or polyamines.

Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of precondensate of polymeric materials under appropriate conditions of agitation to produce capsules of a desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in the condensate separating from solution and surrounding the dispersed core material to produce a coherent film and the desired microcapsules. An example of a core-shell microcapsule produced by this method is an aminoplast microcapsule with a shell formed from the polycondensation product of melamine (2,4,6-triamino-1 ,3,5-triazine) or urea with formaldehyde. Suitable cross-linking agents (e.g. toluene diisocyanate, divinyl benzene, butanediol diacrylate) may also be used and secondary wall polymers may also be used as appropriate, e.g. anhydrides and their derivatives, particularly polymers and co- polymers of maleic anhydride.

One example of a preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with an aminoplast shell surrounding a core containing the fragrance formulation (f2). More preferably such an aminoplast shell is formed from the polycondensation product of melamine with formaldehyde.

Polymeric microparticles suitable for use in the invention will generally have an average particle size between 100 nanometers and 50 microns. Particles larger than this are entering the visible range. Examples of particles in the sub-micron range include latexes and mini-emulsions with a typical size range of 100 to 600 nanometers. The preferred particle size range is in the micron range. Examples of particles in the micron range include polymeric core-shell microcapsules (such as those further described above) with a typical size range of 1 to 50 microns, preferably 5 to 30 microns. The average particle size can be determined by light scattering using a Malvern Mastersizer with the average particle size being taken as the median particle size D (0.5) value. The particle size distribution can be narrow, broad or multimodal. If necessary, the microcapsules as initially produced may be filtered or screened to produce a product of greater size uniformity.

Polymeric microparticles suitable for use in the invention may be provided with a deposition aid at the outer surface of the microparticle. Deposition aids serve to modify the properties of the exterior of the microparticle, for example to make the microparticle more substantive to a desired substrate. Desired substrates include cellulosics (including cotton) and polyesters (including those employed in the manufacture of polyester fabrics).

The deposition aid may suitably be provided at the outer surface of the microparticle by means of covalent bonding, entanglement or strong adsorption. Examples include polymeric core-shell microcapsules (such as those further described above) in which a deposition aid is attached to the outside of the shell, preferably by means of covalent bonding. While it is preferred that the deposition aid is attached directly to the outside of the shell, it may also be attached via a linking species.

Deposition aids for use in the invention may suitably be selected from polysaccharides having an affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an intrinsic affinity for cellulose or may have been derivatised or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked b glycan (generalised sugar) backbone structure with at least 4, and preferably at least 10 backbone residues which are b1-4 linked, such as a glucan backbone (consisting of b1-4 linked glucose residues), a mannan backbone (consisting of b1 -4 linked mannose residues) or a xylan backbone (consisting of b1 -4 linked xylose residues). Examples of such b1 -4 linked polysaccharides include xyloglucans, glucomannans, mannans, galactomannans, b(1-3),(1-4) glucan and the xylan family incorporating glucurono-, arabino- and glucuronoarabinoxylans. Preferred b1 -4 linked polysaccharides for use in the invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind seed xyloglucan (TXG) (which has a b1 -4 linked glucan backbone with side chains of a-D xylopyranose and b-D-galactopyranosyl-(1-2)-a-D-xylo-pyranose, both 1-6 linked to the backbone); and galactomannans of plant origin such as locust bean gum (LBG) (which has a mannan backbone of b1 -4 linked mannose residues, with single unit galactose side chains linked a1-6 to the backbone).

Also suitable are polysaccharides which may gain an affinity for cellulose upon hydrolysis, such as cellulose mono-acetate; or modified polysaccharides with an affinity for cellulose such as hydroxypropyl cellulose, hydroxypropyl methylcellulose, hydroxyethyl

methylcellulose, hydroxypropyl guar, hydroxyethyl ethylcellulose and methylcellulose.

Deposition aids for use in the invention may also be selected from phthalate containing polymers having an affinity for polyester. Such phthalate containing polymers may have one or more nonionic hydrophilic segments comprising oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments comprising terephthalate groups. Typically, the oxyalkylene groups will have a degree of polymerization of from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. A suitable example of a phthalate containing polymer of this type is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide terephthalate.

Mixtures of any of the above described materials may also be suitable.

Deposition aids for use in the invention will generally have a weight average molecular weight (M _w ) in the range of from about 5 kDa to about 500 kDa, preferably from

about 10 kDa to about 500 kDa and more preferably from about 20 kDa to about 300 kDa. One example of a particularly preferred polymeric core-shell microcapsule for use in the invention is an aminoplast microcapsule with a shell formed by the polycondensation of melamine with formaldehyde; surrounding a core containing the fragrance formulation (f2); in which a deposition aid is attached to the outside of the shell by means of covalent bonding. The preferred deposition aid is selected from b1-4 linked polysaccharides, and in particular the xyloglucans of plant origin, as are further described above.

The present inventors have surprisingly observed that it is possible to reduce the total level of fragrance included in the composition of the invention without sacrificing the overall fragrance experience delivered to the consumer at key stages in the laundry process. A reduction in the total level of fragrance is advantageous for cost and environmental reasons.

Accordingly, the total amount of fragrance formulation (f1 ) and fragrance formulation (f2) in the composition of the invention suitably ranges from 0.5 to 1.4%, preferably from 0.5 to 1.2%, more preferably from 0.5 to 1% and most preferably from 0.6 to 0.9% (by weight based on the total weight of the composition).

The weight ratio of fragrance formulation (f1 ) to fragrance formulation (f2) in the composition of the invention preferably ranges from 60:40 to 45:55. Particularly good results have been obtained at a weight ratio of fragrance formulation (f1 ) to fragrance formulation (f2) of around 50:50.

The fragrance (f1 ) and fragrance (f2) are typically incorporated at different stages of formation of the composition of the invention. Typically, the discrete polymeric microparticles (e.g. microcapsules) entrapping fragrance formulation (f2) are added in the form of a slurry to a warmed base formulation comprising other components of the composition (such as surfactants and solvents). Fragrance (f1 ) is typically post-dosed later after the base formulation has cooled.

FURTHER OPTIONAL INGREDIENTS

A composition of the invention may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include foam boosting agents, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlisers and/or opacifiers, and shading dye. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the composition).

PACKAGING AND DOSING

A composition of the invention may be packaged as unit doses in polymeric film soluble in the wash water. Alternatively, a composition of the invention may be supplied in multidose plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.

A method of laundering fabric using a composition of the invention will usually involve diluting the dose of detergent composition with water to obtain a wash liquor, and washing fabrics with the wash liquor so formed.

The dilution step preferably provides a wash liquor which comprises inter alia from about 3 to about 20 g/wash of detersive surfactants (as are further defined above).

In automatic washing machines the dose of detergent composition is typically put into a dispenser and from there it is flushed into the machine by the water flowing into the machine, thereby forming the wash liquor. From 5 up to about 65 litres of water may be used to form the wash liquor depending on the machine configuration. The dose of detergent composition may be adjusted accordingly to give appropriate wash liquor concentrations. For example, dosages for a typical front-loading washing machine (using 10 to 15 litres of water to form the wash liquor) may range from about 10 ml to about 60 ml, preferably about 15 to 40 ml. Dosages for a typical top-loading washing machine (using from 40 to 60 litres of water to form the wash liquor) may be higher, e.g. up to about 100 ml.

A subsequent aqueous rinse step and drying the laundry is preferred. EXAMPLES

Example 1

Formulation according to the invention

Example 2

Base Fragrance Formulation

Example 3

Physical Stability

1. Prepare product formulation making note of the ingredient amounts added, order of addition, mixing time, mixer configuration, process temperature and pH.

2. Dispense product into storage container, preferably transparent for ease of visual observation.

3. Product may be stored at specific temperatures or subject to temperature cycling e.g. 5°C, ambient, 40°C and then periodically assessed for instability.

4. Products will be declared unstable if there is visual evidence of macroscopic phase separation, creaming, separation into multiple layers, etc.

5. Other measures of instability may also be used for example, changes in rheology or drifts in pH especially where these may impact in-use properties such as ease of pouring or ingredient performance.

Example 4

Stability Test Protocol

A high throughput quantitative suspension test conducted in micro titre plates (MTP) and based upon a scaled down version of the classical suspension testing encompassed in BS EN 1276: 1997 is used for evaluating the bactericidal activity of the mixed biocide systems. The approach can be used with any bacterium but in this example the bacterial strain P. aeruginosa ATCC 15442 is used exclusively.

The scaled down version of the full EN 1276 assay is carried out using a Hamilton robotics automated liquid handling system with a 96-well head. The practical differences between the two protocols as summarised in Table 1 below. Table 1 : Comparison of BS EN 1276 and the scaled down MTP method

In the MTP suspension test the following reagents are used:- Neutralizer: Tween 80, 60 g/L; lecithin, 6 g/L; L-histidine, 2 g/L; sodium thiosulphate, 10 g/L; sterilised by autoclaving.

Recover media: Tryptone soya broth 30 g/L sterilised by autoclaving.

Bacterial suspension media: Bacteriological Tryptone Powder, 1 g/L; sodium chloride

8.5 g/L sterilised by autoclaving. Bacterial strain used: Pseudomonas aeruginosa ATCC 15442

Contact Time: 60 minutes ± 10 seconds

Test Temperature: 37°C ± 1 °C

Interfering Substance: Dirty conditions: 0.3% w/v bovine serum albumin in test

Interfering substance prepared in sterile distilled water at 3% and sterilised by

autoclaving.

Temperature and duration of incubation: 37°C ± 1 °C for 20 hour duration

Stock concentrations of formulations given in Table 1 were prepared in 60 ml sterilins and dilutions prepared in a 96-well deep well plates, all stocks and dilutions were prepared using water of standard hardness (40°FH, see EN 1276 for recipe).

Typically, the testing was managed such that the product concentration varied between in 7.0 and 2.0 g/L in 0.5g/L steps via 10 dilutions across 11 cells of the MTP or between 5.0 and 1.5 g/l in 0.5g/L steps via 7 dilutions across 8 cells depending on how the MTP’s are configured.

Bacterial suspensions were prepared from fresh plate cultures on tryptone soya agar and incubated for 18 hours at 37°C. Suspensions were made up to a density of 1.7 McFarland units (1 -1.5 x 10 ⁸ cfu/ml) in tryptone diluent.

Formulations were prepared as detailed above and diluted in a 2.2 ml deep well plate using water of standard hardness for all dilutions. Concentrations were made to allow for a 1.25 in test dilution. Controls of 1 % Virkon solution and water of standard hardness were used.

Upon transfer of the formulations into the test plate, 10OmI of interfering soil and 100 mI of bacterial suspension were transferred into an empty 96-well MTP mixed and left for a contact time of 2 minutes. A 60 mI volume of soil/bacteria was then transferred into the test plate mixed and left for a contact time of 60 minutes while the test plate was transferred to an incubator at 37°C. From the test plate 30 mI was aspirated from all wells and dispensed into the neutralising plate leaving for a contact time of 5 minutes. From the neutralising plate 30 mI from all wells was transferred into the first of 6 dilution plates from here 1 :10 serial dilutions of 30 mI across all wells were made into the remaining 6 dilution plates containing 270 mI tryptic soy broth.

Plates were read for end point optical density at 620nm at time 0 the plates were then incubated static at 37°C for 20 hours before taking an endpoint optical density read at 620nm. The OD values after 0 and 20 hours were used to calculate a AOD value for each formulation and concentration. Log reductions were determined using most probable number (MPN) with an optical density threshold of 0.2 OD units indicating re-growth. The concentration prior to the one at which this threshold is passed indicates the MPN of bacteria that a given concentration of the biocidal mixture and can kill at each Log dilution.

The [Product]MBC R aerag nosa (g/l ) is defined as the minimum biocidal concentration (MBC) at which the product has achieved a 5 Log reduction in the population of P. aeruginosa under the conditions specified in the test. The value quoted in the example is accurate to approximately 0.5 g/L.

In further examples, the bacterium, the contact time between product and bacteria, temperature, the water hardness and concentration of interfering substance (BSA) may be varied according to relevance to consumer washing conditions. Where deviation from the protocol given in Table 1 is made then specific reference to the conditions is given within the appropriate example.

Example 5

Available fragrance measurement by gas chromatography and mass spectrometer detection from formulation by solvent extraction.

Sample preparation

1g sample weighed accurately

Addition of 10 mis 90:10 isooctane:diethyl ether

Extract for 60 minutes by roller mixer.

Decant portion of extract to vial and inject to gas chromatograph. Chromatographic conditions

Column: HP5 (20m x 0.18mm x 0.18pm film thickness)

Oven program : 45°C for 0.5 minute to 250°C @ 20°C/minute

Injection details : 250°C Helium at constant flow of 1 ml/minute 10:1 split ratio Mass spectrometer details dependant of fragrance components.

Example 6

The polyamine used in this experiment was Lonzabac 12 commercially available from Lonza.