Composition

Abstract

A detergent composition comprising an alkoxylated dye and an alkyl ether sulfate, where the alkyl ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylate units, where the alcohol ether sulfate comprises less than 10% by weight of an alcohol ether sulfate having zero ethoxylate groups.

Description

TECHNICAL FIELD

[0001] The present invention relates to detergent compositions comprising improved surfactants. BACKGROUND

[0002] Despite the prior art, there remains a need for improved anionic surfactants for use in detergent compositions.

[0003] The unique color of a detergent composition can be a unique signature of the product for the consumer. There is a need to minimize color change when introducing improved anionic surfactants into colored detergent compositions. SUMMARY

[0004] Thus, in a first aspect, there is provided a detergent composition comprising an alkoxylated dye and an alkyl ether sulfate, wherein the alkyl ether sulfate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylate units, wherein the alcohol ether sulfate comprises less than 10 wt% of alcohol ether sulfate having zero ethoxylate groups.

[0005] Alcohol ether sulfates having a molar average of 2 to 4 ethoxylate groups are prepared by sulfation of the corresponding alcohol ethoxylate. The most widely used materials are based on linear or branched C12-C15 alcohols. Typically, the ethoxylation reaction to form the alcohol ethoxylate is base catalyzed using NaOH, KOH, or NaOCH3. This reaction produces a distribution of ethoxyl chain lengths in the alcohol ethoxylate. Narrow range ethoxylation provides a narrower distribution of ethoxyl chain lengths than NaOH, KOH, or NaOCH3. Most notably, narrow range ethoxylation produces a significantly lower fraction of material having exactly 0 or 1 ethoxylate groups.

[0006] We have surprisingly found that alkoxylated dyes perform more favorably when formulated with surfactants having a narrow range of ethoxylate distribution. In particular, they are more color stable. DETAILED DESCRIPTION

[0007] The alkyl ether sulfate has a molar average of 2.0 to 4.0 ethoxylate units and contains less than 10 wt% of alcohol ether sulfate having zero ethoxylate groups.

[0008] Preferably, the alcohol ether sulfate contains less than 5 wt% of alcohol ether sulfate having exactly zero ethoxylate groups.

[0009] Preferably, the alcohol ether sulfate contains less than 12 wt% of alcohol ether sulfate having exactly one ethoxylate group.

[0010] Preferably the alcohol ether sulphate has a molar average of 2.6 to 3.4, most preferably 2.8 to 3.2 ethoxylate units.

[0011] Preferably the composition comprises at least 60 wt% water of the composition.

[0012] Preferably the alkyl ether sulphate is present at 5-30 wt% of the composition.

[0013] Preferably the polyester-based soil release polymer is present at 0.1-2 wt% of the composition.

[0014] Preferably the composition is a liquid detergent composition.

[0015] Preferably the composition is a laundry liquid unit dose composition.

[0016] Preferably the composition comprises a C1214 alcohol ether sulphate wherein the ratio of C12:14 is 5:1 to 1 :20. More preferably the ratio of C12:14 is 4:1 to 1 :10, most preferably the ratio of C12:14 is 3:1 to 5:4.

[0017] Preferably the alkyl ether sulphate is present at 1-30 wt% of the composition.

[0018] Preferably the composition comprises a salt. Preferably the salt is selected from sodium chloride, potassium chloride and mixtures thereof.

[0019] Preferably the salt is present at 0.1-5 wt% of the composition. More preferably the salt is present at 0.8-4 wt% of the composition.

[0020] Preferably the composition comprises 0.1-3 wt% of a betaine, preferably cocamidopropyl betaine.

[0021] Alcohol ether sulfate The alcohol ether sulphate has the following form: R2-O-(CH2CH2O) p SO3H wherein R2 is an alkyl group and p is a molar average and is 2.0 to 4.0. Preferably greater than 80 wt%, more preferably greater than 95 wt% of R2 is selected from C12 and C14 chains, preferably the chains are straight chain.

[0022] The structure of the alcohol ether sulphate having exactly zero ethoxylate groups has the following structure: R2-O-SO3H.

[0023] The alcohol ether sulphate is formed by sulphation of the corresponding alcohol ethoxylate. The alcohol ethoxylate is formed by ethoxylation of an alcohol using a narrow range ethoxylation catalyst.

[0024] Preferably the alcohol ether sulphate contains less than 10wt%, more preferably less than 4wt% of chains other than C12 and C14, most preferably less than 10wt% of C16, C18 and C20 chains.

[0025] Narrow range ethoxylation catalysts are described in EP3289790 (Procter & Gamble), EP1747183 (Hacros); Santacesatia et al Ind. Eng. Chem. Res. 1992, 31, 2419-2421; US4239917 (Conoco); Li et al ACS Omega. 2021 Nov 9; 6(44): 29774-29780; Hreczuch et al J. Am. Oil Chem. Soc. 1996, 73, 73-78 and WO2022 / 129374 (Unilever). Ca or Ba based catalysts are preferred, most preferably in combination with sulphuric acid.

[0026] Standard 3EO as described in the literature is not a disclosure of pure 3EO, in fact 100% pure 3EO is not commercially available. Instead what is described as 3EO is a mixture with different ethoxylation rates with an average of about 3. This 3EO is ethoxylated using KOH. In order to obtain a narrow range of ethoxylation distribution, a dedicated catalyst must be used.

[0027] The following is a comparison of standard 3EO and narrow range.

[0028] Preferably the sum (n-1, n, n+1) is greater than 50%, more preferably greater than 55% where n is 2 to 4 (n = average moles of ethoxylation).

[0029] Preferably the total level of 2EO, 3EO and 4EO in the total alkyl ether sulphate is greater than 50%, more preferably greater than 55% of the total alcohol ether sulphate as measured by GC with flame ionisation detection (FID).

[0030] Preferably the total proportion of 0EO and 1EO in the total alkyl ether sulphate is less than 25% of the total alcohol ether sulphate as measured by GC with flame ionisation detection (FID).

[0031] It will be appreciated that the measurements are made on the alcohol ethoxylate prior to sulphonation, but that sulphonation does not materially affect the ethoxylation profile.

[0032] The alcohol ether sulphate is also known as alkyl ether sulphate.

[0033] Alkoxylated dye The dye preferably has a maximum extinction coefficient of greater than 5000 L / mol / cm, preferably greater than 10000 L / mol / cm in the range of 400-700 nm.

[0034] The dye of the present application preferably has a maximum extinction coefficient of greater than 5000 L / mol / cm, preferably greater than 10000 L / mol / cm in the range of 400-700 nm.

[0035] The dye is an alkoxylated dye. The alkoxylated dye contains at least one polyalkoxyl containing group covalently bound to the chromophore. The polyalkoxyl containing group can be directly bound to the aromatic ring of the chromophore or more likely indirectly, for example via the N-atom of an amine or amide group. The polyalkoxyl can contain a linker moiety and have the following structure: - linker - (alkoxy) n The alkoxyl monomers preferably have 2-4 carbon atoms and can form mixed polyalkoxylates, such as polyalkoxylates containing ethoxylate, propoxylate and butoxylate monomers. Preferred are dyes with alkoxyl monomers of the same type. Preferred are dyes with ethoxyl monomers.

[0036] Alkoxylated dyes are described in WO 2022056205 (Milliken).

[0037] The blue dye is preferably selected from: and and equivalents thereof having different degrees of ethoxylation, preferably each ethoxyl chain having a molar average of 2 to 15 ethoxyl units.

[0038] Further preferred blue dyes are selected from: wherein R2, R3, X and Y are H or an organic group and at least one of the groups R2, R3, X and Y contains -[CH2CH2O] n H groups. Preferred examples are 1-amino-2-polyethyleneoxy-4-phenylamino-anthraquinone, 1-amino-2-methoxy-4-[-4-polyethyleneoxy-anilyl] anthraquinone, 1-amino-2-polyethyleneoxy-4-(2,4,6-trimethylphenylamino) anthraquinone and N,N'-di-alkoxyl-substituted 1,4-diaminoanthraquinone. More preferred is N,N'-di-alkoxyl-substituted 1,4-diaminoanthraquinone. Most preferably X=Y = H and R2and R3are -CH2CH2CH2O(CH2CH2O)2R1as described in US 7632682, examples 1 and 2.

[0039] The green dye is preferably selected from: ; And its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0040] The preferred red dye is selected from: ; ; And its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0041] Yellow dyes are preferably selected from: ; ; And its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0042] Purple dyes are preferably selected from: ; ; And its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0043] In -[ethoxy] n In this context, "n" typically refers to the average number of alkoxy monomers, where "n" can therefore represent the average value of the distribution. In this case, it is advantageous that the most prevalent molecular species have a number of -[ethoxy] groups corresponding to the distribution average "n". n Partial distributions. Further preferred are those distributions in which the molecular species having a higher molar percentage corresponding to the average number "n" of alkoxylation. For example, if "n" is 4, then distributions of 25% n=2, 50% n=4, and 25% n=6 are more preferred than distributions of 30% n=2, 40% n=4, and 30% n=6. This advantageously applies to the average number of alkoxy-monomers in the alkoxylated dye as a whole and / or the average number of alkoxy-monomers in individual polyalkoxy-containing groups.

[0044] The alkoxylated dye is preferably present in the composition at 0.001-2% by weight, more preferably 0.005-0.1% by weight.

[0045] Preferably, the liquid detergent has an optical density (1 cm) of 0.05 to 2, most preferably 0.1 to 0.4 at the maximum absorption in the range of 400 to 700 nm.

[0046] Blue and violet dyes are most preferred.

[0047] Surfactant The liquid detergent of the present application preferably comprises 2 to 60 wt.%, most preferably 4 to 30 wt.% of total surfactant. Preferred are anionic and non-ionic surfactants.

[0048] Anionic surfactants are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache, published by Surfactant Science Series, CRC press (1995). Preferred anionic surfactants are sulfonate and sulfate surfactants, preferably alkyl benzene sulfonates, alkyl sulfates and alkyl ether sulfates.

[0049] The anionic surfactants are preferably added to the detergent composition in the form of a salt. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of the anionic surfactant can be formed in situ by neutralizing the acid form of the surfactant with a base, such as sodium hydroxide, or an amine, such as mono-, di- or triethanolamine. The weight ratio is calculated for the protonated form of the surfactant. The ethoxy units in the anionic and non-ionic surfactants can be partially replaced by propoxy units.

[0050] Further examples of suitable anionic surfactants are rhamnolipids, alpha-olefin sulfonates, olefin sulfonates, alkenyl sulfonates, alkane-2,3-diyl bis(sulfates), hydroxyalkane sulfonates and disulfonates, fatty alcohol sulfates (FAS), paraffin sulfonates, ester sulfonates, sulfonated fatty acid glycerol esters, methyl ester sulfonate alkyl succinic acid or alkenyl succinic acid, dodecenyl / tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEM's, CITREM's, and diesters and monoesters of sulfosuccinic acid.

[0051] Examples of preferred non-ionic surfactants are alcohol ethoxylates and methyl ester ethoxylates. Preferably, the level of non-ionic surfactant in the formulation is below 2 wt.%. Preferred alcohol ethoxylates are C12 / 14 alcohol with a molar average of 7 to 9 ethoxylates and C16 / C18:1 alcohol ethoxylates with a molar average of 8 to 12 ethoxylates.

[0052] Linear alkylbenzene sulfonate salts are the preferred anionic surfactant other than alcohol ether sulfate.

[0053] Linear alkylbenzene sulfonate LAS (linear alkylbenzene sulfonate) is the preferred anionic surfactant.

[0054] A key intermediate compound in LAS production is the relevant alkene. These alkenes (olefins) can be produced by any of the methods described above and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, ocean carbon, etc.

[0055] While in the above methods, the olefin is alternatively processed by hydroformylation and oxidation to form linear alcohols, the olefin is reacted with benzene and then with a sulfonic acid to form LAS.

[0056] Linear alkylbenzene sulfonate salts having an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologous alkyl chains, each containing an aromatic ring sulfonated in the "para" position and attached to a linear alkyl chain at any position other than the terminal carbon. The linear alkyl chain preferably has a chain length of 11 to 15 carbon atoms, with the major material having a chain length of about C12. Each alkyl chain homolog is composed of a mixture of all possible sulfo-phenyl isomers except the 1-phenyl isomer. LAS is typically formulated into compositions in the acid form (i.e., HLAS) and then at least partially neutralized in situ. Preferably, the linear alkylbenzene sulfonate surfactant is present at 1 to 20 wt%, more preferably 2 to 15 wt%, most preferably 8 to 12 wt% of the composition.

[0057] Methyl ester ethoxylate (MEE) Preferred nonionic surfactants include methyl ester ethoxylates. Methyl ester ethoxylate surfactants are of the form: R3(-C=O)-O-(CH2CH2-O) n -CH3 where R3COO is a fatty acid moiety such as oleic acid, stearic acid, palmitic acid. The fatty acid nomenclature is to describe the fatty acid by 2 numbers A:B, where A is the number of carbons in the fatty acid and B is the number of double bonds it contains. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bond on the chain can be given in parentheses, oleic acid is 18:1(9), linoleic acid is 18:2(9,12), where 9 is the number of the carbon counting from the COOH end.

[0058] The integer n is the mole average number of ethoxylates.

[0059] Methyl ester ethoxylate (MEE) is described in Chapter 8 Synthesis, Properties, and Applications, pages 287-301 of Biobased Surfactants (2nd Edition) by G. A. Smith; Cox M. E. and Weerasooriva U, J. Am. Oil. Chem. Soc. vol 74 (1997), pages 847-859; Hreczuch et al., Tenside Surf. Det. Vol 28 (2001), pages 72-80; C. Kolano. Household and Personal Care Today (2012), pages 52-55; A. Hama et al., J. Am. Oil. Chem. Soc. Vol 72 (1995), pages 781-784. MEE can be produced using a calcium or magnesium based catalyst by reaction of a methyl ester with ethylene oxide. The catalyst can be removed or left in the MEE.

[0060] An alternative route of manufacture is transesterification of a methyl ester or esterification of a carboxylic acid with a polyethylene glycol capped at one end with a methyl group.

[0061] Methyl esters can be made by transesterification of methanol with triglycerides or esterification of methanol with fatty acids. Transesterification of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol 8, Article 101) and references therein. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide and sodium methoxide. Esterases and lipases can also be used. Triglycerides are naturally occurring in plant fats or oils, preferred sources are rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high stearic / high oleic sunflower oil, high oleic sunflower oil, inedible plant oils, tall oil and any mixture thereof and any derivative thereof. Oils from trees are known as tall oils. Used food cooking oil can be used. Triglycerides can also be obtained from algae, fungi, yeast or bacteria. Plant sources are preferred.

[0062] Distillation and fractionation processes can be used to produce methyl esters or carboxylic acids to produce the desired carbon chain distribution. Preferred sources of triglycerides are those containing less than 35 wt% polyunsaturated fatty acids in the oil prior to distillation, fractionation or hydrogenation.

[0063] Fatty acids and methyl esters can be obtained from oil and fat chemical suppliers such as Wilmar, KLK Oleo, Unilever oleochemical Indonesia. Biodiesel is a methyl ester and these sources can be used.

[0064] When the ESB is a MEE, it preferably has a molar average of 8 to 30 ethoxylate groups (EO), more preferably 10 to 20. Most preferred ethoxylates contain 12 to 18 EO.

[0065] Preferably, at least 10 wt%, more preferably at least 30 wt% of the total C18:1 MEE in the composition has 9 to 11 EO, even more preferably at least 10 wt% has exactly 10 EO. For example, when the MEE has a molar average of 10 EO, then at least 10 wt% of the MEE should consist of ethoxylates with 9, 10 and 11 ethoxylate groups.

[0066] The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). Most preferred ethoxylates have a molar average of 9 to 11 EO, even more preferably 10 EO. When the MEE has a molar average of 10 EO, then at least 10 wt% of the MEE should consist of ethoxylates with 9, 10 and 11 ethoxylate groups.

[0067] In case of a broader MEE contribution, it is preferred that at least 40 wt% of the total MEE in the composition is C18:1.

[0068] Furthermore, it is preferred that the MEE component also contains some C16 MEE.

[0069] Therefore, it is preferred that the total MEE component contains 5 to 50 wt% of the total MEE as C16 MEE. Preferably, the C16 MEE is more than 90 wt%, more preferably more than 95 wt% C16:0.

[0070] Furthermore, it is preferred that the total MEE component contains less than 15 wt%, more preferably less than 10 wt%, most preferably less than 5 wt% of the total MEE as polyunsaturated C18, i.e. C18:2 and C18:3. Preferably, C18:3 is present in less than 1 wt%, more preferably less than 0.5 wt%, most preferably substantially not present. The level of polyunsaturation can be controlled by distillation, fractionation or partial hydrogenation of the feedstock (triglyceride or methyl ester) or MEE.

[0071] Furthermore, it is preferred that the C18:0 component is less than 10 wt% of the total MEE present by weight.

[0072] Furthermore, it is preferred that the component with a carbon chain of 15 or shorter is less than 4 wt% of the total MEE present by weight.

[0073] Particularly preferred MEEs have 2 to 26 wt% C16:0 chains, 1 to 10 wt% C18:0 chains, 50 to 85 wt% C18:1 chains and 1 to 12 wt% C18:2 chains of the MEE.

[0074] Preferred sources of alkyl groups of the MEE include distilled palm oil-derived methyl esters and distilled high oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters of canola oil, methyl esters of high oleic sunflower oil, methyl esters of high oleic safflower oil and methyl esters of high oleic soybean oil.

[0075] High oleic oils are available from DuPont (Plenish high oleic soybean oil), Monsanto (Visitive Gold soybean oil), Dow (omega-9 canola oil, omega-9 sunflower oil), National Sunflower Association and Oilseeds International.

[0076] Preferably, greater than 80 wt% of the double bonds in the MEE are in the cis configuration.

[0077] Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0078] The methyl group of the methyl ester can be replaced by an ethyl or propyl group. Methyl is most preferred.

[0079] Preferably, the methyl ester ethoxylate comprises 0.1 to 95 wt% of the methyl ester ethoxylate of the composition. More preferably the composition comprises 2 to 40 wt% MEE and most preferably 4 to 30 wt% MEE.

[0080] Preferably, the composition comprises at least 50 wt% water, but this is dependent on the total surfactant content and adjusted accordingly.

[0081] The anionic surfactant weight is calculated as the protonated form.

[0082] Branched surfactant The composition of the present application preferably comprises a branched C8-11 alcohol ether sulphate surfactant of the form: RO-(EO) n SO3X where R is preferably a branched C8 to C11 alkyl chain (R), preferably C9 or C10; n is 1 to 6, preferably 2.5 to 5, most preferably 3.5 to 4.5; and X is a cation, preferably sodium or amine. The integer n is the molar average. EO represents an ethoxy group.

[0083] Preferably, the branched alcohol ether sulphate surfactant has the structure, wherein p and m are greater than 1, more preferably m is 4 and p is 2 or m = p+2.

[0084] Preferably, the branched alcohol ether sulphate is made from a Guerbet alcohol. Preferably, the alcohol used to make the branched alcohol ether sulphate surfactant has a single alkyl chain length and configuration greater than 80 mol%. Most preferred is a C10 branched alcohol ether sulphate on 2-propyl heptanol with 4 mol average ethoxylation.

[0085] Farbe et al discuss branched alcohols in the Alcohols, Aliphatic chapter of Ullmann's Encyclopedia of Industrial Chemistry.

[0086] Branched alcohols are commercially available from Sasol, Exxon and BASF.

[0087] Preferably, the branched surfactant comprises 1 to 20 wt% of the total surfactant in the composition.

[0088] Preferably, the branched surfactant comprises 0.05 to 3 wt% of the composition, taking into account the typical surfactant loading of the composition as a whole.

[0089] Preferably, the weight ratio of total anionic and / or nonionic surfactant to C8 to C11 branched alcohol ether sulphate is 100:1 to 30:1, more preferably 80:1 to 40:1.

[0090] Zwitterionic surfactant The composition can comprise 0 to 3 wt% of a zwitterionic surfactant.

[0091] Examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines, including C10-C14 alkyl dimethyl betaines and coco dimethyl amidopropyl betaine, C10 to C14 amine oxides and sulfo and hydroxy betaines, such as N-alkyl-N,N-dimethylammonio-1-propane sulfonate, where the alkyl group can be C10 to C14.

[0092] Surfactant ratio Preferably, the weight ratio of total ether sulphate surfactant to total anionic surfactant is 1 to 0.5, preferably 1 to 0.8.

[0093] Source of alkyl chain The alkyl chain of the surfactant is preferably obtained from a renewable source, preferably from a triglyceride. A renewable source is a renewable source in which the material is produced through the natural ecological cycle of a living species, preferably by a plant, an alga, a fungus, a yeast or a bacterium, more preferably a plant, an alga or a yeast.

[0094] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and trees. Oil from trees is called tall oil. Most preferably palm kernel oil and coconut oil are the sources. The desired C12:C14 ratio can be obtained by fractionation / distillation and mixing of components.

[0095] Algal oil is discussed in Saad M.G. et al. Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges. The production of triglycerides from biomass using yeast is described in Masri M. A. et al. Energy Environ. Sci., 2019, 12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents.

[0096] Inedible vegetable oils can be used, and are preferably selected from the group consisting of fruits and seeds of Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seeds), flaxseed, Pongamia pinnata (karanja), Hevea brasiliensis (rubber seeds), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa. L., Cerbera odollam (Seamango), Coriandrum sativum L. (coriander), Croton megalocarpus, Pilu, Crambe, Clove, Scheleichera triguga (kusum), Stillingia, Shorea robusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, algae, Argemone mexicana L.(Mexican prickly poppy), Putranjiva roxburghii (Happy tree), Soapnut (Sapindus mukorossi), Syringe (M. azedarach), Yellow oleander (Thevetia peruviana), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B. napus, Zanthoxylum bungeanum.

[0097] C12C14linear alcohols suitable as an intermediate step in the manufacture of C12C14ether sulfates can be obtained from many different sustainable sources. These include: Primary sugar Primary sugars are obtained from cane or beet and the like and can be fermented to form bioethanol. The bioethanol is then dehydrated to form bioethylene which is then olefin metathesized to form alkenes. These alkenes are then processed by hydroformylation or oxidation to linear alcohols.

[0098] An alternative method can be used which also utilizes primary sugars to form linear alcohols and in which the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are subsequently hydrolyzed to linear fatty acids which are then reduced to form linear alcohols.

[0099] Biomass Biomass, such as forestry products, rice hulls and straw and the like, can be processed by gasification to form syngas. By Fischer-Tropsch reaction, these materials are processed to alkanes which are subsequently dehydrogenated to form alkenes. These alkenes can be processed in the same manner as the alkenes described above [Primary sugars].

[0100] An alternative method converts the same biomass by steam explosion to polysaccharides which can be enzymatically degraded to secondary sugars. These secondary sugars are then fermented to form bioethanol which is subsequently dehydrated to form bioethylene. This bioethylene is then processed to linear alcohols as described above [Primary sugars].

[0101] Waste plastic Waste plastics are pyrolyzed to form pyrolysis oil. The pyrolysis oil is then fractionated to form linear alkanes which are subsequently dehydrogenated to form alkenes. These alkenes are processed as described above [Primary sugars].

[0102] Alternatively, the pyrolysis oil is cracked to form ethylene, which is then processed through olefin metathesis to form the desired alkene. These are then processed into linear alcohols as described above [Primary Sugars].

[0103] Municipal solid waste MSW is converted to syngas by gasification. From the syngas, it can be processed as described above [Primary Sugars], or it is converted to ethanol through an enzymatic process prior to dehydrogenation to ethylene. The ethylene can then be converted to linear alcohols through the Ziegler process.

[0104] MSW can also be converted to pyrolysis oil by gasification, which is then fractionated to form alkanes. These alkanes are then dehydrogenated to form alkenes, and then linear alcohols.

[0105] Ocean carbon There are various sources of carbon from marine communities such as seaweed and kelp. From such marine communities, triglycerides can be isolated from the source, and then hydrolyzed to form fatty acids, which are reduced to linear alcohols in the usual manner.

[0106] Alternatively, the feedstock can be isolated into polysaccharides, which are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol, which is then processed as described above [Primary Sugars].

[0107] Waste oil Waste oil (such as used cooking oil) can be physically isolated into triglycerides, which are broken down into linear fatty acids, and then linear alcohols as described above.

[0108] Alternatively, used cooking oil can undergo the Neste process, whereby the oil is catalytically cracked to form bioethylene. This is then processed as described above.

[0109] Methane capture Methane capture methods capture methane from landfills or fossil fuel production. The methane can be formed into syngas by gasification. The syngas can be processed as described above, whereby the syngas is converted to methanol (Fischer-Tropsch reaction), and then to alkenes, which are then converted to linear alcohols through hydroformylation oxidation.

[0110] Alternatively, the syngas can be converted to alkanes, and then to alkenes through Fischer-Tropsch and subsequent dehydrogenation.

[0111] Carbon capture Carbon dioxide can be captured by any of a number of well-known methods. Carbon dioxide can be converted to carbon monoxide by the reverse water gas shift reaction, and this can then be converted to synthesis gas using hydrogen in an electrolysis reaction. The synthesis gas is then processed as described above, and converted to methanol and / or alkanes prior to reaction to form olefins.

[0112] Alternatively, the captured carbon dioxide is mixed with hydrogen prior to enzymatic processing to form ethanol. This is the process developed by Lanzatech. From this, the ethanol is converted to ethylene, which is then processed to olefins and then as described above to linear alcohols.

[0113] The above process can also be used to obtain the C12 / 14 chains for C12 / 14 ether sulphates.

[0114] Preferably, the composition is visually clear.

[0115] Preferably, the composition contains 10 to 80 wt% water.

[0116] Preferably, the liquid detergent comprises 1 to 5 wt% ethanol. Liquid laundry detergent In the context of the present application, the term "laundry detergent" means a formulated composition intended for and capable of wetting and cleaning household laundry, such as clothes, linens, and other household textiles. It is an object of the present application to provide a composition capable of forming a liquid laundry detergent composition in the manner now described upon dilution.

[0118] In a preferred embodiment, the liquid composition is isotropic.

[0119] The term "linen" is generally used to describe certain types of laundry items, including bed sheets, pillow cases, towels, table cloths, napkins, and uniforms. The textile can include woven, non-woven, and knitted fabrics; and can include natural or synthetic fibers, such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers (such as nylon), acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends.

[0120] Examples of liquid laundry detergents include heavy duty liquid laundry detergents for use in the wash cycle of an automatic washing machine, as well as liquid rinse and liquid color care detergents, such as detergents suitable for washing delicate garments (e.g., those made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

[0121] In the context of the present application, the term "liquid" means that the continuous phase or major portion of the composition is liquid and that the composition is flowable at 15°C and above. Thus, the term "liquid" can include emulsions, suspensions and compositions having a flowable but more stiff consistency, referred to as gels or pastes. The viscosity of the composition is preferably from 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec -1 A pourable liquid detergent composition preferably has a viscosity of from 200 to 1,500 mPa.s, preferably from 200 to 700 mPa.s.

[0122] The composition according to the present application can suitably have an aqueous continuous phase. By "aqueous continuous phase" is meant a continuous phase based on water. Preferably, the composition comprises at least 50 wt% water, more preferably at least 70 wt% water.

[0123] The alkyl ether sulphate can be provided in a single raw material component or by way of a mixture of components.

[0124] When the composition comprises a mixture of C16 / 18 source material for the alkyl ether sulphate as well as the more traditional C12 alkyl chain length material, it is preferred that the C16 / 18 alkyl ether sulphate should make up at least 10 wt% of the total alkyl ether sulphate in the composition, more preferably at least 50 wt% of the alkyl ether sulphate, even more preferably at least 70 wt%, particularly preferably at least 90 wt%, most preferably at least 95 wt%.

[0125] The alcohol ethoxylate can be provided in a single raw material component or by way of a mixture of components.

[0126] Preferably, the choice and amount of surfactants is such that the composition and the diluted mixture are isotropic in nature. Alkoxylated oligoamine cleaning booster Preferably, the composition comprises an alkoxylated oligoamine cleaning booster.

[0128] The alkoxylated oligoamine cleaning booster is a polymer containing at least 2, preferably at least 4 nitrogen atoms, and most preferably at least 4 polyalkoxy groups, wherein the polyalkoxy groups contain from 10 to 30 individual alkoxy units. Preferably, at least one polyalkoxy group is directly attached to a nitrogen atom. Preferably, the alkoxylate groups are selected from ethoxy and propoxy groups, most preferably ethoxy. -[CH2CH2O] n -H.

[0129] Preferably, the alkoxylated oligoamine contains from 2 to 40, more preferably from 2 to 10, most preferably from 3 to 8 nitrogen atoms.

[0130] Such polymers are described in WO2023 / 287834 (DOW), WO2023 / 287835 (DOW), WO2023 / 287836 (DOW), WO2021 / 165493 (BASF), WO2021 / 165468 (BASF), WO2022 / 136389 (BASF), WO2022 / 136409 (BASF), WO2004 / 24858 (Procter and Gamble) and WO2021239547 (Unilever).

[0131] The alkoxylated oligoamine preferably contains permanent positive charges, wherein the positive charges are provided by quaternization of the nitrogen atoms of the amine.

[0132] Preferably, the charges are present when the alkoxylated oligoamine contains from 2 to 10, preferably from 3 to 6 nitrogen atoms. When the alkoxylated oligoamine contains permanent positive charges, it also contains anionic groups obtained by sulfation or sulfonation of the alkoxylate groups.

[0133] Preferably, more than or equal to 50 mol% of the nitrogen amines are quaternized, preferably with methyl groups. Preferably, the polymer contains from 3 to 10, more preferably from 3 to 6, most preferably from 3 to 5 quaternized nitrogen amines. Preferably, the alkoxylate groups are selected from ethoxylate and propoxylate groups, most preferably ethoxylate.

[0134] Preferably, the alkoxylated oligoamine contains ester (COO) groups within the structure, preferably placed such that when all esters are hydrolyzed, at least one, preferably all hydrolyzed fragments have a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

[0135] Preferably, the alkoxylated oligoamine is selected from alkoxylated polyethyleneimines, zwitterionic alkoxylated oligoamines and tetraester alkoxylated oligoamines.

[0136] Alkoxylated polyethyleneimines are made from polyethyleneimines which are materials consisting of ethyleneimine units -CH2CH2NH- and when branched, the hydrogens on the nitrogen are replaced by another ethyleneimine unit chain. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (Mw) of from about 300 to about 10000, preferably from about 500 to about 5000, most preferably from about 1000 to about 3000. w) polyethyleneimine backbone. The polyethyleneimine backbone can be linear or branched. It can be branched to the extent of being a dendrimer. In the case of alkoxylation of the nitrogen atoms, the preferred average degree of alkoxylation is from 10 to 30, preferably 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine in which the average degree of ethoxylation of each ethoxylated nitrogen atom in the polyethyleneimine backbone is from 10 to 30, preferably 15 to 25 ethoxy groups.

[0137] Zwitterionic alkoxylated oligoamines have the form: where R1 is C3 to C8 alkyl, X is (C2H4O) n Y groups, where n is from 15 to 30, preferably 18 to 25, where m is from 1 to 10, preferably 2, 3, 4 or 5, and where Y is selected from OH and SO3 - , and the number of SO3 - groups is greater than the number of OH groups. Preferably, there is 0 or 1 OH group. X and R1 can contain an ester group therein. X can contain a carbonyl group, preferably an ester group. Preferably there is 1 C2H4O unit separating the ester group from N, such that the structural unit is N-C2H4O-ester-(C2H4O) n-1 Y is preferred.

[0138] Such polymers are described in WO2004 / 24858 (Procter and Gamble) and WO2021239547 (Unilever). Preferred example polymers are the sulfated ethoxylated hexamethylene diamine of Example 4 of WO2004 / 24858 and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Ester groups can be included using addition of lactone or sodium chloroacetate (modified Williamson synthesis) to OH or NH groups followed by ethoxylation.

[0139] An example reaction scheme for inclusion of ester groups is The addition of lactone is discussed in WO2021 / 165468. Once ester groups have been included, the alkoxylated ester-containing polyamines can be methylated and sulfated, for example according to Example P6 of WO2021239547. Preferably, the product is neutralised to pH = 7 at the end of the synthesis. If hydrolysis of the ester occurs to any extent, the hydrolysis products can be removed or re-esterified.

[0140] Tetra-ester alkoxylated oligoamines have the form: wherein R1is a polyalkoxy group, R is a polyalkoxy group, x is 0, 1 or 2, and b is 2, 3 or 4. They are described in WO 2023 / 287834 (DOW), WO 2023 / 287835 (DOW), WO 2023 / 287836 (DOW).

[0141] Preferably, the alkoxylated oligoamine cleaning booster is present at 0.01 to 8 wt.%, more preferably 0.5 to 3 wt.% of the composition.

[0142] Aminocarboxylate Preferably, the composition comprises an aminocarboxylate chelant. Preferably, the aminocarboxylate is selected from GLDA and MGDA.

[0143] Preferably, the aminocarboxylate is present in the composition at 0.1 to 15 wt.%, more preferably 0.1 to 10 wt.%, even more preferably 0.3 to 5 wt.%, yet more preferably 0.8 to 3 wt.%, and most preferably 1 to 2.5 wt.% by weight of the composition.

[0144] Glutamic acid diacetic acid (GLDA) The GLDA can be present as a salt of GDLA or a mixture of GDLA and a salt of GDLA. Preferred salt forms include mono-, di-, tri- or tetra-alkali metal salts and mono-, di-, tri- or tetra-ammonium salts of GLDA. The alkali metal salt of glutamic acid diacetic acid GDLA is preferably selected from lithium, potassium, more preferably sodium salts of GLDA.

[0145] Glutamic acid diacetic acid can be partially or preferably completely neutralized with a base. Preferably, 3.5 to 4 COOH groups of GLDA are neutralized with an alkali metal, preferably with sodium. Most preferably, the composition comprises the tetrasodium salt of GLDA.

[0146] The GLDA is at least partially neutralized with an alkali metal, more preferably with sodium or potassium, most preferably with sodium.

[0147] The GLDA salt can be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA or an enantiomerically enriched mixture of isomers.

[0148] Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or the corresponding mono-, di-, tri- or tetra-alkali metal salts or mono-, di-, tri- or tetra-ammonium salts thereof or mixtures thereof, which mainly contain the corresponding L-isomer with an enantiomeric excess in the range of 10% to 95%.

[0149] Preferably, the GLDA salt is essentially L-glutamic acid diacetic acid at least partially neutralized with an alkali metal.

[0150] The sodium salt of GLDA is preferred.

[0151] A suitable commercial source of GLDA in the tetrasodium salt form is DISSOLVINE® GL available from Nouryon.

[0152] Preferably, GLDA is present in the composition at 0.1 to 15 wt.%, more preferably 0.1 to 10 wt.%, even more preferably 0.3 to 5 wt.%, still more preferably 0.8 to 3 wt.%, and most preferably 1 to 2.5 wt.% (by weight of the composition).

[0153] Methylglycinediacetic acid (MGDA) Preferred salt forms include mono-, di-, tri- or tetraalkali metal salts and mono-, di-, tri- or tetraammonium salts of MGDA. The alkali metal salt is preferably selected from the group consisting of lithium, potassium, more preferably sodium salts of MGDA.

[0154] The sodium salt of methylglycinediacetic acid is preferred. Particularly preferred is the trisodium salt of MGDA.

[0155] MGDA can be partially or preferably completely neutralized with the corresponding alkali metal. Preferably, an average of 2.7 to 3 COOH groups per molecule of MGDA are neutralized with an alkali metal, preferably with sodium.

[0156] MGDA can be selected from the group consisting of racemic mixtures of alkali metal salts of MGDA and racemic mixtures of pure enantiomers, such as alkali metal salts of L-MGDA, alkali metal salts of D-MGDA and mixtures of enantiomerically enriched isomers.

[0157] A suitable commercial source of MGDA in the trisodium salt form is TRILON® M available from BASF and Dissolvine® M-40 available from Nouryon.

[0158] Preferably, MGDA is present in the composition at 0.1 to 15 wt.%, more preferably 0.1 to 10 wt.%, even more preferably 0.3 to 5 wt.%, still more preferably 0.8 to 3 wt.%, and most preferably 1 to 2.5 wt.% (by weight of the composition).

[0159] Small amounts of the aminocarboxylate can carry cations other than alkali metals. Thus, it is possible for small amounts (e.g. 0.01 to 5 mole %) to carry alkaline earth metal cations, such as Mg 2+ or Ca 2+ , or Fe(II) or Fe(III) cations. GLDA can contain small amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. In this context, "small amounts" means 0.1 to 1 wt.% in total, referring to the chelating agent aminocarboxylate.

[0160] Organic acid The composition preferably comprises an organic acid. Preferably, the organic acid has the general structure R-CH(OH)-COOH, wherein R is a linear Ci-C5, more preferably C2-C4, most preferably C4 alkyl group.

[0161] Preferably, at least two, more preferably all, of the carbon atoms in the linear Ci-4 are substituted with OH groups. Preferably, R comprises a terminal COOH group.

[0162] Preferred examples are lactic acid, tartaric acid, gluconic acid, mucic acid, glucoheptonic acid. Most preferably, the organic acid is gluconic acid.

[0163] The organic acid can be in its D or L form.

[0164] Gluconic acid can be selected from the group consisting of salts of gluconic acid (gluconates) and pure enantiomers (e.g. alkali metal salts of L-gluconic acid, alkali metal salts of D-gluconic acid) and mixtures of racemic mixtures and enantiomerically enriched isomers. The D-isomer form is preferred.

[0165] Preferably, the organic acid is present in the range of 0.1 to 15 wt%, more preferably 0.1 to 10 wt%, even more preferably 0.2 to 4 wt%, yet more preferably 0.5 to 3 wt%, and most preferably 0.8 to 2 wt% by weight of the composition. Measurement is made in respect of its protonated form.

[0166] In the most preferred embodiment, the composition comprises GLDA and / or MGDA and gluconic acid, more preferably GLDA and gluconic acid.

[0167] External structurant The composition of the present application can further modify its rheology by the use of one or more external structurants which form a structured network within the composition. Examples of such materials include crystallisable glycerides, such as hydrogenated castor oil; microfibrillar cellulose and citrus pulp fibre. The presence of an external structurant can provide a shear-thinning rheology and can also enable materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0168] The composition preferably comprises a crystallisable glyceride.

[0169] The crystallisable glyceride can be used to form an external structured system as described in WO201 1 / 031940, the contents of which (particularly in relation to the manufacture of the ESS) are incorporated by reference. When an ESS is present, it is preferred that the ESS of the present application preferably comprises: (a) a crystallisable glyceride; (b) an alkanolamine; (c) an anionic surfactant; (d) a further component; and (e) an optional component. Each of these components is discussed in detail below.

[0170] As used herein, crystallizable glycerides preferably include "hydrogenated castor oil" or "HCO". As used herein, HCO can most generally be any hydrogenated castor oil so long as it is capable of crystallizing in the ESS pre-mix. Castor oil can include glycerides, especially triglycerides, which contain C10 to C22 alkyl or alkenyl moieties incorporating a hydroxyl group. Hydrogenation conversion of castor oil to make HCO can convert double bonds present in the castor oil acyl moieties in the raw oil to saturated hydroxyalkyl moieties, e.g., hydroxy stearyl groups. In some embodiments, the HCO herein can be selected from the group consisting of: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO can be processed in any suitable starting form, including but not limited to those selected from the group consisting of solids, melts, and mixtures thereof. HCO is typically present in the ESS of the present application at levels of from about 2% to about 10%, from about 3% to about 8%, or from about 4% to about 6%, by weight of the structuring system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered to the final laundry detergent product is less than about 1.0%, typically from 0.1% to 0.8%.

[0171] Useful HCO can have the following properties: a melting point of from about 40 degrees Celsius to about 100 degrees Celsius, or from about 65 degrees Celsius to about 95 degrees Celsius; and / or an iodine value ranging from 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: differential scanning calorimetry. HCO for use in the present application includes those that are commercially available. Non-limiting examples of commercially available HCO for use in the present application include: THIXCIN(R) from Rheox, Inc. Other examples of useful HCO can be found in U.S. Patent 5,340,390. The source of castor oil used for hydrogenation to form HCO can be of any suitable source, such as from Brazil or India. In one suitable embodiment, the castor oil is hydrogenated using a noble metal (e.g., palladium catalyst) and the hydrogenation temperature and pressure are controlled to optimize hydrogenation of the double bonds of the natural castor oil while avoiding unacceptable levels of dehydroxylation.

[0172] The present invention is not intended to be limited to the use of hydrogenated castor oil. Any other suitable crystallizable glyceride can be used. In one example, the structuring agent is a substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents the pure form of the fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly constant, but can vary slightly. Likewise, the hydrogenation process can vary. Any other suitable equivalent material can be used, such as a mixture of triglycerides, at least 80% by weight of which is derived from castor oil. Exemplary equivalent materials comprise, consist essentially of, or consist of, primarily triglycerides; or a mixture of primarily diglycerides and triglycerides; or a mixture of primarily triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides; or a mixture of primarily any of the foregoing glycerides with a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolysis product of any of the glycerides. The foregoing is premised on the major portion (typically at least 80% by weight) of any of the glycerides being chemically identical to the glycerides of fully hydrogenated ricinoleic acid, i.e., the glycerides of 12-hydroxystearic acid. For example, it is known in the art to modify hydrogenated castor oil such that, in a given triglyceride, there are two 12-hydroxystearic acid moieties and one stearic acid moiety. Likewise, it is contemplated that hydrogenated castor oil can not be fully hydrogenated. In contrast, poly(alkoxylated) castor oil is excluded from the present invention when it does not meet the melting criteria.

[0173] The melting point of the crystallizable glyceride used in the present invention can be from about 40 degrees Celsius to about 100 degrees Celsius.

[0174] Hydroxamic acid Preferably, the composition comprises a hydroxamic acid.

[0175] Whenever the term "hydroxamic acid" or "hydroxamate" is used, unless otherwise indicated, it encompasses both the hydroxamic acid and the corresponding hydroxamate (the salt of the hydroxamic acid).

[0176] A hydroxamic acid is a class of chemical compounds in which a hydroxylamine is inserted into a carboxylic acid. The general structure of a hydroxamic acid is as follows: (Formula 1) where R 1 is an organic residue, such as an alkyl or alkenyl group. The hydroxamic acid can exist as its corresponding alkali metal salt or hydroxamate. The preferred salt is the potassium salt.

[0177] A hydroxamate can be conveniently formed from the corresponding hydroxamic acid by replacing the acid hydrogen atom with a cation: (Formula 2) L+ is a monovalent cation, such as an alkali metal (e.g. potassium, sodium), or ammonium or substituted ammonium.

[0178] In the present invention, the hydroxamic acid or its corresponding hydroxamate has the following structure: (Formula 3) where R 1 is a linear or branched C4-C 20 alkyl group, or a linear or branched substituted C4-C 20 alkyl group, or a linear or branched C4-C 20 alkenyl group, or a linear or branched substituted C4-C 20 alkenyl group, or an alkyl ether group CH3(CH2) n (EO) m where n is 2 to 20 and m is 1 to 12, or a substituted alkyl ether group CH3(CH2) n (EO) m where n is 2 to 20 and m is 1 to 12, and the substitution type includes one or more of NH2, OH, S, -O-, and COOH, and R 2 is selected from hydrogen and moieties that form part of a cyclic structure with the branched R 1 group.

[0179] Preferred hydroxamates are those where R 2 is hydrogen and R 1 is a C8to C 14 alkyl group, preferably a n-alkyl group, most preferably those that are saturated.

[0180] The general structure of the hydroxamic acid in the context of the present invention is indicated in Formula 3, and R 1 is as defined above. When R 1 is an alkyl ether group CH3(CH2) n (EO) m where n is 2 to 20 and m is 1 to 12, then the alkyl moiety caps the pendant group. Preferably, R 1 is selected from C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , and C 14 n-alkyl groups, most preferably R 1 is at least C 8-14 n-alkyl. When a C8material is used, this is referred to as octyl hydroxamic acid. The potassium salt is particularly useful.

[0181] Potassium octylhydroxamate However, other hydroxamic acids, although less preferred, are suitable for use in the present application. Such suitable compounds include, but are not limited to, the following compounds: Such hydroxamic acids include lysine hydroxamic acid hydrochloride, methionine hydroxamic acid and norvaline hydroxamic acid and are commercially available.

[0182] The hydroxamate is believed to work by binding to metal ions present in the soil on the fabric. This binding, which is in effect the known chelating agent property of the hydroxamate, has no effect on the removal of soil from the fabric per se. It is the "tail" of the hydroxamate, i.e. the group R 1 Any branching back onto the amate nitrogen is subtracted from the group R 2 The tail is selected to have an affinity for the surfactant system. This means that the soil removal capability of an already optimised surfactant system is further enhanced by the use of the hydroxamate as it effectively tags the difficult to remove particulate matter (clay) as "soil" for removal by the surfactant system acting on the hydroxamate molecules which are now fixed to the particulate via their binding to the metal ions embedded in the clay type particulate. The non-soap soil release surfactant adheres to the hydroxamate, resulting in overall more surfactant interacting with the fabric, leading to better soil release. In this way the hydroxamic acid acts as a linker molecule, facilitating the removal and suspension of particulate soil from the fabric into the wash liquor and hence enhancing the primary detergency.

[0183] The hydroxamate has a higher affinity for transition metals, such as iron, than for alkaline earth metals, such as calcium and magnesium, and so the hydroxamic acid acts primarily to improve the removal of soil, especially particulate soil, from the fabric and not additionally as a builder for calcium and magnesium.

[0184] A preferred hydroxamate is the 80% solids coco hydroxamic acid available from Axis House under the trade name RK853. The corresponding potassium salt is available from Axis House under the trade name RK852. Axis house also supply coco hydroxamic acid as a 50% solids material under the trade name RK858. The 50% potassium coco hydroxamate is available as RK857. Another preferred material is RK842, an alkyl hydroxamic acid from Axis House made from palm kernel oil.

[0185] Preferably, the hydroxamate is present at 0.1 to 3% by weight of the composition, more preferably 0.2 to 2% by weight of the composition.

[0186] Preferably, the weight ratio between the hydroxamic acid salt and the surfactant is 0.05 to 0.3, more preferably 0.75 to 0.2, most preferably 0.8 to 1.2. The weight is calculated on the protonated form.

[0187] Soil release polymer Soil release polymers help improve the detachment of soil from fabrics by modifying the fabric surface during the wash process. Adsorption of the SRP onto the fabric surface is facilitated by the affinity between the chemical structure of the SRP and the target fiber.

[0188] SRPs for use in the present application can include various charged (e.g., anionic) as well as non-charged monomer units, and the structure can be linear, branched, or star-shaped. The SRP structure can also include end-capping groups for controlling molecular weight or altering polymer properties such as surface activity. The weight average molecular weight (M w ) of the SRP can suitably be in the range of about 1000 to about 20,000, and preferably in the range of about 1500 to about 10,000.

[0189] SRPs for use in the present application can suitably be selected from copolyesters of a dicarboxylic acid (e.g., adipic acid, phthalic acid, or terephthalic acid), a diol (e.g., ethylene glycol or propylene glycol), and a polyglycol (e.g., polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units that are substituted with anionic groups, such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by ester interchange / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”), and polyethylene glycol (“PEG”); partially and fully anionically end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT, and sodium 3,6-dioxa-8-hydroxyoctanesulfonate; non- ionically end-capped block polyester oligomeric compounds such as those produced from combinations of DMT, Me end-capped PEG, and EG and / or PG, or DMT, EG and / or PG, Me end-capped PEG, and sodium 5-dimethylsulfonate, and copolymer blocks of terephthaloyl ethylene glycol ester or terephthaloyl propylene glycol ester with poly(ethylene oxide) terephthalate or poly(propylene oxide) terephthalate.

[0190] Other types of SRPs for use in the present application include cellulose derivatives such as hydroxy ether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl esters), e.g., C1-C6 vinyl esters grafted onto a polyalkylene oxide backbone (such as poly(vinyl acetate)); poly(vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

[0191] Preferred SRPs for use in the present application include copolyesters formed by condensation of terephthalate and a diol, preferably 1,2-propanediol, and further comprising endcapping with alkyl endcapped by repeating units of an alkylene oxide. An example of such a material has a structure corresponding to general formula (I): where R 1 and R 2 are independently of each other X-(OC2H4) n -(OC3H6) m ; where X is C 1-4 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.

[0192] Since they are average values, m, n and a are not necessarily integers for the overall polymer.

[0193] Mixtures of any of the above materials can also be used.

[0194] The overall level of the polyester-based SRP can range from 0.1 to 10%, depending on the level of polymer intended for use in the final dilute composition, and desirably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the dilute composition).

[0195] Suitable soil release polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857; WO 2007 / 079850 and WO 2016 / 005271. If used, soil release polymers are typically incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10%, more preferably from 0.1% to 5%, by weight of the composition.

[0196] Enzyme The composition preferably comprises an enzyme selected from cellulases, proteases and amylase / mannanase mixtures.

[0197] In addition, further enzymes can be present, such as those described below.

[0198] Preferably, the composition can comprise an effective amount of one or more enzymes, preferably selected from the group comprising lipase, hemicellulase, peroxidase, hemicellulase, xylanase, xanthanase, lipase, phospholipase, esterase, cutinase, pectinase, carrageenase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanases, beta-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tanninase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase or mixtures thereof.

[0199] Preferably, the enzyme content is 0.1 to 100, more preferably 0.5 to 50, most preferably 5 to 30 mg active enzyme protein per 100 g of finished laundry liquid composition.

[0200] Examples of preferred enzymes are sold under the trade names Purafect Prime®, Purafect®, Preferenz® (DuPont), Savinase®, Pectawash®, Mannaway®, Lipex®, Lipoclean®, Whitzyme® Stainzyme®, Stainzyme Plus®, Natalase®, Mannaway®, Amplify® Xpect®, Celluclean® (Novozymes), Biotouch (AB Enzymes), Lavergy® (BASF).

[0201] Detergent enzymes are discussed in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0202] Nucleases are enzymes capable of cleaving the phosphodiester bond between nucleotide subunits of nucleic acids, and are preferably deoxyribonucleases or ribonucleases. Preferably, the nuclease is a deoxyribonuclease, preferably selected from any one of the classes E.C. 3.1.21.x, wherein x = 1, 2, 3, 4, 5, 6, 7, 8 or 9, E.C. 3.1.22.y, wherein y = 1, 2, 4 or 5, E.C. 3.1.30.z, wherein z = 1 or 2, E.C. 3.1.31.1 and mixtures thereof.

[0203] Proteases hydrolyse bonds within peptides and proteins, which in the case of laundry, results in enhanced removal of protein or peptide-containing stains. Examples of suitable protease families include aspartic proteases; cysteine proteases; glutamic acid proteases; asparagine peptide lyases; serine proteases and threonine proteases. Such protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk). Serine proteases are preferred. Subtilase-type serine proteases are more preferred. The term "subtilase" refers to a sub-group of serine proteases according to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al., Protein Science 6 (1997) 501-523. Serine proteases are a sub-group of the proteases characterized by a serine in the active site that forms a covalent adduct with the substrate. Subtilases can be divided into six sub-divisions, namely the subtilisin family, the thermitase family, the proteinase K family, the lantibiotic peptidase family, the Kexin family and the Pyrolysin family.

[0204] Examples of subtilases are those derived from Bacillus such as Bacillus lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, described in US7262042 and WO09 / 021867, as well as subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, B. licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89 / 06279, and protease PD138 described in (WO93 / 18140). Other useful proteases can be those described in WO92 / 175177, WO01 / 016285, WO02 / 026024 and WO02 / 016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium proteases described in WO89 / 06270, WO94 / 25583 and WO05 / 040372, and the chymotrypsin derived from Cellumonas described in WO05 / 052161 and WO05 / 052146.

[0205] Most preferably, the protease is a subtilisin (EC 3.4.21.62).

[0206] Examples of subtilases are those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus, Bacillus circulans, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gilii, described in US7262042 and WO09 / 021867, as well as subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147, and subtilisin 168 described in WO 89 / 06279, and protease PD138 described in (WO93 / 18140). Preferably, the subtilisin is derived from Bacillus, preferably Bacillus lentus, Bacillus alkalophilus, Bacillus circulans, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gilii, described in US 6,312,936 B1, US 5,679,630, US 4,760,025, US 7,262,042 and WO 09 / 021867. Most preferably, the subtilisin is derived from Bacillus gilii or Bacillus lentus.

[0207] Suitable commercially available proteases include those sold under the trade names Alcalase®, Blaze®; DuralaseTm, DurazymTm, Relase®, Relase® Ultra, Savinase®, Savinase® Ultra, Primase®, Polarzyme®, Kannase®, Liquanase®, Liquanase® Ultra, Ovozyme®, Coronase®, Coronase® Ultra, Neutrase®, Everlase®, and Esperase®, all of which can be sold as Ultra® or Evity® (Novozymes A / S).

[0208] Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Amylases include, for example, alpha-amylases from Bacillus, e.g. the special strains of B. licheniformis described in more detail in GB 1,296,839, or the Bacillus strains disclosed in WO 95 / 026397 or WO 00 / 060060. Amylases are commercially available from Novozymes A / S under the trade names Duramyl™, Termamyl™, Termamyl Ultra™, Natalase™, Stainzyme™, Fungamyl™ and BAN™, from Genencor International Inc. under the trade names Rapidase™ and Purastar™.

[0209] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Suitable cellulases include cellulases from Bacillus, Pseudomonas, Humicola, Trichoderma (see US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, WO 96 / 029397, and WO 98 / 012307), Myceliopthora (WO 98 / 01545), and Sporotrichum (WO 00 / 07063), e.g. the fungal cellulases secreted by the special strains of Humicola insolens described in more detail in GB 1,296,839, or the cellulases disclosed in WO 89 / 09258 and WO 94 / 25612, or the cellulases from Trichoderma agrestre described in WO 88 / 09359. Commercially available cellulases include Celluzyme™, Carezyme™, Celluclean™, Endolase™, Renozyme™ (Novozymes A / S), Clazinase™ and Puradax HA™ (Genencor International Inc.) and KAC-500(B)™ (Kao Corporation). Preferred is Celluclean™. Fusarium Thielavia Acremonium

[0210] Lipase Lipases are lipolytic enzymes, and the terms lipolytic enzyme and lipase are used synonymously herein.

[0211] The composition preferably comprises 0.0005 to 0.5 weight %, preferably 0.005 to 0.2 weight % of a lipase. ​​​

[0212] Cleaning lipolytic enzymes are discussed in Enzymes in Detergency, edited by Jan H. van Ee, Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York).

[0213] The lipolytic enzyme can be selected from a lipase of E.C. class 3.1 or 3.2 or a combination thereof.

[0214] Preferably, the cleaning lipolytic enzyme is selected from: (1) triacylglycerol lipases (E.C. 3.1.1.3) (2) carboxylic ester hydrolases (E.C. 3.1.1.1) (3) cutinases (E.C. 3.1.1.74) (4) sterol esterases (E.C. 3.1.1.13) (5) wax ester hydrolases (E.C. 3.1.1.50) Most preferred is a triacylglycerol lipase (E.C. 3.1.1.3).

[0215] Suitable triacylglycerol lipases can be selected from variants of Humicola lanuginosa (Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, such as from P. alcaligenes or P. pseudoalcaligenes (EP 218272), P. cepacia (EP 331 376), P. stutzeri (GB 1,372,034), P. fluorescens, Pseudomonas strain SD 705 (WO 95 / 06720 and WO 96 / 27002), P. wisconsinensis (WO 96 / 12012), Bacillus lipases, such as from B. subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), B. stearothermophilus (JP 64 / 744992) or B. pumilus (WO 91 / 16422).

[0216] Suitable carboxyl ester hydrolases can be selected from wild-type or variants of endogenous carboxyl ester hydrolases from Bacillus gladioli, Pseudomonas fluorescens, Pseudomonas putida, Bacillus acidocaldarius, Bacillus subtilis, Bacillus stearothermophilus, Streptomyces chrysomallus, Streptomyces diastatochromogenes, and Saccharomyces cerevisiae.

[0217] Suitable keratinases can be selected from wild-type or variant keratinases endogenously derived from Aspergillus strains (especially Aspergillus oryzae), Alternaria strains (especially Alternaria brassicae), Fusarium strains (especially Fusarium solani pisi, Fusarium oxysporum cepa, Fusarium roseum sambucium), Helicobacter strains (especially Helminthosporum sativum), Pyrophyte strains (especially Pyrophyte spp.), Pseudomonas strains (especially Pseudomonas mendoza or Pseudomonas putida), Rhizoctonia strains (especially Rhizoctonia solani), Streptomyces strains (especially Streptomyces scabica), Coprinus strains (especially Coprinus spp.), Bifidobacterium strains (especially Schizospora thermophila), Megaloceros strains (especially Blastomyces oryzae), or Ulocladium consortiale strains (especially wild-type or variant keratinases).

[0218] In a preferred embodiment, the keratinase is selected from variants of the Mendoza Pseudomonas keratinase described in WO 2003 / 076580 (Genencor), such as variants with three substitutions at I178M, F180V and S205G.

[0219] In another preferred embodiment, the keratinase is a wild-type or variant of one of the six endogenous keratinases of Coprinus gracilis described in H. Kontkanen et al., App. Environ. Microbiology, 2009, pp. 2148-2157.

[0220] In another preferred embodiment, the keratinase is a wild-type or variant of two endogenous keratinases from Trichoderma reesei described in WO2009007510 (VTT).

[0221] In the most preferred embodiment the cutinase is derived from a strain of Humicola insolens, in particular a strain of Humicola insolens DSM 1800. Humicola insolens cutinases are described in WO 96 / 13580, which is incorporated herein by reference. The cutinase can be a variant, such as one of the variants disclosed in WO 00 / 34450 and WO 01 / 92502. Preferred cutinase variants include the variants listed in Example 2 of WO 01 / 92502. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0222] Suitable sterol esterases can be derived from a strain of Ophiostoma, such as Ophiostoma piceae, a strain of Pseudomonas, such as Pseudomonas aeruginosa, or a strain of Melanocarpus, such as Melanocarpus albomyces.

[0223] In the most preferred embodiment the sterol esterase is the Melanocarpus albomyces sterol esterase described in H. Kontkanen et al., Enzyme Microb Technol., 39, (2006), 265-273.

[0224] Suitable wax-ester hydrolases can be derived from an oil palm tree.

[0225] The lipid esterase is preferably selected from the group of E.C. classes 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably a lipase of E.C. 3.1.1.3.

[0226] Examples of EC 3.1.1.3 lipases include those described in WIPO publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079, and US 5,869,438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizomucor miehei, Rhizopus deleman, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzae, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanuginosus (synonym: Humicola lanuginosa), and Landerina penisapora, particularly Thermomyces lanuginosus. Certain preferred lipases are provided by Novozymes under the tradenames Lipolase®, Lipolase Ultra®, Lipoprime®, Lipoclean®, and Lipex® (registered trademarks of Novozymes), and LIPASE P "AMANO®" (available from Areario Pharmaceutical Co. Ltd., Nagoya, Japan), AMANO-CES® (available from Toyo Jozo Co., Tagata, Japan); and other Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A and Diosynth Co., Netherlands, and other lipases such as Pseudomonas gladioli. Other useful lipases are described in WIPO publications WO 02062973, WO 2004 / 101759, WO 2004 / 101760, and WO 2004 / 101763.In one embodiment, suitable lipases include the "first cycle lipases" described in WO 00 / 60063 and US Patent 6,939,702 Bl, preferably variants of SEQ ID No. 2, more preferably variants of SEQ ID No. 2 having at least 90% homology to SEQ ID No. 2 comprising a substitution of an electrically neutral or negatively charged amino acid at any of positions 3, 224, 229, 231 and 233 with R or K, most preferred variants comprising T231 R and N233R mutations, such most preferred variant being sold under the tradename Lipex® (Novozymes).

[0227] The above lipases can be used in combination (any mixture of lipases can be used). Suitable lipases are commercially available from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A; Diosynth Co., Oss, The Netherlands and / or prepared according to the examples contained herein.

[0228] As described in WO 2007 / 087243, particularly preferred are lipid esterases with reduced odor production potential and good relative performance. These include lipoclean® (Novozyme).

[0229] Preferred commercially available lipases include Lipolase TM and Lipolase Ultra TM , Lipex TM and Lipoclean TM (Novozymes A / S).

[0230] Fragrance The composition comprises a fragrance, and preferably the fragrance is present at 0.01-5 wt%, more preferably 0.1-1 wt% of the composition.

[0231] Preferably, the fragrance comprises a component selected from the group consisting of ethyl-2-methylpentanoate (matricaria), limonene, (4Z)-cyclopentadec-4-en-1-one, dihydromyrcenol, dimethylbenzylcarbinyl acetate, benzyl acetate, spiro[l,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'- methylenonaphthalene)], benzyl acetate, rose oxide, geraniol, methyl nonyl acetaldehyde, decanal, octanal, undecanal, tricyclodecenyl acetate, t-butylcyclohexyl acetate, cyclamal, beta-ionone, hexyl salicylate, tonal musk, phenafleur, octahydrotetramethylacetophenone (OTNE), benzene, toluene, xylene (BTX) raw materials such as 2-phenylethanol, benzyl acetone and mixtures thereof, cyclododecanone raw materials such as habolonolide, phenolic raw materials such as hexyl salicylate, C5 block or oxygen-containing heterocyclic moiety raw materials such as gamma decalactone, dihydrojasmone methyl ester and mixtures thereof, terpene raw materials such as dihydromyrcenol, linalool, terpinolene, camphor, citronellol and mixtures thereof, alkyl alcohol raw materials such as ethyl-2-methylbutanoate, diacid raw materials such as ethylene brassylate, and mixtures of these components.

[0232] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component ethyl-2-methylpentanoate (matricaria).

[0233] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component limonene.

[0234] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component (4Z)-cyclopentadec-4-en-1-one.

[0235] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component dimethylbenzylcarbinyl acetate.

[0236] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component dihydromyrcenol.

[0237] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component rose oxide.

[0238] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component ethylmethylphenylglycidate.

[0239] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component tricyclo decenyl acetate.

[0240] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component benzyl acetate.

[0241] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component spiro[l,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'- methylenonaphthalene)].

[0242] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component geraniol.

[0243] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component methyl nonyl acetaldehyde.

[0244] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component ambroxan.

[0245] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component beta-ionone.

[0246] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component hexyl salicylate.

[0247] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component tonalid.

[0248] Preferably, the fragrance comprises 0.5 to 30 wt.%, more preferably 2 to 15 wt.%, particularly preferably 6 to 10 wt.% of the fragrance component [2-(cyclohexyloxy)ethyl]benzene.

[0249] Preferably, the fragrance comprises a component selected from the group of benzene, toluene, xylene (BTX) feedstocks. More preferably, the fragrance component is selected from the group consisting of 2-phenylethanol, benzylacetone and mixtures thereof.

[0250] Preferably, the fragrance comprises a component selected from the cyclo-dodecanone raw material class. More preferably, the fragrance component is habolonolide.

[0251] Preferably, the fragrance comprises a component selected from the phenolic raw material class. More preferably, the fragrance component is hexyl salicylate.

[0252] Preferably, the fragrance comprises a component selected from the C5 blocked or oxygen containing heterocyclic moiety raw material class. More preferably, the fragrance component is selected from gamma decalactone, methyl dihydrojasmonate and mixtures thereof.

[0253] Preferably, the fragrance comprises a component selected from the terpene raw material class. More preferably, the fragrance component is selected from linalool, terpinolene, camphor, citronellol and mixtures thereof.

[0254] Preferably, the fragrance comprises a component selected from the alkyl alcohol raw material class. More preferably, the fragrance component is ethyl-2-methyl butyrate.

[0255] Preferably, the fragrance comprises a component selected from the diacid raw material class. More preferably, the fragrance component is ethylene glycol ester of Brazilin acid.

[0256] Preferably, the fragrance components listed above are present in the final detergent composition at 0.0001 to 1 wt% of the composition.

[0257] Fluorescent agent Preferably, the composition comprises a fluorescent agent. More preferably, the fluorescent agent comprises a sulfonated stilbene bisphenyl fluorescent agent such as those discussed in Chapter 7 of Industrial Dyes (K. Hunger, Ed., Wiley VCH 2003).

[0258] Sulfonated stilbene based bisphenyl fluorescent agents are discussed in US5145991 (Ciba Geigy). Preferred is 4,4'-stilbenyl bisphenyl. Preferably, the fluorescent agent contains 2 SO3 - groups. Most preferably, the fluorescent agent has the following structure: wherein X is a suitable counterion, preferably selected from metal ions, ammonium ions or amine salt ions, more preferably alkali metal ions, ammonium ions or amine salt ions, most preferably Na or K.

[0259] Preferably, the fluorescent agent is present at a level of 0.01 wt% to 1 wt% of the composition, more preferably 0.05 to 0.4 wt%, most preferably 0.11 to 0.3 wt%.

[0260] Surfactants based on C16 and / or C18 alkyl groups, whether alcohol ethoxylates or alkyl ether sulphates, are generally available as mixtures of starting materials having C16 and C18 alkyl chain lengths.

[0261] Antifoam The composition can also comprise an antifoam agent, but preferably does not. Antifoam materials are well known in the art and include silicones and fatty acids.

[0262] Preferably, fatty acid soap is present at from 0 to 0.5 wt% of the composition (as measured with reference to the acid added to the composition), more preferably from 0 to 10 wt%, and most preferably is not present.

[0263] Suitable fatty acids in the context of the present application include aliphatic carboxylic acids of the formula RCOOH, wherein R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably from 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 from 50 to 100% (by weight based on the total weight of the mixture) consist of saturated C12-18 fatty acids. Such mixtures are typically derivable from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0264] The fatty acid can be present in the form of its sodium, potassium or ammonium salt and / or in the form of a soluble salt of an organic base such as mono-, di- or triethanolamine.

[0265] Mixtures of any of the above materials can also be used.

[0266] For the purposes of formulation calculations, the fatty acid and / or salt thereof (as defined above) is not included in the level of surfactant or the level of builder in the formulation.

[0267] Preferably, the composition comprises from 0.2 to 10 wt% of the composition of cleaning polymer.

[0268] Preferably, the cleaning polymer is selected from the group consisting of alkoxylated polyethyleneimines, polyester soil release polymers and PEG / vinyl acetate copolymers.

[0269] Preservative Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition Springer.

[0270] The formulation preferably contains a preservative or mixture of preservatives selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and its salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, most preferably sodium benzoate.

[0271] The alternative preferred preservative is selected from sodium benzoate, phenoxyethanol, dehydroacetic acid and mixtures thereof.

[0272] The preservative is present at 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight. Where appropriate, the weight is calculated for the protonated form.

[0273] Preferably, the composition comprises 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight of the composition of sodium benzoate.

[0274] Preferably, the composition comprises 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight of the composition of phenoxyethanol.

[0275] Preferably, the composition comprises 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight of the composition of dehydroacetic acid.

[0276] Preferably, the composition comprises less than 0.1% by weight, more preferably less than 0.05% by weight of an isothiazolinone-based preservative.

[0277] Hydrotrope The compositions of the present application can incorporate non-aqueous carriers such as hydrotopes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1to C5monohydric alcohols (e.g., ethanol and n- or isopropyl alcohol); C2to C6dihydric alcohols (e.g., monopropylene and dipropylene glycol); C3to C9triols (e.g., glycerol); polyethylene glycols having a weight average molecular weight (M w ) in the range of about 200 to 600; C1to C3alkanolamines such as mono-, di- and triethanolamine; and alkyl aryl sulfonate salts having up to 3 carbon atoms in the alkyl group (e.g., sodium and potassium xylene, toluene, ethylbenzene and cumene sulfonate).

[0278] Mixtures of any of the above materials can also be used.

[0279] When included, the non-aqueous carrier can be present in an amount ranging from 0.1 to 3%, preferably 0.5 to 1% by weight based on the total weight of the composition. The amount of hydrotopes used is related to the amount of surfactant present and it is desirable to use hydrotopes content to control viscosity in such compositions. The preferred hydrotopes are monopropylene glycol and glycerol.

[0280] Cocamidopropyl betaine In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the compositions of the present application can also contain one or more co-surfactants (such as amphoteric (zwitterionic) and / or cationic surfactants).

[0281] Specific cationic surfactants include C8to C18alkyldimethylammonium halides and derivatives thereof in which one or both hydroxyethyl groups replace one or both methyl groups, and mixtures thereof. When included, the cationic surfactant can be present in amounts ranging from 0.1 to 5% by weight based on the total weight of the composition.

[0282] Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amido propyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkyl amido propyl hydroxysultaine, acyl taurinates, and acyl glutamates, having alkyl groups containing from about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18, and C18:1, the term "alkyl" being used to include the alkyl portion of higher acyl groups. When included, the amphoteric (zwitterionic) surfactant can be present in amounts ranging from 0.1 to 5% by weight based on the total weight of the composition.

[0283] Mixtures of any of the above materials can also be used.

[0284] Co-surfactant The detergent composition can also optionally contain relatively low levels of organic detergent builder or sequestrant materials. Examples include 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, and citric acid. Other examples are DEQUEST™, an organic phosphonate-type sequestant sold by Monsanto, and alkylhydroxy phosphonates.

[0285] Other suitable organic builders include high molecular weight polymers and copolymers known to have builder properties. For example, such materials include appropriate polyacrylic acids, polymaleic acids, and polyacrylic / maleic copolymers and salts thereof, such as those materials sold under the name SOKALAN™ by BASF. If used, the organic builder material can comprise from about 0.5% to 20%, preferably from 1% to 10%, by weight of the composition. A preferred builder level is less than 10% by weight of the composition, and preferably less than 5% by weight of the composition.

[0286] More preferably, the liquid laundry detergent formulation is a non-phosphate built laundry detergent formulation, i.e. containing less than 1 wt% of phosphate. Most preferably, the laundry detergent formulation is non-built, i.e. containing less than 1 wt% of a builder. Typically in liquid, the preferred chelant is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), for example sold as Dequest 2010. Dequest(R) 2066 (diethylenetriaminepenta(methylene phosphonic acid) or DTPMP heptasodium) is also suitable, but is less preferred as it has a poorer cleaning effect. However, it is preferred that the composition contains less than 0.5 wt% of phosphonate based chelant, more preferably less than 0.1 wt% of phosphonate based chelant. Most preferably, the composition is free of phosphonate based chelant.

[0287] Polymeric thickener The compositions of the present application can comprise one or more polymeric thickening agents. Suitable polymeric thickening agents for use in the present application include hydrophobically modified alkali-swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present application include linear or crosslinked copolymers prepared by addition polymerisation of a monomer mixture comprising 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 the present application denotes a monomer having an ethylenically unsaturated segment (for addition polymerisation with other monomers in the mixture) and a hydrophobic segment. A preferred type of associative monomer includes a polyalkylene oxide segment between the ethylenically unsaturated segment and the hydrophobic segment. Preferred HASE copolymers for use in the present application include linear or crosslinked copolymers prepared by addition polymerisation of (meth)acrylic acid with (i) at least one associative monomer selected from polyalkylene oxide (meth)acrylate esters, preferably polyoxyethylene (meth)acrylate esters, more preferably polyoxyethylene (meth)acrylate esters having a polyoxyethylene moiety of from 5 to 100, preferably from 10 to 80, more preferably from 15 to 60 oxyethylene repeat units; and (ii) at least one other monomer selected from C1-C4 alkyl (meth)acrylate esters, multi-acid vinyl monomers such as maleic acid, maleic anhydride and / or salts thereof, and mixtures thereof. The polyoxyethylene moiety of associative monomer (i) typically comprises from 5 to 100, preferably from 10 to 80, more preferably from 15 to 60 oxyethylene repeat units. 40 C8-C22 alkyl (preferably linear C 12 C8-C22 alkyl (preferably linear C 22 C8-C22 alkyl (preferably linear C

[0288] Mixtures of any of the above materials can also be used.

[0289] When included, the compositions of the present application preferably comprise from 0.01 to 5 wt% of the composition, but depending on the amount intended for use in the final dilution product, and desirably from 0.1 to 3 wt%, by weight based on the total weight of the dilution composition.

[0290] Shading dye Shading dyes can be used to improve the performance of the composition. Preferred shading dyes are violet or blue. It is believed that low levels of these shades of dye deposit on the fabric to mask the yellowing of the fabric. A further advantage of shading dyes is that they can be used to mask any yellowish tint in the composition itself.

[0291] Shading dyes are well known in the art of laundry liquid formulations.

[0292] Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bound to ethoxylate or propoxylated polyethyleneimine as described in WO2011 / 047987 and WO2012 / 119859, alkoxylated mono-azo thiophenes, dye with CAS-No 72749-80-5, Acid Blue 59 and phenoxazine dyes selected from the group consisting of: wherein: X3is selected from the group consisting of: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5; X4is selected from the group consisting of: -H; -CH3; -C2H5; -OCH3; and -OC2H5; Y2is selected from the group consisting of: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0293] Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and WO2008 / 087497.

[0294] Shading dyes are preferably present in the composition in the range 0.0001 to 0.1 wt%. Depending on the nature of the shading dye, there are preferred ranges depending on the efficacy of the shading dye (which depends on the class and the specific efficacy within any particular class).

[0295] Microcapsule One type of microparticle suitable for use in the present application is a microcapsule.

[0296] Microencapsulation can be defined as the process of enclosing a substance within another substance on a very small scale, resulting in capsules with sizes ranging from less than one micron to several hundred microns. The material being encapsulated can be referred to as the core, active ingredient or agent, filler, payload, nucleus or inner phase. The material encapsulating the core can be referred to as the coating, film, shell or wall material.

[0297] Microcapsules generally have at least one continuous shell, usually spherical, surrounding a core. Depending on the materials used and the encapsulation technique, the shell can contain pores, vacancies, or interstitial openings. Multiple shells can be made of the same or different encapsulating materials and can be arranged in layers of varying thickness around the core. Alternatively, microcapsules can be asymmetrically and variably shaped, with a quantity of smaller droplets of core material embedded throughout the microcapsule.

[0298] The shell can have a barrier function to protect the core material from the environment outside the microcapsule, but can also serve as a means to modulate the release of the core material, such as a fragrance. Thus, the shell can be water-soluble or water-swellable and can initiate the release of the fragrance in response to exposure of the microcapsule to a humid environment. Similarly, if the shell is temperature sensitive, the microcapsule can release the fragrance in response to an elevated temperature. The microcapsule can also release the fragrance in response to a shear force applied to the surface of the microcapsule.

[0299] A preferred type of polymeric microparticle suitable for use in the present application is a polymeric core-shell microcapsule, wherein at least one continuous shell of polymeric material, usually spherical, surrounds a core containing a perfume formulation (f2). The shell is typically at most 20% by weight, based on the total weight of the microcapsule. The perfume formulation (f2) is typically from about 10 to about 60% by weight, and preferably from about 20 to about 40% by weight, based on the total weight of the microcapsule. The amount of perfume (f2) can be determined by taking a slurry of the microcapsules, extracting into ethanol and measuring by liquid chromatography.

[0300] Further optional ingredients The compositions of the present application can contain further optional ingredients to enhance performance and / or consumer acceptance. Examples of such ingredients include foam boosters, preservatives (e.g. bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anti-corrosion agents, drape imparting agents, anti-static agents, ironing aids, colorants, pearlescent and / or opacifying agents, and hueing dyes. Each of these ingredients is present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually in amounts up to 5% by weight (based on total weight of the diluted composition) and are thus adjusted according to the dilution ratio using water.

[0301] Automatic dosing In a further aspect, the compositions of the present application can be used in an automatic dosing laundry machine.

[0302] Thus, in a further aspect, there is provided a laundry machine comprising a detergent reservoir, said reservoir containing from 80 ml to 3000 ml of a liquid detergent according to the first aspect.

[0303] In a further aspect, there is provided a method for cleaning fabric, the method comprising filling a reservoir of a washing machine with 80 ml to 3000 ml of a liquid laundry detergent composition according to the first aspect, and performing at least two wash cycles before further liquid laundry detergent is added to the reservoir.

[0304] In a further aspect, there is provided a method for cleaning fabric, the method comprising filling a reservoir of a washing machine with 80 ml to 3000 ml of a liquid laundry detergent composition according to the first aspect, and performing a wash cycle which draws a portion of the liquid laundry detergent from the reservoir and leaves at least 20 ml in the reservoir.

[0305] In a further aspect, there is provided a method for cleaning a first fabric, the method comprising filling a reservoir of a washing machine with 80 ml to 3000 ml of a liquid laundry detergent composition according to the first aspect, and performing a first wash cycle in the washing machine by drawing a portion of the liquid laundry detergent from the reservoir and combining with water to form a first wash liquor and washing said first fabric; optionally rinsing; and removing said first fabric from the washing machine; and performing a further wash cycle to clean a further fabric by drawing a portion of the liquid laundry detergent from the reservoir and combining with water to form a further wash liquor and washing said further fabric; optionally rinsing; and removing said further fabric from the washing machine; optionally repeating the further wash cycle; and adding further liquid laundry detergent to the reservoir.

[0306] The amount of 80 ml to 3000 ml of liquid laundry detergent characterises a plurality of dosages of detergent. Preferably, the reservoir contains 250 ml to 2500 ml, more preferably 400 ml to 2000 ml of liquid laundry detergent.

[0307] The washing machine preferably comprises a detergent reservoir which is capable of storing up to 3000 ml of detergent. Such washing machines are known in the market as automatic dosing washing machines, and are capable of storing sufficient liquid laundry detergent for a plurality of wash cycles, and preferably for a number of wash cycles. A typical example of such a washing machine is found in EP-A-3 071 742 (Electrolux). Preferably, the washing machine is a front loading automatic washing machine.

[0308] Preferably, the laundry washing machine comprises a casing, a washing tub arranged inside the casing with its opening or mouth directly facing a laundry loading / unloading opening realized on a front wall of the casing, a detergent dispensing assembly configured for supplying detergent into the washing tub, a main fresh water supply circuit configured for being connected to a water mains and for selectively directing a flow of fresh water from the water mains to the detergent dispensing assembly and / or to the washing tub, and an electric appliance control panel configured for allowing a user to manually select a desired washing cycle.

[0309] The laundry washing machine detergent dispensing assembly further comprises an automatic dosing detergent dispenser configured for automatically dosing the appropriate amount of detergent to be used during a selected washing cycle based on the selected washing cycle, and the automatic dosing detergent dispenser comprises one or more detergent reservoirs each configured for receiving an amount of detergent for performing a plurality of washing cycles, and for each detergent reservoir, a respective detergent feed pump configured for selectively pumping an amount of detergent from the respective detergent reservoir for performing the selected washing cycle and for pumping / directing said specific amount of detergent into a detergent collection chamber in fluid communication with the washing tub.

[0310] In addition to the reservoir capable of holding the required amount of liquid detergent, the laundry washing machine of the present invention further comprises a motor for driving agitation of the drum. Water is flushed through the laundry washing machine and a predetermined dose of detergent is added to this water to form a wash liquor.

[0311] With an automatic dosing laundry washing machine, the consumer can perform multiple washing cycles before requiring further liquid detergent to be added to the reservoir. Typically, the reservoir is sufficient for five or more washes and possibly up to 20 or more washes depending on the size of the reservoir in the laundry washing machine and the dose used per washing cycle.

[0312] Each washing cycle comprises drawing a volume of liquid laundry detergent from the reservoir sufficient to form a suitable wash liquor to clean the fabric.

[0313] Preferably, the volume is 10 to 75 ml, but this can depend on the amount of fabric, the stains to be cleaned and the amount of surfactant and other cleaning agents in the liquid laundry detergent composition.

[0314] After the first washing cycle is completed, the remaining liquid detergent remains in the laundry washing machine until the next cycle commences at which time a further dose is pumped from the reservoir and mixed with water to form a wash liquor.

[0315] It is also possible that the compositions described herein are loaded into a washing machine via a cartridge that is compatible with the constituent parts of the washing machine. The cartridge can contain the necessary volume of the desired liquid detergent composition and it can be from 200 ml to 3000 ml.

[0316] Examples Example 1 A calcium catalyst was prepared according to EP1747183 with the following composition: n-butanol from Example 1 73.5 wt%, calcium hydroxide 15 wt%, 2-ethylhexanoic acid 3.5 wt%, concentrated sulfuric acid 7.8 wt%, used in this example to make a narrow range ethoxylate.

[0317] 915 g of C14 alcohol (C12 = 10 wt%, C14 = 89 wt%, C16 = 1 wt%) was added to a 2 gallon stainless steel autoclave equipped with an overhead stirrer, internal steam heating, water cooling, and a thermocouple. The C14 alcohol was vacuum dried at 90°C, then 2.1 g of catalyst was added and vacuum stripped at 90°C until all solvent was removed (about 5 minutes). The reactor was heated to 140°C and ethylene oxide was added slowly. After an induction period, a small exothermic reaction was observed, at which point the ethylene oxide addition was continued under a pressure of 2 bar until a total of 3 moles of ethylene oxide was consumed. The temperature was controlled using water cooling and allowed to reach 180°C. When the mole ratio of 3:1 of ethylene oxide to C14 alcohol was reacted to form the alcohol ethoxylate, the temperature was reduced to 90°C and the product was vacuum stripped for 3 hours.

[0318] The narrow range ethoxylation procedure used the (C 11 H 23 COO)2Ba, the methane sulfonic acid catalyst described in US10099964, and the barium oxide / sulfuric acid catalyst described in WO2012028435 (Kolb) were repeated.

[0319] The distribution of ethoxylate of the methane sulfonic acid catalyst was measured and compared to a comparable broad range material made with KOH as catalyst. The results are given in the table below.

[0320] The narrow range material has a lower fraction of AE-O and AE-1 material, where AE-O is unethoxylated alcohol (zero ethoxylate groups) and AE-1 is alcohol ethoxylate with 1 ethoxylate group.

[0321] The resulting material was sulfated using SO3 in a falling film reactor to produce the ether sodium sulfate salt.

[0322] Example 2 A liquid laundry detergent containing 10 wt% of C12 / 14 ether sulphate was produced. The C12 / 14 ether sulphate has a molar ratio of 3:1 C12:C14 alkyl chain. The C12 / 14 ether sulphate was ethoxylated using either a standard ethoxylation catalyst (SLES) or with a narrow range ethoxylation catalyst (NRES) and both samples were present as Na salts. Dyes were added to the formulation selected from: Ethoxylated anthraquinone dye (ED) Sulphonated anthraquinone dye (SD) The dyes were added to give an absorbance of about 1 (1 cm) at the maximum optical absorption in the visible spectrum.

[0323] The UV-VIS spectrum of the liquid laundry detergent was recorded (1 cm path length).

[0324] For both dyes, a broad absorption centred around 620 nm was observed. From the spectrum the wavelength at which the half maximum of the broad absorption was measured to give 2 wavelengths, λL and λH, of the values on the low and high wavelength edges of the absorption.

[0325] For SD, the change from SLES to NRES resulted in a 2 nm shift in λL from 551 to 549 nm and a 1 nm shift in λH from 673 to 672 nm, whereas ED showed only a 1 nm change for λL and no change for λH.

[0326] The colour change of ED was less than that of SD when moving from SLES to NRES.

[0327] Example 3 A typical formulation included:

[0328] 1,2 A C12-18 version was also produced C12-14 alkyl ethoxy (3) sulphate is a narrow range AES as described herein.

[0329] The perfume comprises a fragrance component selected from the group consisting of limonene, tonka musk, octahydro-tetramethyl-acetophenone (OTNE), cyclamen aldehyde, C8 to C12 linear and branched aldehydes, beta-ionone, dihydromyrcenol, hexyl salicylate, and mixtures thereof.

Claims

1. A detergent composition comprising an alkoxylated dye and an alkyl ether sulphate, wherein the alkyl ether sulphate comprises C12 and C14 alkyl chains and has a molar average of 2.0 to 4.0 ethoxylate units, wherein the alcohol ether sulphate comprises less than 10 wt% alcohol ether sulphate with zero ethoxylate groups.

2. A composition according to claim 1 which is a liquid detergent composition.

3. A composition according to claim 1 or 2 which comprises at least 60 wt% water of the composition.

4. A composition according to claim 1 which is a laundry liquid unit dose composition.

5. A composition according to any preceding claim wherein the ratio of C12:14 is from 5:1 to 1 :

20.

6. A composition according to any preceding claim wherein the ratio of C12:14 is from 3:1 to 5:

4.

7. A composition according to any preceding claim wherein the alkyl ether sulphate is present at from 1 to 30 wt% of the composition.

8. A composition according to any preceding claim which comprises a salt.

9. A composition according to claim 8 wherein the salt is selected from sodium chloride, potassium chloride and mixtures thereof.

10. A composition according to claim 8 or 9 wherein the salt is present at from 0.1 to 5 wt% of the composition.

11. A composition according to any preceding claim which has a pH of from 5 to 10, more preferably from 6 to 8, most preferably from 6.1 to 7.

0.

12. A composition according to any preceding claim wherein the alkoxylated dye is present at from 0.001 to 2 wt%.

13. A composition according to any preceding claim wherein the dye is selected from wherein R2, R3, X and Y are H or an organic group, and at least one of the groups R2, R3, X and Y contains a -[CH2CH20] n H groups.

14. A composition according to any preceding claim wherein the dye is selected from and ; ; and ; ; and equivalents thereof having different degrees of ethoxylation, preferably each ethoxylated chain has a molar average of from 2 to 15 ethoxylate units.

15. A method of laundering a fabric comprising the use of a composition according to any preceding claim.

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