Liquid composition comprising linear alkylbenzene sulfonate, methyl ester ethoxylate and alkoxylated zwitterionic polyamine polymer

Abstract

The present invention relates to a liquid composition comprising (A) a linear alkylbenzene sulfonate, (B) a methyl ester ethoxylate, and (C) an additional anionic surfactant, and 0.5 to 10% by weight of an alkoxylated zwitterionic diamine or polyamine polymer wherein the (C) / (A) weight ratio is from 1 to 0 and the (B) / (A) + (B) weight ratio is from 0.2 to 9, wherein the surfactant content in the formulation is from 10 to 60% by weight.

Description

Technical Field

[0001] The present invention relates to improved laundry liquid compositions. Background Art

[0002] Despite the prior art, there remains a need for improved laundry liquid compositions. Summary of the invention

[0003] Thus, in a first aspect, there is provided a laundry detergent composition comprising (A) a linear alkylbenzene sulfonate, (B) a methyl ester ethoxylate, and (C) an additional anionic surfactant, and 0.5 to 10 wt% of an alkoxylated zwitterionic diamine or polyamine polymer, wherein the (C) / (A) weight ratio is from 1 to 0, and the (B) / (A)+(B) weight ratio is from 0.2 to 9, wherein the level of surfactant in the formulation is from 10 to 60 wt%.

[0004] We have surprisingly found that the combination of methyl ester ethoxylates with the defined polyamines provides compositions with lower viscosity, thereby providing easier processing and reduced energy consumption during manufacturing. DETAILED DESCRIPTION

[0005] Alkoxylated zwitterionic polyamine polymers

[0006] Alkoxylated zwitterionic di- or polyamine polymers in which the cationic charge is provided by quaternization of the amine nitrogen atom and the anionic groups, where present, are provided by sulfation or sulfonation of the alkoxylated groups.

[0007] Preferably, the alkoxy group of the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0008] Preferably greater than or equal to 50 mol % of the amine nitrogen is quaternized, preferably with methyl groups. Preferably, the polymer contains 3 to 10, more preferably 3 to 6, most preferably 3 to 5 quaternized amine nitrogens. Preferably, the alkoxylate groups are selected from ethoxy and propoxy, most preferably ethoxy.

[0009] Preferably, the polymer contains ester (COO) groups or acid amide (CONH) groups in the structure, preferably these groups are arranged so that when all ester groups or acid amide groups are hydrolyzed, at least one, preferably all of the hydrolyzed fragments have a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

[0010] Preferably, the polymer has the following form:

[0011]

[0012] wherein R1 is a C3 to C8 alkyl group, X is a (C2H4O)nY group, wherein n is 15 to 30, wherein m is 2 to 10, preferably 2, 3, 4 or 5, and wherein Y is selected from OH and SO3 - , and preferably SO3 - The number of groups is greater than the number of OH groups. Preferably, 0, 1 or 2 OH groups are present. X and R1 may contain an ester group among them. X may contain a carbonyl group, preferably an ester group. Preferably, there is 1 C2H4O unit separating the ester group from N, so that the structural unit N-C2H4O-ester-(C2H4O) n-1 Y is preferred.

[0013] Such polymers are described in WO2021239547 (Unilever), exemplary polymers being sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Ester groups may be included by addition to OH or NH groups using lactones or sodium chloroacetate (modified Williamson synthesis) followed by subsequent ethoxylation.

[0014] An exemplary reaction scheme for inclusion of an ester group is

[0015]

[0016] The addition of lactones is discussed in WO2021 / 165468.

[0017] Methyl Ester Ethoxylate (MEE)

[0018] Preferred methyl ester ethoxylate (MEE) surfactants have the following form:

[0019] R3(-C=O)-O-(CH2CH2-O) n -CH3

[0020] Where R3COO is the fatty acid moiety, e.g. oleic acid, stearic acid, palmitic acid. Fatty acid nomenclature describes the fatty acid by two 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 is given in brackets, 18:1 (9) for oleic acid and 18:2 (9, 12) for linoleic acid, where 9 is the carbon number from the COOH end.

[0021] The integer n is the molar average number of ethoxylates.

[0022] Methyl ester ethoxylate (MEE) is described in Chapter 8, 287-301 pages of Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications by G.A. Smith (AOCS Press 2019); J.Am.Oil.Chem.Soc., vol 74 (1997) page 847-859 by Cox ME and Weerasooriva U; Tenside Surf.Det., vol. 28 (2001), 72-80 pages by Hreczuch et al.; Household and Personal Care Today (2012), 52-55 pages by C.Kolano; J.Am.Oil.Chem.Soc.vol 72 (1995) page 781-784 by A.Hama et al. MEE can be prepared by the reaction of methyl esters with ethylene oxide using a calcium or magnesium-based catalyst. The catalyst may be removed or retained in the MEE.

[0023] Alternative preparation routes are transesterification of methyl esters or esterification of carboxylic acids with polyethylene glycols terminated with a methyl group at one end of the chain.

[0024] Methyl esters can be prepared by the transesterification of methanol and triglycerides or the esterification of methanol and fatty acids. The 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 the 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 present in vegetable fats or oils, and preferred sources are rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high stearic acid / high oleic acid sunflower oil, high oleic acid sunflower oil, non-edible vegetable oils, tall oil and any mixture thereof and any derivative thereof. Oil from trees is called tall oil. Used food cooking oil can be used. Triglycerides can also be obtained from algae, fungi, yeast or bacteria. Plant sources are preferred.

[0025] Distillation and fractionation methods can be used in the preparation of methyl esters or carboxylic acids to produce the desired carbon chain distribution.Preferred triglyceride sources are those containing less than 35% by weight polyunsaturated fatty acids in the oil prior to distillation, fractionation or hydrogenation.

[0026] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, Unileveroleochemical Indonesia. Biodiesel is a methyl ester and these sources can be used.

[0027] When the ESB is MEE, it preferably has a molar average of ethoxylate groups (EO) of 8 to 30, more preferably 10 to 20. The most preferred ethoxylates contain 12 to 18 EO.

[0028] Preferably, at least 10 wt %, more preferably at least 30 wt % of the total C18:1 MEE in the composition has 9 to 11 EOs, even more preferably at least 10 wt % has exactly 10 EOs. For example, when the MEE has a molar average of 10 EOs, then at least 10 wt % of the MEE should consist of ethoxylates having 9, 10 and 11 ethoxylate groups.

[0029] The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). The 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% by weight of the MEE should consist of ethoxylates having 9, 10 and 11 ethoxylate groups.

[0030] In the context of a broader MEE distribution, it is preferred that at least 40 wt% of the total MEE in the composition is C18:1.

[0031] Additionally, it is preferred that the MEE component also comprises some C16 MEE.

[0032] Therefore, it is preferred that the total MEE component comprises 5 to 50 wt% C16MEE based on total MEE.Preferably, the C16MEE is greater than 90 wt%, more preferably greater than 95 wt% C16:0.

[0033] In addition, 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 polyunsaturated C18, i.e. C18:2 and C18:3, based on the total MEE. Preferably, C18:3 is present at less than 1 wt %, more preferably less than 0.5 wt %, and most preferably substantially absent. The degree of polyunsaturation can be controlled by distillation, fractionation or partial hydrogenation of the feedstock (triglycerides or methyl esters) or of the MEE.

[0034] Furthermore, it is preferred that the C18:0 component comprises less than 10 wt % of the total MEE weight present.

[0035] Furthermore, it is preferred that components having a carbon chain of 15 or less comprise less than 4 weight percent of the total MEE weight present.

[0036] Particularly preferred MEEs have 2 to 26% by weight of C16:0 chains, 1 to 10% by weight of C18:0 chains, 50 to 85% by weight of C18:1 chains and 1 to 12% by weight of C18:2 chains, based on the MEE.

[0037] Preferred sources of alkyl groups for MEE include methyl esters derived from distilled palm oil and distilled high oleic acid, 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.

[0038] 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), the National Sunflower Association, and Oilseeds International.

[0039] Preferably, the double bonds in MEE are greater than 80% by weight in the cis configuration. Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0040] The methyl group of the methyl ester may be replaced by an ethyl group or a propyl group. The methyl group is most preferred.

[0041] Preferably, the methyl ester ethoxylate comprises from 0.1 to 95 wt% of methyl ester ethoxylate based on the composition. More preferably, the composition comprises from 2 to 40 wt% MEE, most preferably from 4 to 30 wt% MEE.

[0042] Surfactants

[0043] The aqueous liquid detergents of the present invention preferably contain from 10 to 50 wt% total surfactants, most preferably from 10 to 30 wt% total surfactants.Anionic and nonionic surfactants are preferred.

[0044] Anionic surfactants are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, published by CRC Press. Preferred anionic surfactants are sulfonate surfactants and sulfate surfactants, preferably alkylbenzene sulfonates, alkyl sulfates and alkyl ether sulfates. The alkyl chain is preferably C10-C18. Alkyl ether sulfates are also known as alcohol ether sulfates.

[0045] Commonly used in laundry liquid compositions are C12-C14 alkyl ether sulfates having a straight or branched chain alkyl group containing 12 to 14 carbon atoms (C12-14) and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 EO units per molecule.

[0046] Anionic surfactants are preferably added to the detergent composition in salt form. Preferred cations are alkali metal ions, such as sodium and potassium. However, the anionic surfactants in salt form can be formed in situ by neutralizing the surfactants in acid form with an alkali (e.g. sodium hydroxide) or an amine (e.g. monoethanolamine, diethanolamine or triethanolamine). The weight ratio is calculated with the surfactant in protonated form.

[0047] Nonionic surfactants are discussed in Non-ionic Surfactants: Organic Chemistry, Nico M. van Os, ed. (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press. Preferred nonionic surfactants are alkoxylated, preferably ethoxylated. Preferred nonionic surfactants are alcohol ethoxylates and methyl ester ethoxylates, having C10-C18 alkyl chains. Commonly used in laundry liquid compositions are C12-C15 alcohol ethoxylates, which have straight or branched chain alkyl groups containing 12 to 15 carbon atoms and contain an average of 5 to 12 EO units per molecule. Preferred examples are C12-C15 alcohol ethoxylates having a molar average of 7 to 9 ethoxylate units.

[0048] In the anionic surfactants and nonionic surfactants, the ethoxy units may be partially replaced by propoxy units.

[0049] Other examples of suitable anionic surfactants are rhamnolipids, α-olefin sulfonates, olefin sulfonates, alkene sulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkane sulfonates and disulfonates, fatty alcohol sulfates (FAS), paraffin sulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates alkyl- or alkenyl-succinic acid, dodecenyl / tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEM's, CITREM's and diesters and monoesters of sulfo-succinic acid.

[0050] Other examples of suitable nonionic surfactants include alkoxylated fatty acid alkyl esters, alkyl polyglycosides, alkoxylated amines, ethoxylated glycerides, fatty acid monoethanolamides, fatty acid diethanolamides, ethoxylated fatty acid monoethanolamides, propoxylated fatty acid monoethanolamides, polyhydroxyalkyl fatty acid amides, or N-acyl N-alkyl derivatives of glucosamine, polysorbates (TWEENS).

[0051] The formulation may contain soaps, and zwitterionic or cationic surfactants as minor components, preferably present at levels of 0.1 to 3 wt%. Betaines such as CAPB are preferred zwitterionic surfactants.

[0052] Preferred nonionic and anionic surfactants are further described below.

[0053] C16 / C18 Alcohol Ethoxylate

[0054] Preferred C16 / 18 alcohol ethoxylates have the formula:

[0055] R1-O-(CH2CH2O) q -H

[0056] wherein R1 is selected from saturated, monounsaturated, and polyunsaturated linear C16 and C18 alkyl chains, and wherein q is 4 to 20, preferably 5 to 14, more preferably 8 to 12. The monounsaturation is preferably at position 9 of the chain, with the carbons being counted from the end of the chain to which the ethoxylate is bound. The double bond may be in cis or trans configuration (oleyl or anti-oleyl), preferably cis. Cis or trans alcohol ethoxylates CH3(CH2)7-CH=CH-(CH2)8O-(OCH2CH2) nOH is described as C18:1 (Δ9) alcohol ethoxylate. This follows the nomenclature CX:Y (ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds and ΔZ is the position of the double bond on the chain, where the carbon is counted from the end of the chain to which the OH is bound.

[0057] Preferably, R1 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, saturated C16 alcohol ethoxylates account for at least 90% by weight of the total C16 linear alcohol ethoxylates. Regarding the C18 alcohol ethoxylate content, it is preferred that the main C18 part is C18:1, more preferably C18:1 (Δ9). The proportion of monounsaturated C18 alcohol ethoxylates accounts for at least 50% by weight of the total C16 and C18 alcohol ethoxylate surfactants. Preferably, the proportion of monounsaturated C18 accounts for at least 60% by weight of the total C16 and C18 alcohol ethoxylate surfactants, most preferably at least 75% by weight.

[0058] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt%, more preferably 4 wt% of the total C16 and C18 alcohol ethoxylate surfactants.

[0059] Preferably, the saturated C18 alcohol ethoxylate surfactant comprises at most 20 wt%, more preferably at most 11 wt% of the total C16 and C18 alcohol ethoxylate surfactant.

[0060] Preferably, the saturated C18 content is at least 2 wt% of the total C16 and C18 alcohol ethoxylate surfactant content.

[0061] Alcohol ethoxylates are discussed in Non-ionic Surfactants: Organic Chemistry, edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press. Alcohol ethoxylates are often referred to as alkyl ethoxylates.

[0062] Preferably, the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1, more preferably from 2 to 100, most preferably from 3 to 30. 'C18 alcohol ethoxylate' is the sum of all C18 fractions in the alcohol ethoxylate, and 'C16 alcohol ethoxylate' is the sum of all C16 fractions in the alcohol ethoxylate.

[0063] Linear saturated or monounsaturated C20 and C22 alcohol ethoxylates may also be present. Preferably, the weight fraction of the sum of 'C18 alcohol ethoxylates' / 'C20 and C22 alcohol ethoxylates' is greater than 10.

[0064] Preferably, the C16 / 18 alcohol ethoxylate contains less than 15 wt%, more preferably less than 8 wt%, most preferably less than 5 wt% of polyunsaturated alcohol ethoxylate based on the alcohol ethoxylate. Polyunsaturated alcohol ethoxylates contain hydrocarbon chains with two or more double bonds.

[0065] C16 / 18 alcohol ethoxylates can be synthesized by ethoxylation of alkyl alcohols via the following reaction:

[0066] R1-OH+qethylene oxide→R1-O-(CH2CH2O) q -H

[0067] Alkyl alcohols can be prepared by transesterification of triglycerides to methyl esters, followed by distillation and hydrogenation to alcohols. This process is discussed in Kreutzer, UR, Journal of the American Oil Chemists' Society. 61(2):343-348. The preferred alkyl alcohol for this reaction is oleyl alcohol having an iodine value of 60 to 80, preferably 70 to 75, which is available from BASF, Cognis, Ecogreen.

[0068] The preparation of fatty alcohols is further discussed in Sanchez MA et al J. Chem. Technol. Biotechnol 2017; 92: 27-92 and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim 4th edition, volume 11, page 436 and with reference below.

[0069] Preferably, the ethoxylation reaction is base catalyzed using NaOH, KOH or NaOCH3. Even more preferred are catalysts that provide a narrower ethoxyl distribution than NaOH, KOH or NaOCH3. Preferably, these narrower distribution catalysts include Group II bases such as barium dodecanoate; Group II metal alkoxides; Group II hyrodrotalcites as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0070] Preferably, the narrow ethoxyl distribution has greater than 70 wt%, more preferably greater than 80 wt% in RO-(CH2CH2O) x -H to RO-(CH2CH2O) y -H range of alcohol ethoxylates RO-(CH2CH2O)q -H, wherein q is the molar average degree of ethoxylation, and x and y are absolute numbers, wherein x=qq / 2 and y=q+q / 2. For example, when q=10, then more than 70% by weight of the alcohol ethoxylate should consist of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 ethoxylate groups.

[0071] C16 and / or C18 alcohol ether sulfates

[0072] Preferred ether sulfates have the formula:

[0073] R2-O-(CH2CH2O) p SO3H

[0074] wherein R2 is selected from saturated, monounsaturated, and polyunsaturated linear C16 and C18 alkyl chains, and wherein p is 3 to 20, preferably 4 to 12, more preferably 5 to 10. The monounsaturation is preferably at position 9 of the chain, with the carbons counted from the end of the chain to which the ethoxylate is bound. The double bond may be in cis or trans configuration (oleyl or anti-oleyl), but is preferably cis. Cis or trans ether sulfates CH3(CH2)7-CH=CH-(CH2)8O-(CH2CH2O) n SO3H is described as C18:1 (Δ9) ether sulfate. This follows the nomenclature CX:Y (ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds and ΔZ is the position of the double bonds on the chain, where the carbons are counted from the end of the chain to which the OH is bound.

[0075] Preferably, R2 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, the saturated C16 accounts for at least 90% by weight of the C16 linear alkyl content. Regarding the C18 content, it is preferred that the main C18 part is C18:1, more preferably C18:1 (Δ9). Preferably, the proportion of monounsaturated C18 accounts for at least 50% by weight of the total C16 and C18 alkyl ether sulfate surfactants.

[0076] More preferably, the proportion of monounsaturated C18 is at least 60 wt%, most preferably at least 75 wt% of the total C16 and C18 alkyl ether sulfate surfactants.

[0077] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt%, more preferably at least 4 wt% of the total C16 and C18 alkyl ether sulfate surfactants.

[0078] Preferably, the saturated C18 alkyl ether sulfate surfactants comprise at most 20 wt % of the total C16 and C18 alkyl ether sulfate surfactants, more preferably at most 11 wt %. Preferably, the saturated C18 content is at least 2 wt % of the total C16 and C18 alkyl ether sulfate content.

[0079] Where the composition comprises a mixture of C16 / 18 source materials for the alkyl ether sulphates as well as the more traditional C12 alkyl chain length materials, it is preferred that the total C16 / 18 alkyl ether sulphate content should account for at least 10% by weight of the total alkyl ether sulphates, more preferably at least 50% by weight, even more preferably at least 70% by weight, particularly preferably at least 90% by weight and most preferably at least 95% by weight of the alkyl ether sulphates in the composition.

[0080] Ether sulfates are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, published by CRC Press.

[0081] Linear saturated or monounsaturated C20 and C22 ether sulfates may also be present. Preferably, the weight fraction of the sum of 'C18 ether sulfates' / 'C20 and C22 ether sulfates' is greater than 10.

[0082] Preferably, the C16 and 18 ether sulfates contain less than 15 wt %, more preferably less than 8 wt %, most preferably less than 4 wt %, most preferably less than 2 wt % of polyunsaturated ether sulfates based on the ether sulfate. Polyunsaturated ether sulfates contain hydrocarbon chains with two or more double bonds.

[0083] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. The alcohol ethoxylates can be prepared by ethoxylation of alkyl alcohols. The alkyl alcohols used to prepare the alcohol ethoxylates can be prepared by transesterification of triglycerides to methyl esters, followed by distillation and hydrogenation to alcohols. This method is discussed in Kreutzer, UR's Journal of the American Oil Chemists' Society. 61 (2): 343-348. The preferred alkyl alcohol for the reaction is oleyl alcohol with an iodine value of 60 to 80, preferably 70 to 75, which is available from BASF, Cognis, Ecogreen.

[0084] The degree of polyunsaturation in the surfactant can be controlled by hydrogenation of triglycerides as described in A Practical Guide to Vegetable Oil Processing (Gupta MKAcademic Press 2017). Distillation and other purification techniques can be used.

[0085] Ethoxylation reactions are described in Non-Ionic Surfactant Organic Chemistry (NM van Osed), Surfactant Science Series Volume 72, CRC Press.

[0086] Preferably, the ethoxylation reaction is base catalyzed using NaOH, KOH or NaOCH3. Even more preferred are catalysts that provide a narrower ethoxyl distribution than NaOH, KOH or NaOCH3. Preferably, these narrower distribution catalysts include Group II bases such as barium dodecanoate; Group II metal alkoxides; Group II hydrotalcites as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0087] Preferably, the narrow ethoxyl distribution has greater than 70 wt. %, more preferably greater than 80 wt. % of the ethoxyl groups in R2-O-(CH2CH2O) z SO3H to R2-O-(CH2CH2O) w Ether sulfates in the SO3H range R2-O-(CH2CH2O) p SO3H, wherein q is the molar average degree of ethoxylation, x and y are absolute numbers, wherein z=pp / 2 and w=p+p / 2. For example, when p=6, then more than 70% by weight of the ether sulfate should consist of ether sulfates having 3, 4, 5, 6, 7, 8, 9 ethoxylate groups.

[0088] Ether sulfate weight in protonated form: R2-O-(CH2CH2O) p SO3H is calculated. In the formulation, it is in the ionic form with the corresponding counterion R2-O-(CH2CH2O) p SO3- is present, and preferred counterions are Group I and II metals, amines, most preferably sodium.

[0089] Preferably, the composition comprises at least 50 wt% water, but this will depend on the total surfactant content and will be adjusted accordingly.

[0090] The composition may comprise additional surfactants, preferably other anionic and / or nonionic surfactants, such as alkyl ether sulfates or alcohol ethoxylates containing C12 to C18 alkyl chains. In the case where the surfactant source comprises a C18 chain, it is preferred that at least 30 wt% of the total C18 surfactant is a methyl ester ethoxylate surfactant.

[0091] Preferably, the methyl ester ethoxylate surfactant is used in combination with an anionic surfactant. Preferably, the weight fraction of methyl ester ethoxylate surfactant / total anionic surfactant is 0.1 to 9, more preferably 0.15 to 2, most preferably 0.2 to 1. "Total anionic surfactant" refers to the total content of anionic surfactants of any kind, preferably ether sulfates, linear alkylbenzene sulfonates, alkyl ether carboxylates, alkyl sulfate esters, rhamnolipids and mixtures thereof.

[0092] Anionic surfactant weights are calculated in the protonated form.

[0093] Source of alkyl chains

[0094] The alkyl chains of the C16 / 18 surfactant are preferably obtained from renewable sources, preferably from triglycerides. Renewable sources are sources where the material is produced by the natural ecological cycle of living species, preferably by plants, algae, fungi, yeast or bacteria, more preferably plants, algae or yeast.

[0095] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably, palm oil and rapeseed oil are sources.

[0096] Algal oil is discussed in Saad MG et al., Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges. Methods for producing triglycerides from biomass using yeast are 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.

[0097] Inedible vegetable oils may be used and are preferably selected from the fruits and seeds of: Jatropha curcas, Calophylluminophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seed), linseed, Pongamia pinnata (karanja), Heveabrasiliensis (rubber seed), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Simmondsia chinensis). chinensis)(Jojoba), Arugula(Eruca sativa.L.), Cerberaodollam(Sea mango), Coriander(Coriander(Coriandrum sativum L.), Croton megalocarpus, Pilu, Crambe, Syringa, 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 mustard), Syagrus, Tung, Idesia polycarpa var. vestita, algae, Argemone mexicana L. (Mexican prickly poppy), Putranjiva roxburghii (Lucky bean tree), Sapindus mukorossi (Soapnut), M.azedarach (syringe), Thevettia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B. napus, Zanthoxylum bungeanum.

[0098] SLES and PAS

[0099] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are generally obtainable by sulfating alcohol ethoxylates. These alcohol ethoxylates are generally obtainable by ethoxylating linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating the linear alcohols. Therefore, forming the linear alcohol is a central step in obtaining both PAS and alkali metal alkyl ether sulfate surfactants.

[0100] Linear alcohols suitable as an intermediate step in the manufacture of alcohol ethoxylates and hence anionic surfactants such as sodium lauryl ether sulfate can be obtained from a number of different sustainable sources. These include:

[0101] Primary sugar

[0102] Primary sugars are obtained from cane sugar or sugar beets, etc., and can be fermented to form bioethanol. The bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form alkene. These alkene are then processed into linear alcohols by hydroformylation or oxidation.

[0103] 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 then hydrolyzed into linear fatty acids which are then reduced to form linear alcohols.

[0104] Biomass

[0105] Biomass, such as forest products, rice husks and straw (to name a few), can be processed into synthesis gas by gasification. These are processed into alkanes by the Fischer-Tropsch reaction, which in turn are dehydrogenated to form olefins. These olefins can be processed in the same manner as the olefins described above [primary sugars].

[0106] An alternative process converts the same biomass into polysaccharides by steam explosion, which can be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which in turn is dehydrated to form bioethylene. The bioethylene is then processed into linear alcohols as described above [primary sugars].

[0107] Waste plastics

[0108] Waste plastics are pyrolyzed to form pyrolysis oil. The pyrolysis oil is then fractionated to form linear alkanes, which are dehydrogenated to form olefins. These olefins are processed as described above [primary sugars].

[0109] Alternatively, the pyrolysis oil is cracked to form ethylene which is then processed by olefin metathesis to form the desired olefins. These are then processed into linear alcohols as described above [primary sugars].

[0110] Municipal Solid Waste

[0111] MSW is converted to syngas by gasification. From the syngas, it can be processed to ethylene as described above [primary sugars] or it can be converted to ethanol by enzymatic methods and then dehydrogenated to ethylene. The ethylene can then be converted to linear alcohols by the Ziegler process.

[0112] MSW can also be converted into pyrolysis oil by gasification and then fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.

[0113] Ocean Carbon

[0114] There are various carbon sources from marine communities such as seaweed and kelp. From these marine communities, triglycerides can be isolated from the source and then the triglycerides are hydrolyzed to form fatty acids which are reduced to linear alcohols in the usual manner.

[0115] Alternatively, the feedstock can be separated into polysaccharides which are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol and then processed as described above [primary sugars].

[0116] Waste oil

[0117] Waste oils, such as used cooking oils, can be physically separated into triglycerides, which are split to form linear fatty acids and then to form linear alcohols as described above.

[0118] Alternatively, the used cooking oil may be subjected to the Neste process, whereby the oil is catalytically cracked to form bio-ethylene. The bio-ethylene is then processed as described above.

[0119] Methane capture

[0120] Methane capture processes capture methane from landfills or from fossil fuel production. The methane can be formed into synthesis gas by gasification. The synthesis gas can be processed as described above, whereby the synthesis gas is converted into methanol (Fischer-Tropsch reaction), then into olefins, and then into linear alcohols by hydroformylation oxidation.

[0121] Alternatively, the synthesis gas may be converted to alkanes and then to olefins by Fischer-Tropsch and subsequent dehydrogenation.

[0122] Carbon capture

[0123] Carbon dioxide can be captured by any of a variety of well-known methods. The carbon dioxide can be converted to carbon monoxide by the reverse water-gas shift reaction, and the carbon monoxide can 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, which are then reacted to form olefins.

[0124] Alternatively, the captured carbon dioxide is mixed with hydrogen and then enzymatically treated to form ethanol. This is a process that has been developed by Lanzatech. Thus, the ethanol is converted to ethylene, then processed to olefins, and then processed to linear alcohols as described above.

[0125] The above process can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0126] Linear alkylbenzene sulfonate

[0127] LAS (Linear Alkyl Benzene Sulfonate) is the preferred anionic surfactant and is present in the compositions of the present invention.

[0128] The key intermediate compounds in LAS production are the related olefins. These alkene (olefin) can be prepared by any of the above methods and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, ocean carbon (for example).

[0129] However, instead of the olefin being processed by hydroformylation and oxidation to form a linear alcohol in the above process, the olefin is reacted with benzene and then with a sulfonate to form LAS.

[0130] Linear alkylbenzene sulfonate with alkyl chain length of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing such aromatic ring, which is sulfonated at the "para-position" and connected with a linear alkyl chain at any position except the terminal carbon. This linear alkyl chain preferably has a chain length of 11 to 15 carbon atoms, wherein the main material has a chain length of about C12. Each alkyl chain homologue is composed of a mixture of all possible sulfophenyl isomers except 1-phenyl isomers. LAS is usually formulated into the composition in acid (i.e. HLAS) form, then at least partially neutralized in situ. Preferably, the linear alkylbenzene sulfonate surfactant is present in 1 to 20 % by weight, more preferably 2 to 15 % by weight, most preferably 8 to 12 % by weight by the composition.

[0131] Surfactant ratio

[0132] Preferably, the weight ratio of total nonionic surfactant to total anionic surfactant (weight of nonionic surfactant / weight of anionic surfactant) is from 0 to 2, preferably from 0.2 to 1.5, most preferably from 0.3 to 1.

[0133] Preferably, the weight ratio of total nonionic surfactant to total alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0134] Preferably, the weight ratio of total C16 / 18 nonionic surfactant to total alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0135] Preferably, the weight ratio of total nonionic surfactant to total C16 / 18 alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0136] Preferably, the weight ratio of total C18:1 nonionic surfactant to total C18:1 alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0137] Preferably, the weight ratio of total nonionic surfactant to linear alkylbenzene sulfonate (if present) (weight of nonionic surfactant / weight of linear alkylbenzene sulfonate) is from 0.1 to 2, preferably from 0.3 to 1, most preferably from 0.45 to 0.85.

[0138] Preferably, the weight ratio of total C16 / 18 nonionic surfactant to linear alkylbenzene sulfonate (if present) (weight of nonionic surfactant / weight of linear alkylbenzene sulfonate) is from 0.1 to 2, preferably from 0.3 to 1, most preferably from 0.45 to 0.85.

[0139] Preferably, the composition is visually clear.

[0140] Liquid laundry detergent

[0141] In the context of the present invention, 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 invention to provide compositions which upon dilution are capable of forming liquid laundry detergent compositions in the manner now described.

[0142] In a preferred embodiment, the liquid composition is isotropic.

[0143] The term "linen" is often used to describe specific types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles may include woven, nonwoven, and knitted fabrics; and may include natural or synthetic fibers, such as silk, flax, cotton, polyester, polyamide fibers such as nylon, acrylic, acetate, and blends thereof, including blends of cotton and polyester.

[0144] 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 delicate detergents and liquid color care detergents, such as those 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.

[0145] In the context of the present invention, the term "liquid" means that the continuous phase or the main part of the composition is liquid, and the composition is flowable at 15°C and above. Thus, the term "liquid" may include emulsions, suspensions, and compositions with a flowable but stiffer consistency known as gels or pastes. The viscosity of the composition is 25°C in 21 seconds. -1 The shear rate is preferably 200 to about 10,000 mPa.s. The shear rate is the shear rate normally applied to the liquid when pouring from a bottle. The pourable liquid detergent composition preferably has a viscosity of 200 to 1,500 mPa.s, preferably 200 to 700 mPa.s.

[0146] The composition according to the invention may suitably have an aqueous continuous phase. "Aqueous continuous phase" refers to a continuous phase that has water as its matrix. Preferably, the composition comprises at least 50% by weight of water, more preferably at least 70% by weight of water.

[0147] The alkyl ether sulfate may be provided as a single raw material component or by way of a mixture of components.

[0148] Where the composition comprises a mixture of C16 / 18 derived materials for the alkyl ether sulphates as well as the more traditional C12 alkyl chain length materials, it is preferred that the C16 / 18 alkyl ether sulphates should comprise at least 10 wt % of the total alkyl ether sulphates, more preferably at least 50 wt %, even more preferably at least 70 wt %, particularly preferably at least 90 wt % and most preferably at least 95 wt % of the alkyl ether sulphates in the composition.

[0149] The alcohol ethoxylate may be provided as a single raw material component or by way of a mixture of components.

[0150] Where the composition comprises a mixture of C16 / 18 derived materials for the alcohol ethoxylate as well as the more traditional C12 alkyl chain length materials, it is preferred that the C16 / 18 alcohol ethoxylate should comprise at least 10 wt % of the total alcohol ethoxylate, more preferably at least 50 wt %, even more preferably at least 70 wt %, particularly preferably at least 90 wt % and most preferably at least 95 wt % of the alcohol ethoxylate in the composition.

[0151] Preferably, the choice and amount of surfactant is such that the composition and diluted mixture are isotropic in nature.

[0152] Hydroxamate

[0153] Preferably, the composition comprises a hydroxamate.

[0154] Whenever the term "hydroxamic acid" or "hydroxamate" is used, unless otherwise indicated, this includes both the hydroxamic acid and the corresponding hydroxamate (salt of the hydroxamic acid).

[0155] Hydroxamic acids are 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:

[0156]

[0157] Where R 1 is an organic residue, such as an alkyl or alkylene group. The hydroxamic acid may be present as its corresponding alkali metal salt or hydroxamate. The preferred salt is the potassium salt.

[0158] Hydroxamates can be conveniently formed from the corresponding hydroxamic acid by replacing the acid hydrogen atom with a cation:

[0159]

[0160] L + is a monovalent cation, such as an alkali metal (eg, potassium, sodium), or ammonium or substituted ammonium.

[0161] In the present invention, hydroxamic acid or its corresponding hydroxamate has the following structure:

[0162]

[0163] Where R 1 yes

[0164] Straight or branched C4-C 20 Alkyl, or

[0165] Straight or branched substituted C4-C 20 Alkyl, or

[0166] Straight or branched C4-C 20 Alkenyl, or

[0167] Straight or branched substituted C4-C 20 Alkenyl, or

[0168] Alkyl ether group CH3(CH2) n (EO) m , wherein n is 2 to 20 and m is 1 to 12, or

[0169] Substituted alkyl ether group CH3(CH2) n (EO) m , wherein n is 2 to 20 and m is 1 to 12, and the type of substitution includes one or more of NH2, OH, S, -O- and COOH,

[0170] And R 2 is selected from hydrogen and a moiety that forms a branched R 1 Part of the ring structure of a group.

[0171] Preferred hydroxamates are those in which R 2 is hydrogen and R 1 C8 to C 14 The alkyl group is preferably n-alkyl, and most preferably saturated.

[0172] The general structure of the hydroxamic acid in the context of the present invention is indicated in Formula 3, and R 1 As defined above. 1 It is an alkyl ether group CH3(CH2) n (EO) m , wherein n is 2 to 20 and m is 1 to 12, then the alkyl moiety terminates the side group. 1 Selected from C4, C5, C6, C7, C8, C9, C 10 , C 11, C 12 and C 14 n-alkyl, most preferably R 1 At least C 8-14 When the C8 material is used, this is known as octyl hydroxamic acid. The potassium salt is particularly useful.

[0173]

[0174] Octanohydroxamic acid K salt

[0175] However, other hydroxamic acids, although less preferred, are also suitable for use in the present invention. Such suitable compounds include, but are not limited to, the following compounds:

[0176] Such hydroxamic acids include lysine hydroxamate HCl, methionine hydroxamate, and norvaline hydroxamate, and are commercially available.

[0177] Hydroxamates are believed to work by binding to metal ions present in the soil on fabrics. This binding is actually known as the chelating agent property of the hydroxamate, which itself does not have any effect on removing the soil from the fabric. The key is the "tail" of the hydroxamate, i.e. the group R 1 Reduced by group R 2 Any branching folded back to the amate nitrogen. The tail is selected to have an affinity for the surfactant system. This means that the soil removal ability of the optimized surfactant system is further enhanced by using the hydroxamate, because it actually marks the difficult-to-remove particulate matter (clay) as "dirt" to be removed by the surfactant system acting on the hydroxamate molecules, which are now fixed to the particles via their binding to the metal ions embedded in the clay-type particles. Non-soap detergent surfactants will adhere to the hydroxamate, resulting in more surfactant interacting with the fabric overall, resulting in better soil release. In this way, the hydroxamic acid plays the role of a linker molecule that promotes the removal and suspension of particulate soil from the fabric into the wash liquor, thereby enhancing initial detergency.

[0178] Hydroxamates have a higher affinity for transition metals such as iron than for alkaline earth metals such as calcium and magnesium, and therefore hydroxamic acid functions primarily to improve the removal of soils, especially particulate soils, from fabrics rather than acting additionally as a builder for calcium and magnesium.

[0179] A preferred hydroxamate is 80% solid cocoa 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 supplies cocoa hydroxamic acid as a 50% solid material under the trade name RK858. The 50% cocoa hydroxamic acid potassium salt is available as RK857. Another preferred material is RK842, an alkyl hydroxamic acid made from palm kernel oil from Axis House.

[0180] Preferably the hydroxamate is present in 0.1 to 3 wt % of the composition, more preferably 0.2 to 2 wt % of the composition.

[0181] Preferably, the weight ratio between hydroxamate and surfactant is from 0.05 to 0.3, more preferably from 0.75 to 0.2, most preferably from 0.8 to 1.2. The weight is calculated based on the protonated form.

[0182] Enzymes

[0183] The composition comprises enzymes selected from the group consisting of cellulases, proteases and amylase / mannanase mixtures.

[0184] Additionally, additional enzymes may be present, such as those described below.

[0185] Preferably, the composition may comprise an effective amount of one or more enzymes, preferably selected from lipase, hemicellulase, peroxidase, hemicellulase, xylanase, xantanase, lipase, phospholipase, esterase, cutinase, pectinase, carrageenase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tannase, nuclease (e.g., deoxyribonuclease and / or ribonuclease), phosphodiesterase, or mixtures thereof.

[0186] Preferably the enzyme level is from 0.1 to 100, more preferably from 0.5 to 50, most preferably from 5 to 30 mg active enzyme protein per 100 g of final laundry liquid composition.

[0187] Examples of preferred enzymes are sold under the trade names: Purafect (DuPont), Stainzyme (Novozymes), Biotouch (ABEnzymes), (BASF).

[0188] Detergent enzymes are discussed in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0189] Nucleases are enzymes capable of cleaving phosphodiester bonds 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 EC3.1.21.x (where x=1, 2, 3, 4, 5, 6, 7, 8 or 9), EC3.1.22.y (where y=1, 2, 4 or 5), EC3.1.30.Z (where z=1 or 2), EC3.1.31.1 and mixtures thereof.

[0190] Proteases hydrolyze bonds within peptides and proteins, which in laundry situations results in enhanced removal of stains containing proteins or peptides. Examples of suitable protease families include aspartic proteases; cysteine ​​proteases; glutamic proteases; asparagine (aspargine) peptide cleavage enzymes; 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. According to Siezen et al., Protein Engng. 4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501 -523, the term "subtilase" refers to a subgroup of serine proteases. Serine proteases are a subgroup of proteases characterized by having a serine in the active site that forms a covalent adduct with the substrate. Subtilases can be divided into six subclassifications, namely the Subtilisin family, Thermitase family, Proteinase K family, Lantibiotic peptidase family, Kexin family and Pyrolysin family.

[0191] 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; and 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 (WO 93 / 18140). Other useful proteases may be those described in WO 92 / 175177, WO 01 / 016285, WO 02 / 026024 and WO 02 / 016547. Examples of trypsin-like proteases are trypsin (e.g. of porcine or bovine origin) and the Fusarium protease (described in WO 89 / 06270, WO 94 / 25583 and WO 05 / 040372), and the chymotrypsin derived from Cellumonas described in WO 05 / 052161 and WO 05 / 052146.

[0192] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0193] Examples of subtilases are those derived from Bacillus such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described in US7262042 and WO09 / 021867; and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 described in WO89 / 06279; and protease PD138 described in (WO93 / 18140). Preferably, the subtilisin is derived from Bacillus, preferably Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, as described in US 6,312,936 Bl, US 5,679,630, US 4,760,025, US7,262,042 and WO 09 / 021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0194] Suitable commercially available proteases include those sold under the trade name DuralaseTm, DurazymTm, Ultra, Ultra, Ultra, Ultra, and Those that are sold, all can or (Novozymes A / S) sales.

[0195] 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 obtained from Bacillus, such as a special strain of Bacillus licheniformis described in more detail in GB 1,296,839, or a strain of Bacillus species disclosed in WO 95 / 026397 or WO 00 / 060060. Commercially available amylases are Duramyl TM Termamyl TM ,Termamyl Ultra TM 、Natalase TM 、Stainzyme TM 、Fungamyl TM and BAN TM (Novozymes A / S), Rapidase TMand Purastar TM (From Genencor International Inc.).

[0196] 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, Fusarium, Thielavia, Acremonium, such as the fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila and Fusarium oxysporum disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, WO96 / 029397 and WO 98 / 012307. Commercially available cellulases include Celluzyme TM 、Carezyme TM 、Celluclean TM 、Endolase TM 、Renozyme TM (Novozymes A / S), Clazinase TM and Puradax HA TM (Genencor International Inc.), and KAC-500(B) TM (Kao Corporation). Celluclean TM is preferred.

[0197] Lipase

[0198] Lipases are lipid esterases, and the terms "lipid esterase" and "lipase" are used synonymously herein.

[0199] The composition preferably comprises 0.0005 to 0.5 wt%, preferably 0.005 to 0.2 wt% lipase.

[0200] Detergent lipid esterases are discussed in Enzymes in Detergency edited by Jan H. Van Ee, Onno Misset and Erik J. Baas (1997 Marcel Dekker, New York).

[0201] The lipid esterase may be selected from the group consisting of lipases in EC class 3.1 or 3.2, or combinations thereof.

[0202] Preferably, the cleaning lipid esterase is selected from:

[0203] (1) Triacylglycerol lipase (EC3.1.1.3)

[0204] (2) Carboxyl ester hydrolase (EC3.1.1.1)

[0205] (3) Cutinase (EC 3.1.1.74)

[0206] (4) Sterol esterase (EC3.1.1.13)

[0207] (5) Wax-ester hydrolase (EC 3.1.1.50)

[0208] Triacylglycerol lipase (EC 3.1.1.3) is most preferred.

[0209] Suitable triacylglycerol lipases may be selected from variants of Humicola lanuginosa (Thermomyces lanuginosus) lipase. Other suitable triacylglycerol lipases can be selected from: variants of Pseudomonas lipases, for example from Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes (EP 218 272), Pseudomonas cepacia (EP 331 376), Pseudomonas stutzeri (GB 1,372,034), Pseudomonas fluorescens, Pseudomonas species strain SD 705 (WO 95 / 06720 and WO 96 / 27002), Pseudomonas wisconsinensis (WO 96 / 12012); Bacillus lipase, for example from Bacillus subtilis (B. subtilis) (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), Bacillus stearothermophilus (B. stearothermophilus) (JP 64 / 744992) or Bacillus pumilus (WO91 / 16422).

[0210] Suitable carboxyl ester hydrolases can be selected from wild-type or variants of the following endogenous carboxyl ester hydrolases: Burkholderia gladioli (B. gladioli), Pseudomonas fluorescens, Pseudomonas putida (P. putida), Bacillus acidocaldarius (B. acidocaldarius), Bacillus subtilis, Bacillus stearothermophilus, Streptomyces chrysomallus, Streptomyces diastatochromogenes (S. diastatochromogenes) and Saccaromyces cerevisiae.

[0211] Suitable cutinases may be selected from the wild type or variants of the following endogenous cutinases: strains of Aspergillus, in particular Aspergillus oryzae; strains of Alternaria, in particular Alternaria brassiciola; strains of Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum culmorum or Fusarium roseum sambucium; strains of Helminthosporum, in particular Helminthosporum occidentalis. sativum; strains of the genus Humicola, in particular Humicola insolens; strains of the genus Pseudomonas, in particular Pseudomonas mendocina or Pseudomonas putida; strains of the genus Rhizoctonia, in particular Rhizoctonia solani; strains of the genus Streptomyces, in particular Streptomyces scabies; strains of the genus Coprinopsis, in particular Coprinopsis cinerea; strains of the genus Thermobifida, in particular Thermobifida fusca; strains of the genus Magnaporthe, in particular Magnaporthe grisea; or strains of the genus Ulocladium, in particular Ulocladium consortiale.

[0212] In a preferred embodiment the Cutinase is selected from variants of the Pseudomonas mendocina Cutinase described in WO 2003 / 076580 (Genencor), such as a variant having three substitutions at I178M, F180V and S205G.

[0213] In another preferred embodiment, the cutinase is the wild type or variant of the six cutinases endogenous to Coprinus cinereus described in H. Kontkanen et al, App. Environ. Microbiology, 2009, p2148-2157.

[0214] In another preferred embodiment, the Cutinase is the wild type or variant of the two Cutinases endogenous to Trichoderma reesei described in WO2009007510 (VTT).

[0215] In a most preferred embodiment, the Cutinase is derived from a strain of Humicola insolens, in particular Humicola insolens strain DSM 1800. Humicola insolens Cutinase is described in WO 96 / 13580, which is incorporated herein by reference. The Cutinase may 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 Cutinase includes Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0216] Suitable sterol esterases may be derived from a strain of Ophiostoma, such as Ophiostomapiceae; a strain of Pseudomonas, such as Pseudomonas aeruginosa; or a strain of Melanocarpus, such as Melanocarpus albomyces.

[0217] In a 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.

[0218] Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.The lipid esterase is preferably selected from the lipases of EC class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably EC 3.1.1.3.

[0219] 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, Rhizmucor miehei, Rhizopus deleman, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosus) and Landerina penisapora, in particular Thermomyces lanoginosus. Particularly preferred lipases are produced by Novozymes under the trade name Lipolase and (registered trademark of Novozymes); and from Areario Pharmaceutical Co. Ltd., Nagoya, Japan as LIPASE P Available from Toyo Jozo Co., Tagata, Japan Commercially available; and additional Chromobacter viscosum lipase from Amersham Pharmacia Biotech., Piscataway, New Jersey, USA and Diosynth Co., Netherlands; and other lipases, such as Pseudomonas gladioli. Additional available lipases are described in WIPO publications WO 02062973, WO 2004 / 101759, WO 2004 / 101760 and WO 2004 / 101763. In one embodiment, suitable lipases include "first cycle lipases" described in WO 00 / 60063 and U.S. Pat. No. 6,939,702B1, 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 substitution of an electrically neutral or negatively charged amino acid at any one of positions 3, 224, 229, 231 and 233 by R or K, most preferably variants comprising T23 IR and N233R mutations, such most preferred variants being marketed under the trade name (Novozymes) sales.

[0220] The above lipases can be used in combination (any mixture of lipases can be used). Suitable lipases can be purchased from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co. Ltd., Nagoya, Japan; Toyo Jozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, USA; Diosynth Co., Oss, Netherlands; and / or prepared according to the examples included herein.

[0221] Lipid esterases with reduced odor generation potential and good relative performance as described in WO 2007 / 087243 are particularly preferred. These include (Novozyme).

[0222] Preferred commercially available lipases include Lipolase TM and Lipolase Ultra TM 、Lipex TM and Lipoclean TM (Novozymes A / S).

[0223] spices

[0224] Preferably, the composition comprises a fragrance.

[0225] Perfume is present in an amount of 0.01 to 5% by weight of the composition.

[0226] Preferably, the fragrance comprises a component selected from the group consisting of: ethyl-2-methylvalerate (2-methylvalerate ethyl ester (manzanate)); limonene; (4Z)-cyclopentadeca-4-en-1-one; dihydromyrcenol; dimethylbenzyl carbonate acetate; benzyl acetate; spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)]; benzyl acetate; rose oxide; geraniol; methylnonyl acetaldehyde; cyclacet (verdyl acetate) acetate); cyclamal; β-ionone; hexyl salicylate; tonalid; [2-(cyclohexyloxy)ethyl]benzene (phenafleur); octahydrotetramethylacetophenone (OTNE); benzene; toluene; xylene (BTX) raw materials such as 2-phenylethanol, γ-methylphenoxanol and mixtures thereof; cyclododecanone raw materials such as habolonolide; phenolic plastic raw materials such as hexyl salicylate; heterocyclic moiety raw materials containing C5 blocks or oxygen such as γ-decanolide, methyl dihydrojasmonate and mixtures thereof; terpene raw materials such as dihydromyrcenol, linalool, terpinene, camphor, citronellol and mixtures thereof; alkyl alcohol raw materials such as ethyl-2-methylbutyrate; diacid raw materials such as ethylene glycol brazic acid; and mixtures of these components.

[0227] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance ethyl-2-methylvalerate (ethyl 2-methylvalerate).

[0228] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance limonene.

[0229] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance (4Z)-cyclopentadeca-4-en-1-one.

[0230] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance dimethylbenzyl carbonate acetate.

[0231] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance dihydromyrcenol.

[0232] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance oxidized rose.

[0233] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance verdyl acetate.

[0234] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance benzyl acetate.

[0235] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

[0236] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance geraniol.

[0237] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance methylnonyl acetaldehyde.

[0238] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance cyclacet (verdyl acetate).

[0239] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance cyclamen aldehyde.

[0240] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance β-ionone.

[0241] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance hexyl salicylate.

[0242] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance Musk Tonalite.

[0243] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of the fragrance [2-(cyclohexyloxy)ethyl]benzene.

[0244] Preferably, the fragrance comprises a component selected from the group consisting of benzene, toluene, xylene (BTX) raw materials. More preferably, the fragrance component is selected from the group consisting of 2-phenylethanol, γ-methylphenylpentanol and mixtures thereof.

[0245] Preferably, the fragrance comprises a component selected from the class of cyclododecanone raw materials. More preferably, the fragrance component is habolonolide.

[0246] Preferably, the fragrance comprises a component selected from the class of phenolic plastic raw materials. More preferably, the fragrance component is hexyl salicylate.

[0247] Preferably, the perfume comprises a component selected from the class of raw materials containing heterocyclic moieties containing C5 blocks or oxygen. More preferably, the perfume component is selected from gamma-decanolide, methyl dihydrojasmonate and mixtures thereof.

[0248] Preferably, the fragrance comprises a component selected from the class of terpene raw materials. More preferably, the fragrance component is selected from linalool, terpinene, camphor, citronellol and mixtures thereof.

[0249] Preferably, the fragrance comprises a component selected from the class of alkyl alcohol raw materials. More preferably, the fragrance component is ethyl-2-methylbutyrate.

[0250] Preferably, the fragrance comprises a component selected from the class of diacid raw materials. More preferably, the fragrance component is ethylene glycol brazyl.

[0251] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight, particularly preferably 6 to 10% by weight of octahydrotetramethylacetophenone (OTNE). OTNE is an abbreviation for fragrance materials with CAS numbers 68155-66-8, 54464-57-2 and 68155-67-9 and EC list number 915-730-3.

[0252] Preferably, OTNE is present in the form of a multi-component isomer mixture comprising:

[0253] 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 54464-57-2)

[0254] 1-(1,2,3,5,6,7,8,8a-Octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 68155-66-8)

[0255] 1-(1,2,3,4,6,7,8,8a-Octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 68155-67-9)

[0256] Such OTNE and its method of manufacture are fully described in US 3,907,321 (IFF).

[0257] Fragrance molecule 01 is a specific isomer of OTNE, commercially available from IFF. Another commercially available fragrance, Escentric 01, contains not only OTNE, but also ambroxan, pink pepper, green lime, and balsamic notes such as benzoin frankincense and incense.

[0258] Typically, commercially available perfume raw materials contain 1 to 8 wt% of the perfume raw material OTNE.

[0259] Preferably, the above listed perfume components are present in the finished detergent composition at from 0.0001 to 1 % by weight of the composition.

[0260] Fluorescent agent

[0261] Preferably, the composition comprises a fluorescent agent. More preferably, the fluorescent agent comprises a sulphonated distyrylbiphenyl fluorescent agent, such as those discussed in Chapter 7 of Industrial Dyes (K. Hunger ed, Wiley VCH 2003).

[0262] Sulfonated distyrylbiphenyl fluorescent agents are discussed in US Pat. No. 5,145,991 (Ciba Geigy).

[0263] 4,4'-distyryl biphenyl is preferred. Preferably, the fluorescent agent contains 2 SO3 - Group.

[0264] Most preferably, the fluorescent agent has the following structure:

[0265]

[0266] wherein X is a suitable counter ion, 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.

[0267] Preferably, the fluorescent agent is present in an amount of 0.01 wt% to 1 wt%, more preferably 0.05 wt% to 0.4 wt%, most preferably 0.11 wt% to 0.3 wt% of the composition.

[0268] Surfactants based on C16 and / or C18 alkyl groups, whether alcohol ethoxylates or alkyl ether sulfates, are typically available as mixtures with C16 and C18 alkyl chain length stocks.

[0269] Defoaming agent

[0270] The composition may also comprise an anti-foaming agent, but preferably it does not.Anti-foaming materials are well known in the art and include silicones and fatty acids.

[0271] Preferably the fatty acid soap is present at from 0 to 0.5 wt% of the composition (measured relative to the acid added to the composition), more preferably from 0 to 0.1 wt%, most preferably 0 wt%.

[0272] In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a linear or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms, and 0 or 1 double bonds. 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, wherein 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can typically be derived from natural fats and / or optionally hydrogenated natural oils (e.g. coconut oil, palm kernel oil or tallow).

[0273] The fatty acids may be present in the form of their sodium, potassium or ammonium salts and / or in the form of soluble salts with organic bases such as mono-, di- or tri-ethanolamine.

[0274] Mixtures of any of the above materials may also be used.

[0275] For the purpose of formula description, fatty acids and / or their salts (as defined above) are not included in the surfactant level or in the builder level in the formulation.

[0276] Preferably, the composition comprises from 0.2 to 10% by weight of the composition of a cleaning polymer.

[0277] Preferably, the cleaning polymer is selected from the group consisting of alkoxylated polyethyleneimines, polyester soil release polymers, and PEG / vinyl acetate copolymers.

[0278] preservative

[0279] Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition Springer.

[0280] The formulation contains a preservative, or a mixture of preservatives, selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and their salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, most preferably sodium benzoate.

[0281] Alternatively preferred preservatives are selected from sodium benzoate, phenoxyethanol, dehydroacetic acid and mixtures thereof.

[0282] The preservative is present at 0.1 to 3 wt%, preferably 0.3 to 1.5 wt%. Where appropriate, weights are calculated in protonated form.

[0283] Preferably, the composition comprises from 0.1% to 3% by weight, preferably from 0.3% to 1.5% by weight of the composition of sodium benzoate.

[0284] Preferably, the composition comprises from 0.1% to 3%, preferably from 0.3% to 1.5% by weight of the composition of phenoxyethanol.

[0285] Preferably, the composition comprises from 0.1% to 3% by weight, preferably from 0.3% to 1.5% by weight of dehydroacetic acid, based on the composition.

[0286] Preferably, the composition comprises less than 0.1 wt%, more preferably less than 0.05 wt% of isothiazolinone-based preservatives.

[0287] Polymer cleaning enhancers

[0288] Anti-redeposition polymers stabilize soil in the wash solution, thereby preventing the soil from redeposition. Suitable soil release polymers for use in the present invention include alkoxylated polyamines, preferably alkoxylated polyethyleneimines. Polyethyleneimines are materials consisting of ethyleneimine units -CH2CH2NH-, and in the case of branching, the hydrogen on the nitrogen is replaced by another chain of ethyleneimine units. Preferred alkoxylated polyethyleneimines for use in the present invention have a weight average molecular weight (MW) of about 300 to about 10,000. w). The polyethyleneimine backbone can be linear or branched. It can be branched to the extent that it is a dendritic polymer. The alkoxylation can generally be ethoxylation or propoxylation, or a mixture of the two. When the nitrogen atoms are alkoxylated, the preferred average degree of alkoxylation is 10 to 30, preferably 15 to 25 alkoxy groups per modification. The preferred material is ethoxylated polyethyleneimine, wherein the average degree of ethoxylation is 10 to 30, preferably 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.

[0289] Mixtures of any of the above materials may also be used.

[0290] More preferably, the polyamine is an alkoxylated zwitterionic diamine or polyamine polymer in which the positive charge is provided by quaternization of the amine nitrogen atom and the anion, if present, is provided by sulfation or sulfonation of the alkoxylated groups.

[0291] Preferably, the alkoxy group of the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0292] Preferably, greater than or equal to 50 mol % of the amine nitrogen is quaternized, preferably with methyl. Preferably, the polymer contains 2 to 10, more preferably 2 to 6, most preferably 3 to 5 quaternized amine nitrogens. Preferably, the alkoxylate group is selected from ethoxy and propoxy, most preferably ethoxy.

[0293] Preferably, the polymer contains ester (COO) groups or acid amide (CONH) groups within the structure, preferably these groups are placed so that when all ester groups or acid amide groups are hydrolyzed, at least one, preferably all of the hydrolyzed fragments have a molecular weight of less than 4000, preferably less than 2000, most preferably less than 1000.

[0294] Preferably, the polymer has the following form:

[0295]

[0296] wherein R1 is a C3 to C8 alkyl group, X is a (C2H4O)nY group, wherein n is 15 to 30, wherein m is 2 to 10, preferably 2, 3, 4 or 5, and wherein Y is selected from OH and SO3 - , and preferably SO3 - The number of groups is greater than the number of OH groups. Preferably, 0, 1 or 2 OH groups are present. X and R1 may contain an ester group among them. X may contain a carbonyl group, preferably an ester group. Preferably, there is 1 C2H4O unit separating the ester group from N, so that the structural unit N-C2H4O-ester-(C2H4O) n-1 Y is preferred.

[0297] Such polymers are described in WO2021239547 (Unilever). Exemplary polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO 2021239547. Acid amide and ester groups may be included by addition to OH or NH groups using lactones or sodium chloroacetate, respectively (modified Williamson synthesis), followed by subsequent ethoxylation.

[0298] An exemplary reaction scheme involving an ester group is

[0299]

[0300] The addition of lactones is discussed in WO2021 / 165468.

[0301] The compositions of the present invention will preferably comprise from 0.025 to 8% by weight of one or more anti-redeposition polymers, for example the alkoxylated polyethyleneimines or zwitterionic polyamines described above.

[0302] Soil release polymers

[0303] Soil release polymers help improve soil removal from fabrics by modifying the fabric surface during washing. The adsorption of SRPs on the fabric surface is facilitated by the affinity between the chemical structure of the SRP and the target fibers.

[0304] The SRP used in the present invention may include a variety of charged (e.g., anionic) and uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also contain end-capping groups to control the molecular weight or to change the polymer properties such as surface activity. The weight average molecular weight (M) of the SRP is w ) may suitably be in the range of about 1000 to about 20,000, preferably in the range of about 1500 to about 10,000.

[0305] The SRP used in the present invention can be suitably selected from copolyesters of dicarboxylic acids (e.g. adipic acid, phthalic acid or terephthalic acid), diols (e.g. ethylene glycol or propylene glycol) and polyglycols (e.g. polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, for example, sulfonated isophthaloyl units. Examples of such materials include: oligoesters prepared by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and polyethylene glycol ("PEG"); partially- and fully-anionically terminated oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and Na-3,6-dioxa-8-hydroxyoctane sulfonate; nonionically terminated block polyester oligomeric compounds, such as those prepared from DMT, Me-terminated PEG, and EG and / or PG, or DMT, EG and / or PG, Me-terminated PEG, and Na-dimethyl-5-sulfoisophthalate; and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0306] Other types of SRPs useful in the present invention include cellulose derivatives, such as hydroxyether cellulose polymers, C1-C4 alkyl celluloses, and C4 hydroxyalkyl celluloses; polymers having poly(vinyl ester) hydrophobic segments, such as graft copolymers of poly(vinyl esters), such as C1-C6 vinyl esters grafted onto a polyalkylene oxide backbone (e.g., 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.

[0307] Preferred SRPs for use in the present invention include copolyesters formed from the condensation of terephthalate and a diol, preferably 1,2-propylene glycol, and further include endcaps formed from repeating units of alkylene oxides endcapped with alkyl groups. Examples of such materials have structures corresponding to formula (I):

[0308]

[0309] Where R 1 and R 2 Independently of each other are X-(OC2H4) n -(OC3H6) m ;

[0310] Where X is C 1-4 Alkyl, preferably methyl;

[0311] n is a number from 12 to 120, preferably from 40 to 50;

[0312] m is a number from 1 to 10, preferably from 1 to 7; and

[0313] a is a number from 4 to 9.

[0314] Because they are average values, m, n and a are not necessarily integers for the polymer as a whole.

[0315] Mixtures of any of the above materials may also be used.

[0316] When included, the overall level of SRP may range from 0.1 to 10%, depending on the level of polymer intended for use in the final let-down composition, and ideally is 0.3 to 7%, more preferably 0.5 to 5% (by weight based on the total weight of the let-down composition).

[0317] 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 employed, soil release polymers will typically be incorporated into the liquid laundry detergent compositions herein at a concentration of 0.01% to 10%, more preferably 0.1% to 5%, by weight of the composition.

[0318] Hydrotropes

[0319] The compositions of the present invention may include non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (e.g., ethanol and n-propanol or isopropanol); C2 to C6 diols (e.g., monopropylene glycol and dipropylene glycol); C3 to C9 triols (e.g., glycerol); polyethylene glycols having a weight average molecular weight (Mw) of about 200 to 600; C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylaryl sulfonates having up to 3 carbon atoms in the lower alkyl group (e.g., sodium xylene, toluene, ethylbenzene and cumene (cumene) sulfonates, and potassium xylene, toluene, ethylbenzene and cumene (cumene) sulfonates).

[0320] Mixtures of any of the above materials may also be used.

[0321] When included, the non-aqueous carrier may be present in an amount of 0.1 to 3%, preferably 0.5 to 1% (by weight based on the total weight of the composition). The level of hydrotrope used is related to the level of surfactant, and it is desirable to use the hydrotrope level to control the viscosity of such compositions. Preferred hydrotropes are monopropylene glycol and glycerol.

[0322] Co-surfactant

[0323] In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the compositions of the present invention may also contain one or more co-surfactants (eg, amphoteric (zwitterionic) and / or cationic surfactants).

[0324] Specific cationic surfactants include: C8 to C18 alkyl dimethyl ammonium halides; and their derivatives in which one or two hydroxyethyl groups replace one or two methyl groups; and mixtures thereof. When included, the cationic surfactant is present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0325] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkyl amidopropyl hydroxysulfobetaines, acyl taurates and acyl glutamates, which have an alkyl group 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 may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0326] Mixtures of any of the above materials may also be used.

[0327] Builders and Chelating Agents

[0328] The detergent composition may also optionally contain relatively low levels of organic detergent builders or chelating materials. Examples include alkali metals, citrates, succinates, malonates, carboxymethylsuccinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylates and citric acid. Other examples are DEQUEST TM (organic phosphonate-type chelating agents sold by Monsanto), and alkylhydroxyphosphonates.

[0329] Other suitable organic builders include the higher molecular weight polymers and copolymers known to have builder properties. For example, such materials include suitable polyacrylic acid, polymaleic acid and polyacrylic acid / polymaleic acid copolymers and their salts, such as those marketed by BASF under the name SOKALAN TMThe organic builder material can account for about 0.5% to 20% by weight of the composition, preferably 1% to 10% by weight. The preferred builder content is less than 10% by weight, preferably less than 5% by weight, according to the composition. More preferably, the liquid laundry detergent formulation is a non-phosphate-assisted laundry detergent formulation, i.e., contains less than 1% by weight of phosphate. Most preferably, the laundry detergent formulation is not assisted, i.e., contains less than 1% by weight of builder. Typically, in liquids, a preferred chelating agent is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), such as sold as Dequest 2010. Also suitable but less preferred is Dequest (R) 2066 (diethylenetriamine penta (methylenephosphonic acid) or DTPMP heptasodium), because it produces poor cleaning results. However, it is preferred that the composition comprises less than 0.5 wt% phosphonate based chelating agents, more preferably less than 0.1 wt% phosphonate based chelating agents.Most preferably, the composition is free of phosphonate based chelating agents.

[0330] Polymer thickener

[0331] The compositions of the present invention may include one or more polymeric thickeners. Suitable polymeric thickeners for use in the present invention include hydrophobically modified alkali swellable emulsion (HASE) copolymers. Exemplary HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization 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 invention refers to a monomer having an ethylenically unsaturated portion (for addition polymerization with other monomers in the mixture) and a hydrophobic portion. A preferred type of associative monomer includes a polyoxyalkylene portion between the ethylenically unsaturated portion and the hydrophobic portion. Preferred HASE copolymers for use in the present invention include linear or crosslinked copolymers prepared by addition polymerization of (meth)acrylic acid with: (i) at least one associative monomer selected from a linear or branched C8-C 40 Alkyl (preferably linear C 12 -C 22 (ii) at least one additional monomer selected from the group consisting of C1-C4 alkyl (meth)acrylates, polyacid vinyl monomers (e.g., maleic acid, maleic anhydride and / or their salts), and mixtures thereof. The polyethoxylated portion of the associative monomer (i) typically comprises from about 5 to about 100, preferably from about 10 to about 80, more preferably from about 15 to about 60 oxyethylene repeating units.

[0332] Mixtures of any of the above materials may also be used.

[0333] When included, the compositions of the present invention will preferably comprise from 0.01 to 5 wt % of a polymeric thickener based on the composition, but depending on the amount intended for use in the final diluted product, and desirably from 0.1 to 3 wt % by weight based on the total weight of the diluted composition.

[0334] Color dye

[0335] Shading dyes can be used to improve the performance of the composition. Preferred dyes are violet or blue. It is believed that low levels of dyes of these shades deposited on fabrics will mask the yellowing of the fabric. Another advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself.

[0336] Hueing dyes are well known in the art of laundry liquid formulations.

[0337] Suitable and preferred dye classes 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 ethoxylated or propoxylated polyethylene imine as described in WO 2011 / 047987 and WO 2012 / 119859, alkoxylated monoazothiophenes, dyes with CAS number 72749-80-5, acid blue 59 and phenazine dyes selected from the group consisting of:

[0338]

[0339] in:

[0340] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5;

[0341] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and -OC2H5;

[0342] Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0343] Alkoxylated thiophene dyes are discussed in WO 2013 / 142495 and WO 2008 / 087497.

[0344] The hueing dye is preferably present in the composition in the range of 0.0001 to 0.1 wt%.Depending on the nature of the hueing dye there will be a preferred range depending on the potency of the hueing dye, which depends on the species and the specific potency within any particular species.

[0345] External structurants

[0346] The compositions of the present invention may further modify their rheology by using one or more external structurants that form a structural network within the composition. Examples of such materials include crystallizable glycerides, such as hydrogenated castor oil; microfiber cellulose and citrus pulp fibers. The presence of an external structurant may provide shear-thinning rheology and may also enable materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0347] The composition preferably comprises a crystallizable glyceride.

[0348] Crystallizable glycerides can be used to form an external structuring system as described in WO2011 / 031940, the contents of which (particularly with respect to the manufacture of ESS) are incorporated herein by reference. Where an ESS is present, it is preferred that the ESS of the present invention preferably comprises: (a) one or more crystallizable glycerides; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

[0349] As used herein, "one or more crystallizable glycerides" preferably include "hydrogenated castor oil" or "HCO". As used herein, "HCO" can most generally be any hydrogenated castor oil as long as it can be crystallized in the ESS premix. Castor oil can include glycerides, particularly triglycerides, containing C10 to C22 alkyl or alkenyl moieties, the alkyl or alkenyl moieties containing hydroxyl groups. Castor oil is hydrogenated to prepare HCO to convert double bonds that may be present in the feedstock oil as a ricinoleyl moiety to convert the ricinoleyl moiety into a saturated hydroxyalkyl moiety, for example, a hydroxystearyl. In some embodiments, the HCO herein may be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. The HCO can be processed in any suitable starting form, including but not limited to those selected from a solid state, a molten state, and mixtures thereof. HCO is typically present in the ESS of the present invention at a level 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%.

[0350] Useful HCO may have the following characteristics: a melting point of about 40°C to about 100°C, or about 65°C to about 95°C; and / or an iodine value range of 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 used in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO used in the present invention include: THIXCIN (R) from Rheox, Inc. Other examples of useful HCO can be found in U.S. Patent No. 5,340,390. The source of castor oil used for hydrogenation to form HCO can have any suitable origin, such as from Brazil or India. In a suitable embodiment, castor oil is hydrogenated using a noble metal such as a palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds of natural castor oil while avoiding unacceptable levels of dehydroxylation.

[0351] The present invention is not intended to relate only to the use of hydrogenated castor oil. Any other suitable one or more crystallizable glycerides may be used. In one example, the structuring agent is a substantially pure triglyceride of 12-hydroxystearic acid. This molecule represents a pure form of a fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is fairly constant, but may vary slightly. Likewise, the hydrogenation procedure may vary. Any other suitable equivalent material may be used, such as a mixture of triglycerides, wherein at least 80% by weight is from castor oil. Exemplary equivalent materials mainly contain triglycerides, or are essentially composed of triglycerides; or mainly contain a mixture of diglycerides and triglycerides, or are essentially composed of a mixture of diglycerides and triglycerides; or mainly contain a mixture of triglycerides and diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides, or are essentially composed of a mixture of triglycerides and diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides; or mainly contain any of the aforementioned glycerides and a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolyzate of any of the aforementioned glycerides, or are essentially composed of any of the aforementioned glycerides and a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolyzate of any of the aforementioned glycerides. The premise in the above is that the major portion (usually at least 80% by weight) of any of the glycerides is chemically identical to the glyceride of fully hydrogenated ricinoleic acid, i.e., the glyceride of 12-hydroxystearic acid. For example, it is well known in the art to modify hydrogenated castor oil so that two 12-hydroxystearic acid-moieties and one stearic acid moiety are present in a given triglyceride. Likewise, it is conceivable that hydrogenated castor oil may not be fully hydrogenated. In contrast, when these do not meet the melting criteria, the present invention does not include poly(alkoxylated) castor oils.

[0352] The one or more crystallizable glycerides used in the present invention may have a melting point of about 40°C to about 100°C.

[0353] Microcapsules

[0354] A type of microparticle suitable for use in the present invention is a microcapsule. Microencapsulation can be defined as a method in which a substance is surrounded or wrapped in another substance on a very small scale, thereby producing a capsule ranging in size from less than one micron to hundreds of microns. Encapsulated material can be referred to as a core, active ingredient or reagent, filler, payload, core or internal phase. The material encapsulating the core can be referred to as a coating, film, shell or wall material.

[0355] Microcapsules typically have at least one generally spherical continuous shell surrounding a core. Depending on the material and encapsulation technique employed, the shell may contain holes, vacancies or interstitial openings. Multiple shells may be made of the same or different encapsulating materials and may be arranged in layers of varying thickness around the core. Alternatively, the microcapsules may be asymmetrically and variably shaped, wherein a certain amount of smaller core material droplets are embedded throughout the microcapsule.

[0356] The shell may have a barrier function to protect the core material from the environment outside the microcapsule, but it may also serve as a means of regulating the release of the core material, such as a fragrance. Thus, the shell may be water-soluble or water-swellable and may initiate fragrance release in response to exposure of the microcapsule to a humid environment. Similarly, if the shell is temperature sensitive, the microcapsule may release fragrance in response to elevated temperatures. The microcapsule may also release fragrance in response to shear forces applied to the surface of the microcapsule.

[0357] A preferred type of polymer microparticle suitable for use in the present invention is a polymer core-shell microcapsule in which at least one generally spherical continuous shell of a polymer material surrounds a core containing a fragrance formulation (f2). The shell will typically account for up to 20% by weight, based on the total weight of the microcapsule. The fragrance formulation (f2) will typically account for about 10% to about 60% by weight, preferably about 20% to about 40% by weight, based on the total weight of the microcapsule. The amount of fragrance (f2) can be measured by taking a slurry of the microcapsule, extracting it into ethanol and measuring it by liquid chromatography.

[0358] Additional optional ingredients

[0359] The composition of the present invention may include other optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include foam enhancers, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, anticorrosives, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or sunscreens and tinting dyes. Each of these ingredients will exist in an amount that effectively achieves its purpose. Typically, these optional ingredients are individually included in an amount of up to 5% (by weight based on the gross weight of the dilution composition), and are therefore adjusted with water according to the dilution ratio.

[0360] Example

[0361] As described in WO2021 / 239547, a laundry detergent was produced with 25% by weight of total surfactant and with and without the addition of 1% by weight of a zwitterionic ethoxylated polymer based on tetrapropylene imine. The pH value of the formulation was 7. The surfactant used was linear alkylbenzene sulfonate (LAS) neutralized with triethanolamine. Sodium oleyl ether sulfate (ES) with an average value of 6 moles of ethoxylation. The oleyl alcohol used had the following composition: C16:0 17% by weight, C18:0 10% by weight, C18:1 63% by weight, C18:2 7% by weight, and the remaining C12:0, C14:0, C18:3 and C20. The methyl ester ethoxylate is based on refined bleached deodorized palm oil (composition C16:0 45 wt%, C18:0 4 wt%, C18:1 40 wt%, C18:2 10 wt%, the remainder being C12:0, C14:0, C18:3 and C20) with an average value of 10 moles of ethoxylation.

[0362] After the formulation was prepared, the viscosity was measured (21 Hz) and the change in viscosity was expressed as a fraction α, where:

[0363] α = Viscosity with EPPI / Viscosity without EPPI

[0364] The results are summarized in the table below.

[0365]

[0366] In LAS, the addition of zwitterionic ethoxylated polymers reduced the viscosity by 40%.

[0367] In anionic surfactant / MEE blends where the wt% of LAS ≥ the wt% of ether sulfate, the addition of zwitterionic ethoxylated polymer reduced viscosity by more than 40%.

Claims

1. A liquid composition comprising: (A) a linear alkylbenzene sulfonate, (B) a methyl ester ethoxylate, and (C) another anionic surfactant, and 0.5 to 10 wt. % of an alkoxylated zwitterionic diamine or polyamine polymer, wherein the (C) / (A) weight ratio is 1 to 0, and the (B) / (A)+(B) weight ratio is 0.2 to 9, wherein the content of the surfactant in the formulation is 10 to 60 wt. %.

2. The composition according to claim 1, wherein the weight ratio (B) / (A)+(B) is from 0.25 to 8.

3. A composition according to any one of the preceding claims, wherein the surfactant is present in the formulation in an amount of from 15 to 30% by weight of the composition.

4. A composition according to any one of the preceding claims, wherein the alkoxy group of the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

5. A composition according to any one of the preceding claims, said composition having a pH of from 5 to 10, more preferably from 6 to 8, most preferably from 6.1 to 7.0.

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