Washing machine and washing method

Abstract

A washing machine including a detergent reservoir, the reservoir comprising from 80 ml to 3000 ml of a liquid detergent comprising a methyl ester ethoxylate.

Description

[0001] The present invention relates to a washing machine and a detergent combination.

[0002] Despite the prior art, there remains a need for improved laundry liquid compositions for use in automatic dosing washing machines.

[0003] Thus, in a first aspect there is provided a washing machine comprising a detergent reservoir, the reservoir containing from 80ml to 3000ml of liquid detergent comprising methyl ester ethoxylate.

[0004] In a second aspect, there is provided a method for cleaning fabrics comprising filling the tank of a washing machine with 80 ml to 3000 ml of a liquid detergent composition comprising methyl ester ethoxylate,

[0005] and performing at least two wash cycles before adding additional liquid detergent to the sump.

[0006] In a third aspect, there is provided a method for cleaning fabrics comprising filling the tank of a washing machine with 80 ml to 3000 ml of a liquid laundry detergent composition comprising methyl ester ethoxylate,

[0007] and performing a wash cycle which draws a portion of the liquid detergent from the sump but leaves at least 20 ml in the sump.

[0008] The amount of 80 ml to 3000 ml of liquid detergent characterizes the amount of detergent for more than one dose.Preferably, the reservoir contains 250 ml to 2500 ml, more preferably 400 ml to 2000 ml of liquid detergent.

[0009] The washing machine preferably comprises a detergent storage tank capable of storing up to 3000 ml of detergent. Such washing machines are known in the market as automatic dosing washing machines and are capable of storing enough liquid detergent for more than one wash cycle, preferably for a plurality of wash cycles. Preferably, the washing machine is a front loading automatic washing machine.

[0010] Preferably, the washing machine comprises a housing; a washing tub, which is arranged in the housing and whose opening or mouth directly faces the clothes loading / unloading opening realized on the front wall of the housing; a detergent dispensing assembly, which is configured to supply detergent into the washing tub; a main tap water supply circuit, which is configured to be connected to the main water pipe and is used to selectively guide the tap water flow from the main water pipe to the detergent dispensing assembly and / or the washing tub; and an appliance control panel, which is configured to allow a user to manually select a desired washing cycle.

[0011] The washing machine detergent dispensing assembly also includes an automatic dosing detergent dispenser, which is configured to automatically dose an appropriate amount of detergent for use during a selected wash cycle based on the selected wash cycle, and which includes: one or more detergent storage tanks, each of which is configured to receive a certain amount of detergent for performing multiple wash cycles; and for each detergent storage tank, a corresponding detergent supply pump, which is configured to selectively draw an amount of detergent for performing the selected wash cycle from the corresponding detergent storage tank and pump / direct the specific amount of detergent into a detergent collection chamber that is fluidly connected to the washing tub.

[0012] Using an automatic dosing washing machine, a consumer can perform multiple wash cycles before needing to add additional liquid detergent to the reservoir. Typically, the reservoir is sufficient for five or more washes, and possibly as many as 20, depending on the size of the reservoir in the washing machine and the dosage used for each wash cycle.

[0013] Each wash cycle involves drawing a volume of liquid laundry detergent from the sump sufficient to form a suitable wash liquor for cleaning fabrics.

[0014] Preferably, the volume is from 10 to 75 ml, but this may depend on the amount of fabric, the stains to be cleaned and the amount of surfactants and other cleaning agents in the liquid laundry composition.

[0015] After the first wash cycle is complete, the remaining liquid detergent remains in the washing machine until the next cycle begins, when another dose is pumped from the reservoir and mixed with water to form the wash liquor.

[0016] We have surprisingly found that in such an automatic dosing washing machine, liquid detergents are subject to significant physical stress, meaning that some liquid detergents are better suited to this format than others.

[0017] Typical physical stresses include temperature (where temperatures inside the washing machine near the sump can easily reach over 50°C and higher), and agitation due to wash cycles as well as periods of non-use where the detergent may sit in the sump for long periods without any agitation at all.

[0018] A further feature of liquid detergents in such washing machines is that they must be free-flowing when needed (ie between wash cycles) and must not clog additional conduits in the automatic dosing device of said washing machine.

[0019] It is also necessary that the liquid detergent remain satisfactorily in the reservoir during maintenance.

[0020] This type of situation is unusual because it is normal for any liquid to be added to the reservoir at the start of the cycle, only for it to be flushed away very quickly by the wash water. It is therefore uncommon for a washing machine to contain more than a single dose of product.

[0021] Surfactants

[0022] The liquid detergent of the present invention preferably comprises 2 to 60 wt%, more preferably 4 to 50 wt%, and most preferably 10 to 30 wt% total surfactants. Preferred are anionic and nonionic surfactants.

[0023] 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 and sulfate surfactants, preferably alkylbenzene sulfonates, alkyl sulfates and alkyl ether sulfates. The alkyl chain is preferably C10-C18. Alkyl ether sulfates are also called alcohol ether sulfates.

[0024] Typically used in laundry liquid compositions are C12-C14 alkyl ether sulfates having a straight or branched 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 is ethoxylated with an average of 3 EO units per molecule.

[0025] Anionic surfactants are preferably added to the detergent composition in the form of salts. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of anionic surfactants can be formed in situ by neutralizing the acid form of the surfactant with a base (such as sodium hydroxide or an amine such as monoethanolamine, diethanolamine or triethanolamine). The weight ratio is calculated for the protonated form of the surfactant.

[0026] Nonionic surfactants are discussed in Non-ionic Surfactants: Organic Chemistry, Nico M. van Os, ed. (Marcel Dekker 1998), Surfactant Science Series, CRC Press. Preferred nonionic surfactants are alkoxylates, preferably ethoxylated. Preferred nonionic surfactants are alcohol ethoxylates and methyl ester ethoxylates, which have 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.

[0027] In anionic and nonionic surfactants, the ethoxy units may be partially replaced by propoxy units.

[0028] Further examples of suitable anionic surfactants are rhamnolipids, α-olefinsulfonates, olefinsulfonates, alkenesulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkanesulfonates and disulfonates, fatty alcohol sulfates (FAS), alkanesulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates alkyl- or alkenyl-succinic acid, dodecenyl / tetradecenylsuccinic acid (DTSA), fatty acid derivatives of amino acids, DATEM's, CITREM's and diesters and monoesters of sulfosuccinic acid.

[0029] Further 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).

[0030] The formulation may contain soap and zwitterionic or cationic surfactants as minor components, preferably in an amount of 0.1 to 3% by weight. Betaines such as CAPB are preferred zwitterionic surfactants.

[0031] Preferred nonionic and anionic surfactants are further described below.

[0032] C16 / C18 Alcohol Ethoxylate

[0033] Preferred C16 / 18 alcohol ethoxylates have the formula:

[0034] R1-O-(CH2CH2O) q -H

[0035] 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 counted from the end of the chain to which the ethoxylate is attached. The double bond may be in cis or trans configuration (oleyl or trans-oleyl), preferably cis. Cis or trans alcohol ethoxylates CH3(CH2)7-CH=CH-(CH2)8O-(OCH2CH2) n OH 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, with the carbons counted from the end of the chain to which the OH is attached.

[0036] Preferably, R1 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, saturated C16 alcohol ethoxylate is at least 90% by weight of the total C16 linear alcohol ethoxylate. 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 ethoxylate 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.

[0037] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt%, more preferably 4 wt% of the total C16 and C18 alcohol ethoxylate surfactants.

[0038] Preferably, the saturated C18 alcohol ethoxylate surfactant comprises at most 20 wt % of the total C16 and C18 alcohol ethoxylate surfactants, and more preferably at most 11 wt %.

[0039] Preferably, the saturated C18 content is at least 2 wt% of the total C16 and C18 alcohol ethoxylate content.

[0040] Alcohol ethoxylates are discussed in Non-ionic Surfactants: Organic Chemistry, Nico M. van Os, ed. (Marcel Dekker 1998), Surfactant Science Series, CRC Press. Alcohol ethoxylates are often referred to as alkyl ethoxylates.

[0041] 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 moieties in the alcohol ethoxylate, and "C16 alcohol ethoxylate" is the sum of all C16 moieties in the alcohol ethoxylate.

[0042] 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.

[0043] Preferably, the C16 / 18 alcohol ethoxylate comprises less than 15 wt %, more preferably less than 8 wt %, most preferably less than 5 wt % of polyunsaturated alcohol ethoxylate of the alcohol ethoxylate.The polyunsaturated alcohol ethoxylate comprises a hydrocarbon chain having two or more double bonds.

[0044] C16 / 18 alcohol ethoxylates can be synthesized by ethoxylation of alkyl alcohols via the following reaction:

[0045] R1-OH+qethylene oxide→R1-O-(CH2CH2O) q -H

[0046] Alkyl alcohols can be produced by transesterification of triglycerides into methyl esters followed by distillation and hydrogenation into 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.

[0047] The production 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, Vol. 11, pp. 436 et seq.

[0048] 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 involve Group II bases such as Ba dodecanoate; Group II metal alkoxides; Group II hydrotalcites such as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0049] 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, where q is the molar average degree of ethoxylation, x and y are absolute values, where x = qq / 2, and y = q+q / 2. For example, when q = 10, more than 70% by weight of the alcohol ethoxylate should be composed of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 ethoxylate groups.

[0050] C16 and / or C18 alcohol ether sulfates

[0051] Preferred ether sulfates have the formula:

[0052] R2-O-(CH2CH2O) p SO3H

[0053] 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 attached. The double bond may be in cis or trans configuration (oleyl or antioleyl), 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 bond on the chain, with the carbons counted from the end of the chain to which the OH is attached.

[0054] Preferably, R2 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, saturated C16 is a linear alkyl group of at least 90 wt% of the C16 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 wt% of the total C16 and C18 alkyl ether sulfate surfactants.

[0055] 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.

[0056] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt%, more preferably 4 wt% of the total C16 and C18 alkyl ether sulfate surfactants.

[0057] Preferably, the saturated C18 alkyl ether sulfate surfactants comprise at most 20 wt% of the total C16 and C18 alkyl ether sulfate surfactants, and 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.

[0058] Where the composition comprises a mixture of C16 / 18 derived materials for the alkyl ether sulphate as well as the more traditional C12 alkyl chain length materials, it is preferred that the total C16 / 18 alkyl ether sulphate content 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.

[0059] Ether sulfates are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, in press by CRC Press.

[0060] 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.

[0061] Preferably, the C16 and C18 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 of the ether sulfates. Polyunsaturated ether sulfates contain hydrocarbon chains having two or more double bonds.

[0062] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. Alcohol ethoxylates can be produced by ethoxylation of alkyl alcohols. Alkyl alcohols used to prepare alcohol ethoxylates can be produced by transesterification of triglycerides into methyl esters, followed by distillation and hydrogenation into alcohols. This process is discussed in Kreutzer, UR's Journal of the American Oil Chemists' Society. 61 (2): 343-348. Preferred alkyl alcohols for the reaction are oleyl alcohols having an iodine value of 60 to 80, preferably 70 to 75, which are available from BASF, Cognis, Ecogreen.

[0063] As described in A Practical Guide to Vegetable Oil Processing (Gupta MK Academy Press 2017), the degree of polyunsaturation in the surfactant can be controlled by hydrogenation of triglycerides. Distillation and other purification techniques can be used.

[0064] Ethoxylation reactions are described in Non-Ionic Surfactant Organic Chemistry (NM van Osed), Surfactant Science Series Volume 72, CRC Press.

[0065] 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 Ba dodecanoate; Group II metal alkoxides; Group II hydrotalcites such as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0066] Preferably, the narrow ethoxyl distribution has greater than 70 wt%, more preferably greater than 80 wt% in R2-O-(CH2CH2O) z SO3H to R2-O-(CH2CH2O) w Ether sulfates in the SO3H range R2-O-(CH2CH2O) p SO3H, where q is the molar average degree of ethoxylation, x and y are absolute values, where z = pp / 2, and w = p+p / 2. For example, when p = 6, more than 70% by weight of the ether sulfate should be composed of ether sulfates having 3, 4, 5, 6, 7, 8, 9 ethoxylate groups.

[0067] The weight of the ether sulfate is calculated in the protonated form: R2-O-(CH2CH2O) p SO3H. In the formulation, it is in the ionic form with the corresponding counter ion R2-O-(CH2CH2O) p SO 3- When present, preferred counterions are Group I and Group II metals, amines, and most preferably sodium.

[0068] Methyl Ester Ethoxylate (MEE)

[0069] Preferred methyl ester ethoxylate surfactants have the following form:

[0070] R3-(C=O)-O-(CH2CH2-O) n -CH3

[0071] Where R3COO is the fatty acid moiety, such as 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 can be given in parentheses, oleic acid is 18:1 (9), linoleic acid is 18:2 (9, 12), where 9 is the carbon number starting from the COOH end.

[0072] The integer n is the molar average number of ethoxylates.

[0073] Methyl ester ethoxylate (MEE) is described in Chapter 8 of Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications by G.A. Smith, pages 287-301 (AOCS press 2019); J.Am.Oil.Chem.Soc.vol 74 (1997) by Cox ME and Weerasooriva U, pages 847-859; Tenside Surf.Det. Vol. 28 (2001) by Hreczuch et al., pages 72-80; Household and Personal Care Today (2012) by C.Kolano., pages 52-55; J.Am.Oil.Chem.Soc.vol 72 (1995) by A.Hama et al., pages 781-784. MEE can be produced by the reaction of methyl esters with ethylene oxide using calcium or magnesium-based catalysts. The catalyst may be removed or left in the MEE.

[0074] Alternative preparation routes are transesterification of methyl esters or esterification of carboxylic acids with polyethylene glycols, which terminate at one end of the chain with a methyl group.

[0075] Methyl esters can be produced by the transesterification of methanol with triglycerides or the esterification of methanol with fatty acids. Fattah et al. (Front. Energy Res., June 2020, Vol. 8 Article 101) discuss the transesterification of triglycerides with fatty acid methyl esters and glycerol and quote it here. 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, inedible 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.

[0076] Distillation and fractionation processes can be used for the production of methyl esters or carboxylic acids to produce the desired carbon chain distribution.Preferred sources of triglycerides are those containing less than 35% by weight polyunsaturated fatty acids in the oil prior to distillation, fractionation or hydrogenation.

[0077] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, Unileveroleochemical Indonesia. Biodiesel is methyl ester and can be used from these sources.

[0078] When the ESB is MEE, it preferably has a molar average of 8 to 30, more preferably 10 to 20 ethoxylate groups (EO). The most preferred ethoxylates contain 12 to 18 EO.

[0079] Preferably, at least 10 wt %, more preferably at least 30 wt % of the total C18:1 MEE in the composition has 9 to 11 EO, even more preferably at least 10 wt % is exactly 10 EO. For example, when the MEE has a molar average of 10 EO, then at least 10 wt % of the MEE should be composed of ethoxylates having 9, 10 and 11 ethoxylate groups.

[0080] 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 wt. % of the MEE should consist of ethoxylates having 9, 10 and 11 ethoxylate groups.

[0081] In the case of a broader MEE distribution, it is preferred that at least 40 wt% of the total MEE in the composition is C18:1.

[0082] Furthermore, it is preferred that the MEE component also comprises some C16 MEE.

[0083] Therefore, it is preferred that the total MEE component comprises 5 to 50 wt% C16 MEE of the total MEE.Preferably, the C16 MEE is greater than 90 wt%, more preferably greater than 95 wt% C16:0.

[0084] Furthermore, it is preferred that the total MEE component comprises less than 15 wt %, more preferably less than 10 wt %, most preferably less than 5 wt % of the total MEE of polyunsaturated C18, i.e. C18:2 and C18:3. Preferably, C18:3 is present at less than 1 wt %, more preferably less than 0.5 wt %, 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 MEE.

[0085] Furthermore, it is preferred that the C18:0 component is less than 10 wt % of the total MEE present.

[0086] Furthermore, it is preferred that components having carbon chains of 15 or less comprise less than 4 weight percent of the total MEE weight present.

[0087] 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 of the MEE.

[0088] Preferred sources of alkyl groups for MEE include methyl esters derived from distilled palm oil and distilled high oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters of canola oil, methyl esters of high oleic sunflower oil, methyl esters of high oleic safflower oil, and methyl esters of high oleic soybean oil.

[0089] 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.

[0090] Preferably, more than 80% by weight of the double bonds in MEE are in cis configuration.

[0091] Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0092] The methyl group of the methyl ester may be replaced by an ethyl group or a propyl group. The methyl group is most preferred.

[0093] Preferably, the methyl ester ethoxylate comprises from 0.1 to 95 wt% of the composition. More preferably, the composition comprises from 2 to 40 wt% MEE, most preferably from 4 to 30 wt% MEE.

[0094] Preferably the composition comprises at least 50 wt% water, but this will depend on the total surfactant level and will be adjusted accordingly.

[0095] The composition may comprise further surfactants, and preferably other anionic and / or nonionic surfactants, for example alkyl ether sulfates or alcohol ethoxylates comprising 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.

[0096] 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 any type of anionic surfactant, preferably ether sulfates, linear alkylbenzene sulfonates, alkyl ether carboxylates, alkyl sulfates, rhamnolipids and mixtures thereof.

[0097] The weights of anionic surfactants are calculated in the protonated form.

[0098] Sodium alkyl sulfate

[0099] The composition preferably comprises sodium alkyl sulfate (SAS). SAS comprises an alkyl chain having a length of 10 to 18 carbon atoms, which may be linear or branched. As described below, the alkyl chain may be derived from a renewable source.

[0100] Preferably, the weight average alkyl chain length is from 10 to 14, more preferably 12.

[0101] SAS is present in the composition at 0.1 to 25 wt % of the composition. In addition to SAS, the composition may also contain LAS, in which case it is preferred that SAS accounts for 50 wt % of the total LAS plus SAS (based on the protonated form), more preferably 70 wt % of the total SAS plus LAS, and most preferably 95 wt %.

[0102] Source of alkyl chains

[0103] The alkyl chains of the C16 / 18 surfactant are preferably obtained from renewable sources, preferably from triglycerides. A renewable source is a source in which the material is produced by the natural ecological cycle of living species, preferably by plants, algae, fungi, yeast or bacteria, more preferably by plants, algae or yeast.

[0104] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and trees. The oil from trees is known as tall oil. Most preferably, the source is palm oil and rapeseed oil.

[0105] Saad MG et al. discuss algal oil in Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges. Masri MA et al. describe a method for producing triglycerides from biomass using yeast in Energy Environ. Sci., 2019, 12, 2717 Asustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents.

[0106] Inedible vegetable oils may be used and are preferably selected from the fruits and seeds of the following plants: 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 leaf), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa.L.), Cerbera odollam (Seamango), Coriander (Coriandrum sativum L.), Croton megalocarpus, Pilu, Crambe, Syringa, Scheleichera triguga (kusum), Stillingia, Shorea robusta (Sal), Terminalia belericaroxb, Cuphea, Camellia, Champaca, Simaroubagalauca, Garcinia indica, Rice bran, Hingan (balanites), Desertdate, Cardoon, Asclepias syriaca)(Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, algae, Argemonemexicana L.)(Mexican prickly poppy), Putranjivaroxburghii(Lucky bean tree), Sapindus mukorossi(Soapnut), M.azedarach(syringe), Thevettia peruviana(Yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, B.napus, Zanthoxylum bungeanum. .

[0107] SLES and PAS

[0108] SLES and other such alkali metal alkyl ether sulfate anionic surfactants can generally be obtained by sulfating alcohol ethoxylates. These alcohol ethoxylates can generally be obtained by ethoxylating linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating the linear alcohols. Thus, the formation of linear alcohols is a central step in obtaining both PAS and alkali metal alkyl ether sulfate surfactants.

[0109] Linear alcohols suitable as an intermediate step in making alcohol ethoxylates and hence anionic surfactants such as sodium lauryl ether sulfate can be obtained from a number of different sustainable sources. These include:

[0110] Primary sugar

[0111] Primary sugars are obtained from sucrose 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 alkenes. These alkenes are then processed into linear alcohols by hydroformylation or oxidation.

[0112] An alternative method that also utilizes primary sugars to form linear alcohols can be used, wherein the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed into linear fatty acids, and they are then reduced to form linear alcohols.

[0113] Biomass

[0114] Biomass, for example, forest products, rice husks and wheat straw, etc., can be processed into synthesis gas by gasification. These are processed into alkanes by the FischerTropsc reaction, which are in turn dehydrogenated to form alkenes. These alkenes can be processed in the same manner as the alkenes described above [primary sugars].

[0115] An alternative approach is to convert 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. This bioethylene is then processed into linear alcohols as described above [primary sugars].

[0116] Waste plastics

[0117] Waste plastics are pyrolyzed to form pyrolysis oil. This is then fractionated to form linear alkanes, which are dehydrogenated to form alkenes. These alkenes are processed as described above [primary sugars].

[0118] Alternatively, the pyrolysis oil is cracked to form ethylene which is then processed by olefin metathesis to form the desired alkenes. These are then processed to linear alcohols as described above [primary sugars].

[0119] Municipal solid waste

[0120] MSW is converted to syngas by gasification. From the syngas, it can be processed as described above [primary sugars], or it can be converted to ethanol by an enzymatic process before being dehydrogenated to ethylene. The ethylene can then be converted to linear alcohols by the Ziegler process.

[0121] MSW can also be converted to pyrolysis oil by gasification and then fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins and then linear alcohols.

[0122] Ocean Carbon

[0123] There are various carbon sources from marine flora such as seaweed and macroalgae. From such marine flora, triglycerides can be isolated from the source and then hydrolyzed to form fatty acids which are then reduced to straight chain alcohols in the usual manner.

[0124] 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].

[0125] Waste oil

[0126] Waste oils such as used cooking oils can be physically separated into triglycerides which are split as described above to form straight chain fatty acids and then straight chain alcohols.

[0127] Alternatively, used cooking oil can be subjected to the Neste process, whereby the oil is catalytically cracked to form bio-ethylene. It is then processed as described above.

[0128] Methane capture

[0129] Methane capture processes capture methane from landfills or fossil fuel production. Methane can be formed into synthesis gas by gasification. Synthesis gas can be processed as described above, whereby the synthesis gas is converted into methanol (Fischer Tropsch reaction) and then into olefins before being oxidized into linear alcohols by hydroformylation.

[0130] Alternatively, the synthesis gas can be converted to alkanes and then alkenes via Fischer Tropsch and then dehydrogenation.

[0131] Carbon capture

[0132] Carbon dioxide can be captured by any of a variety of methods, all well known. Carbon dioxide can be converted to carbon monoxide by the reverse water gas shift reaction, and it can then be converted to synthesis gas using hydrogen in an electrolysis reaction. The synthesis gas is then processed as described above and converted to methanol and / or paraffins before reacting to form olefins.

[0133] Alternatively, the captured carbon dioxide is mixed with hydrogen before being enzymatically processed to form ethanol. This is a process developed by Lanzatech. Thus, ethanol is converted to ethylene and then processed into olefins and then linear alcohols as described above.

[0134] The above process can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0135] Linear alkylbenzene sulfonate

[0136] LAS (linear alkylbenzene sulfonate) is a generally preferred anionic surfactant.

[0137] The key intermediate compounds in LAS manufacturing are the related alkenes. These alkenes (olefins) can be produced by any of the above methods and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, ocean carbon, etc.

[0138] In contrast to the above processes where olefins are processed by hydroformylation and oxidation to form linear alcohols, olefins are reacted with benzene and then sulfonated to form LAS.

[0139] Alkyl chain length is the linear alkyl benzene sulfonate of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologous alkyl chain homologues, each of which contains an aromatic ring that is sulfonated in the "para-position" and is connected to the linear alkyl chain at any position except the terminal carbon. The linear alkyl chain preferably has a chain length of 11 to 15 carbon atoms, and 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 the 1-phenyl isomer. LAS is usually formulated into the composition in the form of acid (i.e. HLAS), then at least partially in situ neutralization. If used outside SAS, the linear alkyl benzene sulfonate surfactant is present with 1 to 20% by weight of the composition, more preferably 2 to 15% by weight, most preferably 8 to 12% by weight.

[0140] Surfactant ratio

[0141] 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.

[0142] Preferably, the weight ratio of total nonionic surfactant to total alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0143] 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) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0144] 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) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0145] 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) is from 0.5 to 2, preferably from 0.7 to 1.5, most preferably from 0.9 to 1.1.

[0146] 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.

[0147] 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.

[0148] Preferably, the composition is visually clear.

[0149] Liquid laundry detergent

[0150] 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.

[0151] In a preferred embodiment, the liquid composition is isotropic.

[0152] The term "linens" is often used to describe certain 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 cotton and polyester blends.

[0153] Examples of liquid laundry detergents include heavy duty liquid laundry detergents for use in the wash cycle of an automatic washing machine, and liquid delicates and liquid color care detergents, such as those suitable for washing delicate garments (e.g., garments made of silk or wool) by hand or in the wash cycle of an automatic washing machine.

[0154] The term "liquid" in the context of the present invention means that the continuous phase or major part of the composition is liquid and that the composition is flowable at 15°C and above. Thus, the term "liquid" may encompass emulsions, suspensions and compositions with a flowable but harder consistency, known as gels or pastes. The viscosity of the composition is preferably 25°C and 21 seconds. -1 The shear rate is 200 to about 10,000 mPa.s. This shear rate is the shear rate usually applied to the liquid when pouring from the bottle. The pourable liquid detergent composition preferably has a viscosity of 200 to 1,500 mPa.s, preferably 200 to 700 mPa.s.

[0155] The composition according to the invention may suitably have an aqueous continuous phase. "Aqueous continuous phase" refers to a continuous phase based on water. Preferably, the composition comprises at least 50 wt% water, more preferably at least 70 wt% water.

[0156] The alkyl ether sulfate may be provided as a single raw material component or as a mixture of components.

[0157] Where the composition comprises a mixture of C16 / 18 derived materials for the alkyl ether sulphate as well as the more traditional C12 alkyl chain length materials, it is preferred that the C16 / 18 alkyl ether sulphate should comprise at least 10 wt % of the total alkyl ether sulphate in the composition, 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 sulphate.

[0158] The alcohol ethoxylate may be provided as a single raw material component or as a mixture of components.

[0159] 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 in the composition, more preferably at least 50 wt %, even more preferably at least 70 wt %, particularly preferably at least 90 wt %, most preferably at least 95 wt % of the alcohol ethoxylate in the composition.

[0160] Preferably, the choice and amount of surfactant is such that the composition and diluted mixture are isotropic in nature.

[0161] The composition comprises one of the following:

[0162] -benzoic acid;

[0163] - Methyl ester ethoxylate;

[0164] - ethanol;

[0165] -Phenoxyethanol.

[0166] Preferably, the composition comprises two, and more preferably three, of the following:

[0167] -benzoic acid;

[0168] -Methyl ester ethoxylate;

[0169] - ethanol; and

[0170] -Phenoxyethanol.

[0171] Most preferably, the composition comprises all four.

[0172] benzoic acid

[0173] Preferably, the composition comprises benzoic acid. The benzoic acid is present in 0.01-2% by weight of the composition. The benzoic acid may also be present as a salt, for example as sodium benzoate.

[0174] Ethanol

[0175] Preferably, the composition comprises ethanol.Preferably, the ethanol is present in 0.1-5% by weight of the composition.

[0176] Phenoxyethanol

[0177] Preferably, the composition comprises phenoxyethanol.Preferably, phenoxyethanol is present in 0.1-5% by weight of the composition.

[0178] Alkoxylated polyamine

[0179] Preferably, the composition comprises an alkoxylated polyamine as an anti-redeposition polymer to stabilize soil in the washing liquor, thereby preventing redeposition of soil. Soil release polymers suitable 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 a chain of another ethyleneimine unit. 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 of a dendrimer. 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 in the polyethyleneimine backbone is 10 to 30, preferably 15 to 25 ethoxy groups per ethoxylated nitrogen atom.

[0180] Mixtures of any of the above materials may also be used.

[0181] More preferably, the polyamine is an alkoxylated cationic or zwitterionic di- or polyamine polymer in which the positive charge is provided by quaternization of the amine nitrogen atom and the anionic groups, if present, are provided by sulfation or sulfonation of the alkoxylated groups.

[0182] Preferably, the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0183] Preferably, greater than or equal to 50 mol % of the nitrogen amines are quaternized, preferably with methyl groups. Preferably, the polymer comprises 2 to 10, more preferably 2 to 6, most preferably 3 to 5 quaternized nitrogen amines. Preferably, the alkoxylate groups are selected from ethoxy and propoxy groups, most preferably ethoxy.

[0184] Preferably, the polymer contains ester (COO) or amide (CONH) groups in the structure, preferably these groups are placed so that when all ester or 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.

[0185] Preferably, the polymer has the following form:

[0186]

[0187] Wherein R1 is C3 to C8 alkyl, X is (C2H4O) n A Y 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, there are 0, 1 or 2 OH groups. X and R1 may contain ester groups therein. 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.

[0188] Such polymers are described in WO2021239547 (Unilever), exemplary polymers being sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Amide and ester groups can be included using lactones or sodium chloroacetate (modified Williamson synthesis) to add to the OH or NH groups, respectively, followed by subsequent ethoxylation.

[0189] An exemplary reaction scheme for inclusion of an ester group is

[0190]

[0191] The addition of lactones is discussed in WO2021 / 165468.

[0192] The compositions of the invention preferably comprise from 0.025 to 8% by weight of one or more anti-redeposition polymers, such as, for example, the alkoxylated polyethyleneimines or zwitterionic polyamines described above.

[0193] Aminocarboxylate chelating agents

[0194] Preferably, the composition comprises an aminocarboxylate chelating agent.Preferably, the aminocarboxylate chelating agent is selected from GLDA and MGDA.

[0195] Preferably, the aminocarboxylate is present in the composition in an amount of 0.1 to 15 wt %, more preferably 0.1 to 10 wt %, even more preferably 0.3 to 5 wt %, more preferably 0.8 to 3 wt %, and most preferably 1 to 2.5 wt % (based on the weight of the composition).

[0196] Glutamic acid diacetic acid (GLDA)

[0197] GLDA can be present in the form of a salt of GDLA or a mixture of GDLA and a salt of GDLA. Preferred salt forms include mono-, di-, tri- or tetra-alkali metal salts and mono-, di-, tri- or tetra-ammonium salts of GLDA. The alkali metal salt of glutamic acid diacetate GDLA is preferably selected from lithium salts, potassium salts, and more preferably sodium salts of GLDA.

[0198] Glutamic acid diacetic acid can be partially or preferably completely neutralized with the corresponding base. Preferably, an average of 3.5 to 4 COOH groups of GLDA are neutralized with an alkali metal, preferably sodium. Most preferably, the composition comprises the tetrasodium salt of GLDA.

[0199] GLDA is at least partially neutralized with an alkali metal, more preferably with sodium or potassium, most preferably with sodium.

[0200] The GLDA salt may be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA, or an enantiomerically enriched isomer mixture.

[0201] Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or its corresponding mono-, di-, tri- or tetra-alkali metal salt or mono-, di-, tri- or tetra-ammonium salt or a mixture thereof, said mixture comprising predominantly the corresponding L-isomer in an enantiomeric excess ranging from 10 to 95%.

[0202] Preferably, the GLDA salt is essentially L-glutamic acid diacetic acid at least partially neutralized with an alkali metal.

[0203] The sodium salt of GLDA is preferred.

[0204] A suitable commercial source of GLDA in the form of the tetrasodium salt is available from Nouryon GL.

[0205] Preferably, GLDA is present in the composition in an amount of 0.1 to 15 wt %, more preferably 0.1 to 10 wt %, even more preferably 0.3 to 5 wt %, still more preferably 0.8 to 3 wt %, and most preferably 1 to 2.5 wt % (based on the weight of the composition).

[0206] Methylglycine diacetic acid (MGDA)

[0207] Preferred salt forms include mono-, di-, tri- or tetra-alkali metal salts and mono-, di-, tri- or tetra-ammonium salts of MGDA. The alkali metal salt is preferably selected from lithium salts, potassium salts, and more preferably sodium salts of MGDA.

[0208] The sodium salt of methylglycine diacetic acid is preferred. Particularly preferred is the trisodium salt of MGDA.

[0209] MGDA can be partially or preferably completely neutralized with the corresponding alkali metal. Preferably, an average of 2.7 to 3 COOH groups per molecule of MGDA are neutralized with an alkali metal, preferably with sodium.

[0210] MGDA can be selected from alkali metal salts of MGDA and racemic mixtures of pure enantiomers (such as alkali metal salts of L-MGDA, alkali metal salts of D-MGDA), and mixtures of enantiomerically enriched isomers.

[0211] A suitable commercial source of MGDA in the form of the trisodium salt is available from BASF as M and purchased from Nouryon M-40.

[0212] Preferably, MGDA is present in the composition in an amount of 0.1 to 15 wt %, more preferably 0.1 to 10 wt %, even more preferably 0.3 to 5 wt %, still more preferably 0.8 to 3 wt %, most preferably 1 to 2.5 wt % (based on the weight of the composition).

[0213] Small amounts of aminocarboxylates may carry cations other than alkali metals. Thus, it is possible that small amounts (e.g. 0.01 to 5 mol %) carry alkaline earth metal cations, such as Mg 2+ or Ca 2+ , or Fe(II) or Fe(III) cations. GLDA may contain a small amount of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. "A small amount" in this case refers to a total amount of 0.1 to 1% by weight, which refers to the chelating agent aminocarboxylate.

[0214] In addition to the aminocarboxylate chelating agents, the detergent compositions may optionally contain relatively low levels of organic detergent builders or chelating agents. Examples include alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other examples include DEQUEST TM , an organic phosphonate-type chelating agent sold by Monsanto, and an alkylhydroxyphosphonate.

[0215] Other suitable organic builders include the high molecular weight polymers and copolymers known to have builder properties. For example, such materials include suitable polyacrylic acids, polymaleic acids and polyacrylic acid / polymaleic acid copolymers and their salts, such as those marketed by BASF under the name SOKALAN TM Those sold. If used, organic builder materials 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 of the composition, preferably less than 5% by weight. 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 non-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), for example, sold as Dequest2010. Also suitable but less preferred (due to its poor cleaning effect) is Dequest (R) 2066 (diethylenetriamine penta (methylenephosphonic acid) or DTPMP heptasodium). However, it is preferred that the composition contains less than 0.5% by weight of a phosphonate-based chelating agent, and more preferably less than 0.1% by weight of a phosphonate-based chelating agent. Most preferably, the composition does not contain a phosphonate-based chelating agent.

[0216] External structurants

[0217] The compositions of the present invention can further modify their rheology by using one or more external structurants that form a structured network within the composition. Examples of such materials include crystallizable glycerides, such as hydrogenated castor oil; microfibrous cellulose and citrus pulp fibers. The presence of an external structurant can provide shear-thinning rheology and can also allow materials such as encapsulates and visual cues to be stably suspended in the liquid.

[0218] The composition preferably comprises a crystallizable glyceride.

[0219] As described in WO2011 / 031940 (the contents of which, particularly with respect to the manufacture of ESS, are incorporated herein by reference), crystallizable glycerides can be used to form an external structuring system. When an ESS is present, it is preferred that the ESS of the present invention preferably comprises: (a) a crystallizable glyceride; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components will be discussed in detail below.

[0220] Crystallizable glycerides used herein preferably include "hydrogenated castor oil" or "HCO". The HCO used herein can most generally be any hydrogenated castor oil, as long as it can be crystallized in the ESS premix. Castor oil can include glycerides, especially triglycerides, which contain C10 to C22 alkyl or alkenyl moieties (which incorporate hydroxyl groups). The hydrogenation of castor oil to prepare HCO converts double bonds (which may be present in raw oils such as castor oil-based moieties), converting the castor oil-based moieties into saturated hydroxyalkyl moieties (e.g., hydroxystearyl). In some embodiments, the HCO herein can be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO can be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. The level of HCO present in the ESS of the present invention is typically from about 2% to about 10% by weight, from about 3% to about 8% by weight, or from about 4% to about 6% by weight of the structured system. In some embodiments, the corresponding percentage of hydrogenated castor oil delivered to the finished laundry detergent product is less than about 1.0%, typically between 0.1% and 0.8%.

[0221] Useful HCO may have the following properties: a melting point of about 40 degrees Celsius to about 100 degrees Celsius, or about 65 degrees Celsius to about 95 degrees Celsius; and / or an iodine value ranging from 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: differential scanning calorimetry. HCO 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. Further 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 be any suitable origin, such as from Brazil or India. In a suitable embodiment, castor oil is hydrogenated using a noble metal (e.g., 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.

[0222] The present invention is not intended to involve the use of only hydrogenated castor oil. Any other suitable crystallizable glycerides can be used. In one example, the structuring agent is a triglyceride of substantially pure 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 there may be some changes. Likewise, the hydrogenation process can vary. Any other suitable equivalent material can be used, such as a mixture of triglycerides, wherein at least 80% by weight is from castor oil. Exemplary equivalent materials mainly contain or are substantially composed of triglycerides; or mainly contain or are substantially composed of a mixture of diglycerides and triglycerides; or mainly contain or are substantially composed of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of a glyceride mixture) of monoglycerides; or mainly contain or are substantially 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 glycerides. The above-mentioned proviso is that the major part of any of the glycerides, usually at least 80% by weight, is chemically identical to the glycerides of fully hydrogenated ricinoleic acid, i.e., the glycerides of 12-hydroxystearic acid. For example, it is well known in the art that hydrogenated castor oil is modified so that in a given triglyceride, there are two 12-hydroxystearic acid moieties and one stearic acid moiety. Equally, it is foreseeable that hydrogenated castor oil may not be fully hydrogenated. On the contrary, when poly (oxyalkylation) castor oil does not meet the melting standard, the present invention does not include poly (alkoxylation) castor oil.

[0223] The crystallizable glycerides used in the present invention may have a melting point of about 40 degrees Celsius to about 100 degrees Celsius.

[0224] Hydroxamic acid

[0225] Preferably, the composition comprises a hydroxamic acid.

[0226] Whenever the term "hydroxamic acid" or "hydroxamate" is used, this encompasses both the hydroxamic acid and the corresponding hydroxamate (salt of the hydroxamic acid), unless otherwise indicated.

[0227] Hydroxamic acid is a class of compounds in which hydroxylamine is inserted into carboxylic acid. The general structure of hydroxamic acid is as follows:

[0228]

[0229] Where R 1 is an organic residue, such as an alkyl or alkenyl group. The hydroxamic acid may be present as its corresponding alkali metal salt or hydroxamate. The preferred salt is the potassium salt.

[0230] Hydroxamates can be conveniently formed from the corresponding hydroxamic acid by replacing the acid hydrogen atom with a cation:

[0231]

[0232] L + is a monovalent cation, for example, an alkali metal (eg, potassium, sodium) or ammonium or substituted ammonium.

[0233] In the present invention, hydroxamic acid or its corresponding hydroxamate has the following structure:

[0234]

[0235] Where R 1 yes

[0236] Straight or branched C4-C 20 Alkyl, or

[0237] Straight or branched chain substituted C4-C 20 Alkyl, or

[0238] Straight or branched C4-C 20 Alkenyl, or

[0239] Straight or branched chain substituted C4-C 20 Alkenyl, or

[0240] Alkyl ether group CH3(CH2) n (EO) m , wherein n is 2 to 20 and m is 1 to 12, or a substituted alkyl ether group CH3(CH2) n (EO) m , wherein n is 2 to 20, m is 1 to 12, and the type of substitution includes one or more of NH2, OH, S, -O- and COOH,

[0241] And R 2 Selected from hydrogen and forming a branched chain R 1 The portion of the ring structure of the group.

[0242] Preferred hydroxamates are those wherein R 2 is hydrogen, R 1 It is C8-C 14 The alkyl groups, preferably n-alkyl groups, are most preferably those that are saturated.

[0243] In the context of the present invention, the general structure of a hydroxamic acid 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 n-alkyl. When a C8 material is used this is known as octyl hydroxamic acid. The potassium salt is particularly useful.

[0244]

[0245] Octylhydroxamic acid potassium salt

[0246] 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: Such hydroxamic acids include lysine hydroxamate, methionine hydroxamate and norvaline hydroxamate, and are commercially available.

[0247] Hydroxamic acid is believed to work by binding to metal ions present in soil on fabrics. This binding action (which is actually the known chelating property of hydroxamic acid) does not in itself have any use in removing soil from fabrics. The key is the "tail" of the hydroxamic acid, the group R 1 Subtract the group R 2 Any branch that folds back onto the oxime nitrogen. The tail is selected to have an affinity for the surfactant system. This means that the detergency of an already optimized surfactant system is further enhanced by the use of hydroxamic acid, because it actually marks the difficult-to-remove particulate matter (clay) as "dirt" so that it can be removed by the surfactant system acting on the hydroxamic acid molecules that are now fixed on the particles by binding to the metal ions embedded in the clay-type particles. Non-soap detersive surfactants adhere to the hydroxamic acid, thereby generally causing more surfactant to interact with the fabric, resulting in better decontamination. Thus, hydroxamic acid is used as a connecting molecule, thereby promoting the removal of particulate soil from the fabric and suspension in the wash liquor, and thus improving the primary detergency.

[0248] Hydroxamic acids have a higher affinity for transition metals such as iron than for alkaline earth metals such as calcium and magnesium, and therefore hydroxamic acids act primarily to improve the removal of soils, especially particulate soils, from fabrics rather than additionally acting as builders for calcium and magnesium.

[0249] The preferred hydroxamic acid is coconut hydroxamic acid at 80% solids, which is 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 coconut hydroxamic acid as a 50% solid material under the trade name RK858. 50% coconut hydroxamic acid potassium salt is available as RK857. Another preferred material is RK842 from Axis House, an alkyl hydroxamic acid made from palm kernel oil.

[0250] Preferably, the hydroxamic acid is present in 0.1 to 3% by weight of the composition, more preferably 0.2 to 2% by weight of the composition.

[0251] Preferably, the weight ratio of hydroxamic acid to 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.

[0252] Alkoxylated cationic or zwitterionic polyamine polymers

[0253] Preferably, the composition comprises an alkoxylated cationic or zwitterionic polyamine polymer. Preferably, the polyamine is an alkoxylated cationic or zwitterionic diamine or polyamine polymer in which the positive charge is provided by quaternization of the amine nitrogen atom and the anionic groups, if present, are provided by sulfation or sulfonation of the alkoxylated groups.

[0254] Preferably, the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0255] Preferably, greater than or equal to 50 mol % of the nitrogen amines are quaternized, preferably with methyl groups. Preferably, the polymer comprises 2 to 10, more preferably 2 to 6, most preferably 3 to 5 quaternized nitrogen amines. Preferably, the alkoxylate groups are selected from ethoxy and propoxy, most preferably ethoxy.

[0256] Preferably, the polymer contains ester (COO) or amide (CONH) groups in the structure, preferably, these groups are arranged so that when all ester or 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.

[0257] Preferably, the polymer has the following form:

[0258]

[0259] Wherein R1 is C3 to C8 alkyl, X is (C2H4O) nA Y 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, there are 0, 1 or 2 OH groups. X and R1 may contain ester groups therein. 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) is preferred. n-1 Y.

[0260] Such polymers are described in WO2021239547 (Unilever). Exemplary polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Ester groups can be included using lactones or sodium chloroacetate (modified Williamson synthesis), added to the OH or NH groups, followed by subsequent ethoxylation.

[0261] Enzymes

[0262] The composition preferably comprises an enzyme selected from the group consisting of cellulases, proteases and amylase / mannanase mixtures.

[0263] Furthermore, further enzymes may be present, such as those described below.

[0264] 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, pentosanases, malic enzyme, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tannase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase or mixtures thereof.

[0265] Preferably, the enzyme level is from 0.1 to 100 mg, more preferably from 0.5 to 50 mg, most preferably from 5 to 30 mg active enzyme protein per 100 g of finished laundry liquid composition.

[0266] Examples of preferred enzymes are sold under the following trade names: Biotouch (AB Enzymes),

[0267] Detergent enzymes are discussed in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0268] 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 of 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.

[0269] Proteases hydrolyze bonds within peptides and proteins, which, in the case of laundry, results in enhanced removal of stains containing proteins or peptides. Examples of suitable protease families include aspartic proteases; cysteine ​​proteases; glutamic proteases; aspartic peptide lysing enzymes; serine proteases and threonine proteases. These protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk / ). Serine proteases are preferred. Subtilase-type serine proteases are more preferred. The term "subtilase" refers to a subgroup of serine proteases according to Siezen et al., Protein Engng.4 (1991) 719-737 and Siezen et al. Protein Science 6 (1997) 501-523. Serine proteases are a subgroup of proteases characterized by having serine in the active site that forms a covalent adduct with a substrate. Subtilases can be divided into six subclasses, namely the subtilisin family, the thermophilic protease family, the proteinase K family, the lantibiotic peptidase family, the Kexin family, and the Pyrolysin family.

[0270] 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 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 (eg 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 Cellulomonas described in WO 05 / 052161 and WO 05 / 052146.

[0271] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0272] 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 WO 89 / 06279, and protease PD138 described in (WO 93 / 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 B1, 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.

[0273] Suitable commercially available proteases include those sold under the following trade names: DuralaseTm, DurazymTm,

[0274] Can be used as or sell.

[0275] Suitable amylases (alpha and / or beta) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also included. Amylases include, for example, alpha-amylases obtained from Bacillus, for example, a special strain of Bacillus licheniformis described in more detail in GB 1,296,839, or a Bacillus strain 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 TM and Purastar TM (From Genencor International Inc.).

[0276] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also included. Suitable cellulases include cellulases from Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, Acremonium, for example, 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, US5,776,757, WO 89 / 09259, WO 96 / 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.

[0277] Lipase

[0278] Preferably, the composition comprises a lipase.

[0279] Lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously herein.

[0280] The composition preferably comprises 0.0005 to 0.5 wt%, preferably 0.005 to 0.2 wt% lipase.

[0281] 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).

[0282] The lipid esterase may be selected from the lipases in EC class 3.1 or 3.2, or a combination thereof.

[0283] Preferably, the cleaning lipid esterase is selected from:

[0284] (1) Triacylglycerol lipase (EC3.1.1.3)

[0285] (2) Carboxyl ester hydrolase (EC3.1.1.1)

[0286] (3) Cutinase (EC 3.1.1.74)

[0287] (4) Sterol esterase (EC3.1.1.13)

[0288] (5) Wax-ester hydrolase (EC 3.1.1.50)

[0289] Triacylglycerol lipase (EC 3.1.1.3) is most preferred.

[0290] 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 strain SD 705 (WO 95 / 06720 and WO 96 / 27002), Pseudomonas wisconsinensis (WO 96 / 12012); variants of 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 (B. pumilus) (WO 91 / 16422).

[0291] Suitable carboxyl ester hydrolases can be selected from the wild-type carboxyl ester hydrolases or variants endogenous to Burkholderia gladioli, Pseudomonas fluorescens, Pseudomonas putida, Bacillus acidocaldarius, Bacillus subtilis, Bacillus stearothermophilus, Streptomyces chrysomallus, S. diastatochromogenes and Saccharomyces cerevisiae.

[0292] Suitable cutinases may be selected from wild-type cutinases or variants endogenous to strains of Aspergillus, in particular strains of Aspergillus oryzae; Alternaria, in particular strains of Alternaria brassiciola; Fusarium, in particular Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum or Fusarium roseum. sambucium; Helminthosporium, in particular Helminthosporumsativum; Humicola, in particular Humicola insolens; Pseudomonas, in particular Pseudomonas mendocina or Pseudomonas putida; Rhizoctonia, in particular Rhizoctonia solani; Streptomyces, in particular Streptomyces scabies; Coprinus, in particular Coprinus cinerea; Thermobifida, in particular Thermobifida fusca; Magnaporthe, in particular Magnaporthe grisea; or Ulocladium, in particular Ulocladium consortiale.

[0293] In a preferred embodiment the Cutinase is a variant selected from the Pseudomonas mendocina Cutinase described in WO 2003 / 076580 (Genencor), such as a variant having three substitutions at I178M, F180V and S205G.

[0294] In another preferred embodiment, the cutinase is a wild type or variant of the six cutinases endogenous to Coprinus cinereus described in H. Kontkanen et al., App. Environ. Microbiology, 2009, p2148-2157.

[0295] In another preferred embodiment, the Cutinase is a wild type or variant of the two Cutinases endogenous to Trichoderma reesei described in WO2009007510 (VTT).

[0296] In a most preferred embodiment, the cutinase is derived from a strain of Humicola insolens, in particular the strain DSM 1800 of Humicola insolens. 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 cutinsases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0297] Suitable sterol esterases may be derived from Ophiostoma, such as a strain of Ophiostoma piceae; Pseudomonas, such as a strain of Pseudomonas aeruginosa; or Melanocarpus, such as a strain of Melanocarpus albomyces.

[0298] 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.

[0299] Suitable wax-ester hydrolases may be derived from Simmondsia chinensis.

[0300] 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.

[0301] 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 those produced by Absidia reflexa, Absidia corymbefera, Rhizmucormiehei, Rhizopus deleman, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum, oxysporum), Fusarium heterosporum, Aspergillus oryzea, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, in particular Thermomyces lanoginosus. Certain preferred lipases are produced by Novozymes under the trade name Lipolase and (a registered trademark of Novozymes); and LIPASE P It is available from Areaio Pharmaceutical Co. Ltd., Nagoya, Japan; AMANO- Commercially available from Toyo Jozo Co., Tagata, Japan; and additional Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, USA and Diosynth Co., Netherlands; and other lipases, such as Pseudomonas gladioli. Additional useful lipases are described in WIPO publications WO 02062973, WO 2004 / 101759, WO 2004 / 101760 and WO 2004 / 101763. In one embodiment, suitable lipases include "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 with R or K, and most preferably variants comprising T231R and N233R mutations, such most preferably variants are sold under the trade name (Novozymes) sales.

[0302] 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 contained herein.

[0303] As described in WO 2007 / 087243, lipid esterases with reduced odor generation potential and good relative performance are particularly preferred. These include (Novozyme).

[0304] Preferred commercially available lipases include Lipolase TM and Lipolase Ultra TM 、Lipex TM and Lipoclean TM (Novozymes A / S).

[0305] Fragrance

[0306] Preferably, the fragrance comprises a component selected from the group consisting of ethyl 2-methylvalerate (matricarbate), limonene, (4Z)-cyclopentadecan-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, tricyclodecenyl acetate (tricyclodecene acetate), cyclamal, beta ionone, hexyl salicylate, tonalid, [2-(cyclohexyloxy)ethyl]benzene (phe The present invention relates to a raw material comprising: a raw material comprising octahydrotetramethylacetophenone (OTNE), benzene, toluene, xylene (BTX), such as 2-phenylethanol, phenoxanol and mixtures thereof, a raw material comprising cyclododecanone, such as habolonolide, a raw material comprising phenols, such as hexyl salicylate, a raw material comprising a C5 block or oxygen-containing heterocyclic moiety, such as gamma-decanolide, methyl dihydrojasmonate and mixtures thereof, a raw material comprising terpenes, such as dihydromyrcenol, linalool, terpinolene, camphor, citronellol and mixtures thereof, a raw material comprising an alkyl alcohol, such as ethyl-2-methylbutyrate, a raw material comprising a diacid, such as ethylene glycol brazic acid, and mixtures thereof.

[0307] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance ethyl-2-methylvalerate (matricarbide).

[0308] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance (4Z)-cyclopentadeca-4-en-1-one.

[0309] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance dimethylbenzyl carbonate acetate.

[0310] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance dihydromyrcenol.

[0311] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance rose oxide.

[0312] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance tricyclodecenyl acetate.

[0313] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance benzyl acetate.

[0314] Preferably, the aromatic agent comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the aromatic agent spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

[0315] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance geraniol.

[0316] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance methylnonyl acetaldehyde.

[0317] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance tricyclodecenyl acetate (tricyclodecenyl acetate).

[0318] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance cyclamen aldehyde.

[0319] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance beta-ionone.

[0320] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance hexyl salicylate.

[0321] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance Musk Tonalite.

[0322] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance [2-(cyclohexyloxy)ethyl]benzene.

[0323] 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, phenylpentyl alcohol and mixtures thereof.

[0324] Preferably, the fragrance comprises a component selected from the class of cyclododecanone raw materials. More preferably, the fragrance component is habolonolide.

[0325] Preferably, the fragrance comprises a component selected from the class of phenolic raw materials. More preferably, the fragrance component is hexyl salicylate.

[0326] Preferably, the fragrance comprises a component selected from the group consisting of C5 block or oxygen-containing heterocyclic moiety raw materials. More preferably, the fragrance component is selected from the group consisting of gamma decalactone, methyl dihydrojasmonate, and mixtures thereof.

[0327] Preferably, the fragrance comprises a component selected from the class of terpene raw materials. More preferably, the fragrance component is selected from linalool, terpinolene, camphor, citronellol and mixtures thereof.

[0328] Preferably, the fragrance comprises a component selected from the class of alkyl alcohol raw materials. More preferably, the fragrance component is ethyl-2-methylbutyrate.

[0329] Preferably, the fragrance comprises a component selected from the class of diacid raw materials. More preferably, the fragrance component is ethylene glycol brazyl.

[0330] Preferably, the fragrance contains 0.5 to 30% by weight, more preferably 2 to 15% by weight and 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. Preferably, OTNE is present as a multi-component isomer mixture comprising:

[0331] ·1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 54464-57-2)

[0332] ·1-(1,2,3,5,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 68155-66-8)

[0333] ·1-(1,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 68155-67-9)

[0334] Such OTNE and its method of manufacture are fully described in US Pat. No. 3,907,321 (IFF).

[0335] The fragrance Molecule 01 is a specific isomer of OTNE and is available from IFF. Another commercial fragrance, Escentric 01, contains OTNE but also contains ambroxan, pink pepper, lime with balsamic notes such as benzoin, frankincense and incense.

[0336] Typically, commercially available fragrance raw materials contain 1 to 8 wt% of fragrance raw material OTNE.

[0337] Preferably, the above listed fragrance components are present in the finished detergent composition at from 0.0001 to 1 % by weight of the composition.

[0338] Fluorescent agent

[0339] Preferably, the composition comprises a fluorescent agent. More preferably, the fluorescent agent comprises a sulfonated distyrylbiphenyl fluorescent agent, such as those discussed in Chapter 7 of Industrial Dyes (K. Hunger ed., Wiley VCH 2003).

[0340] Sulfonated distyrylbiphenyl fluorescent agents are discussed in US Pat. No. 5,145,991 (Ciba Geigy).

[0341] 4,4'-distyryl biphenyl is preferred. Preferably, the fluorescent agent contains 2 SO3 - Group.

[0342] Most preferably, the fluorescent agent has the following structure:

[0343]

[0344] 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.

[0345] Preferably, the fluorescent agent is present at a level of 0.01 to 1 wt %, more preferably 0.05 to 0.4 wt %, most preferably 0.11 to 0.3 wt % of the composition.

[0346] 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.

[0347] Defoaming agent

[0348] The composition may also contain an anti-foaming agent, but preferably it is free of such an agent.Anti-foaming agent materials are well known in the art and include silicones and fatty acids.

[0349] Preferably the fatty acid soap is present in from 0 to 0.5% by weight of the composition (as measured with reference to the acid added to the composition), more preferably from 0 to 0.1% by weight, and most preferably zero.

[0350] In the context of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, wherein R is a straight 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 of which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0351] 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 monoethanolamine, diethanolamine or triethanolamine.

[0352] Mixtures of any of the above materials may also be used.

[0353] For the purpose of formulation calculation, fatty acids and / or salts thereof (as defined above) are not included in the level of surfactant or in the level of builder in the formulation.

[0354] Preferably, the composition comprises from 0.2 to 10% by weight of the composition of a cleaning polymer.Preferably, the cleaning polymer is selected from alkoxylated polyethyleneimines, polyester soil release polymers and copolymers of PEG / vinyl acetate.

[0355] preservative

[0356] Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th edition, Springer.

[0357] The formulation contains a preservative or a mixture of preservatives selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and its salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, most preferably sodium benzoate.

[0358] Preferred preservatives are selected from the group consisting of sodium benzoate, phenoxyethanol, dehydroacetic acid and mixtures thereof.

[0359] The preservative is present at 0.1 to 3 wt%, preferably at 0.3 to 1.5 wt%. Where appropriate, weights are calculated for the protonated form.

[0360] Preferably, the composition comprises from 0.1 to 3% sodium benzoate, preferably from 0.3% to 1.5% by weight of the composition.

[0361] Preferably, the composition comprises 0.1 to 3%, preferably 0.3% to 1.5% by weight of the composition of phenoxyethanol.

[0362] Preferably, the composition comprises from 0.1 to 3%, preferably from 0.3% to 1.5% by weight of the composition, of dehydroacetic acid.

[0363] Preferably, the composition comprises less than 0.1 wt% of isothiazolinone-based preservatives, more preferably less than 0.05 wt%.

[0364] Soil Release Polymers

[0365] Soil release polymers help improve the release of soil from fabrics by modifying the fabric surface during the wash process. The affinity between the chemical structure of the SRP and the target fibers promotes the adsorption of the SRP on the fabric surface.

[0366] The SRPs 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 include end-capping groups to control molecular weight or change 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.

[0367] 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 such as, for example, sulfonated isophthaloyl units. Examples of such materials include oligoesters produced by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate ("DMT"), propylene glycol ("PG"), and poly(ethylene glycol) ("PEG"); partially and fully anionically terminated oligoesters, such as oligomers from ethylene glycol ("EG"), PG, DMT, and sodium 3,6-dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block polyester oligomeric compounds, such as those produced by combinations of DMT, Me terminated PEG, and EG and / or PG, or DMT, EG and / or PG, Me terminated PEG, and sodium dimethyl-5-sulfoisophthalate, and copolymerized blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0368] 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), for example, C1-C6 vinyl esters (such as poly(vinyl acetate)) grafted onto a polyalkylene oxide backbone; 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.

[0369] Preferred SRPs for use in the present invention include copolyesters formed by the condensation of terephthalate and a diol, preferably 1,2-propylene glycol, and further comprising endcaps formed by alkyl-terminated alkylene oxide repeating units. Examples of such materials have structures corresponding to formula (I):

[0370]

[0371] Where R 1 and R 2Independently of each other are X-(OC2H4) n -(OC3H6) m ;

[0372] Where X is C 1-4 Alkyl, preferably methyl;

[0373] n is a number from 12 to 120, preferably from 40 to 50;

[0374] m is a number from 1 to 10, preferably from 1 to 7; and

[0375] a is a number from 4 to 9.

[0376] Because they are average values, m, n and a are not necessarily integers for the polymer as a whole.

[0377] Mixtures of any of the above materials may also be used.

[0378] When included, the overall level of SRP can range from 0.1 to 10%, depending on the level of polymer intended for use in the final letdown composition, and is ideally 0.3 to 7%, more preferably 0.5 to 5% (by weight based on the total weight of the letdown composition).

[0379] Suitable soil release polymers are described in more detail in U.S. Pat. Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850 and WO 2016 / 005271. If used, soil release polymers are typically incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10%, more preferably 0.1% to 5% by weight of the composition.

[0380] Hydrotropes

[0381] The compositions of the present invention may be blended with non-aqueous carriers such as hydrotropes, cosolvents 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); weight average molecular weight (M w ) ranges from 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 (such as sodium and potassium xylene, toluene, ethylbenzene, and cumene (cumene) sulfonates).

[0382] Mixtures of any of the above materials may also be used.

[0383] When a non-aqueous carrier is included, it may be present in an amount ranging from 0.1 to 3%, preferably 0.5 to 1% (by weight based on the total weight of the composition). The level of hydrotrope used is related to the level of surfactant, and it is desirable to use the level of hydrotrope to control the viscosity of such a composition. Preferred hydrotropes are monopropylene glycol and glycerol.

[0384] Co-surfactant

[0385] In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the compositions of the present invention may contain one or more co-surfactants (such as amphoteric (zwitterionic) and / or cationic surfactants).

[0386] Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof (in which one or two hydroxyethyl groups replace one or two methyl groups), and mixtures thereof. When a cationic surfactant is included, it may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0387] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sultaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycocinates, alkylamidopropyl hydroxysultaines, acyl taurates and acyl glutamates having 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 amphoteric (zwitterionic) surfactants are included, they may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

[0388] Mixtures of any of the above materials may also be used.

[0389] Polymer thickener

[0390] 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 segment (for addition polymerization with other monomers in the mixture) and a hydrophobic segment. A preferred type of associative monomer includes a polyoxyalkylene segment between the ethylenically unsaturated segment and the hydrophobic segment. 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 C8-C8 selected from a linear or branched C8-C8 40 Alkyl (preferably straight chain C 12 -C 22 The associative monomer (i) is prepared by addition polymerization of an associative monomer of (i) polyethoxylated (meth)acrylate (C1-C4 alkyl) polyethoxylated (meth)acrylate; and (ii) at least one further monomer selected from C1-C4 alkyl (meth)acrylate, polyacid vinyl monomer (such as maleic acid, maleic anhydride and / or its salts) and mixtures thereof. The polyethoxylated portion of the associative monomer (i) generally 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.

[0391] Mixtures of any of the above materials may also be used.

[0392] When included, the compositions of the present invention preferably comprise from 0.01 to 5 wt % of the composition, but depending on the amount intended for use in the final diluted product, it is ideally from 0.1 to 3 wt % by weight based on the total weight of the diluted composition.

[0393] Color dye

[0394] 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 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.

[0395] Hueing dyes are well known in the art of laundry liquid formulations.

[0396] 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 of CAS-No 72749-80-5, acid blue 59 and phenazine dyes selected from the following:

[0397]

[0398] in:

[0399] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5;

[0400] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and -OC2H5;

[0401] Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0402] Alkoxylated thiophene dyes are discussed in WO 2013 / 142495 and WO 2008 / 087497.

[0403] 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 will depend on the species and the specific potency within any particular species.

[0404] Microcapsules

[0405] One type of microparticle suitable for use in the present invention is a microcapsule.

[0406] Microencapsulation can be defined as the process of surrounding or encapsulating one substance within another at a very small scale, resulting in capsules ranging in size from less than one micron to several hundred microns. The encapsulated material can be referred to as the core, active ingredient or agent, filler, payload, core, or inner phase. The material encapsulating the core can be referred to as a coating, membrane, shell, or wall material.

[0407] Microcapsules typically have at least one generally spherical continuous shell surrounding a core. Depending on the materials and encapsulation techniques employed, the shell may contain pores, 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, microcapsules may be asymmetrically and variably shaped, with a certain amount of smaller core material droplets embedded throughout the microcapsule.

[0408] 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 the fragrance in response to elevated temperatures. The microcapsule may also release the fragrance in response to shear forces applied to the surface of the microcapsule.

[0409] A preferred type of polymer microparticle suitable for use in the present invention is a polymer core-shell microcapsule in which at least one continuous shell of a generally spherical polymer material surrounds a core containing a fragrance preparation (f2). The shell generally accounts for up to 20% by weight, based on the total weight of the microcapsule. The fragrance preparation (f2) generally accounts 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 obtaining a slurry of the microcapsule, extracting it into ethanol and measuring it by liquid chromatography.

[0410] Further optional ingredients

[0411] The compositions of the present invention may include further optional ingredients to enhance performance and / or consumer acceptance. Examples of these ingredients include foam boosters, preservatives (e.g., bactericides), polyelectrolytes, shrink preventers, wrinkle preventers, antioxidants, sunscreens, corrosion inhibitors, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or sunscreens and tinting dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are included individually in an amount of up to 5% (by weight based on the gross weight of the diluted composition) and are therefore adjusted according to the dilution ratio with water.

[0412] In a second aspect, there is provided a method for cleaning fabrics comprising filling the tank of a washing machine with 80 to 2000 ml of a liquid laundry detergent composition comprising methyl ester ethoxylate,

[0413] And performing at least two wash cycles before adding additional liquid detergent to the sump.

[0414] Preferably, the method comprises adding at least 5 ml of liquid laundry detergent to the wash liquor during the wash cycle. More preferably, the method comprises dosing at least 10 ml and most preferably at least 15 ml of liquid laundry detergent.

[0415] The additional liquid detergent may be the same or different to the initial laundry liquid composition, but preferably it is the same or substantially similar.

[0416] Preferably, the additional liquid laundry composition comprises methyl ester ethoxylate.

[0417] Preferably, the method comprises carrying out at least five wash cycles before adding said further liquid detergent to the sump.

[0418] Preferably, each wash cycle involves drawing a volume of liquid laundry detergent from the sump sufficient to form a suitable wash liquor and clean the fabrics.

[0419] Preferably, the volume is from 10 to 75 ml, but this may depend on the amount of fabric, the stains to be cleaned and the amount of surfactants and other cleaning agents in the liquid laundry composition.

[0420] After the first wash cycle is complete, the remaining liquid detergent remains in the washing machine until the next cycle begins, when an additional dose is pumped from the reservoir and mixed with water to form the wash liquor.

[0421] In a third aspect, there is provided a method for cleaning fabrics, the method comprising filling the tank of a washing machine with 80 to 3000 ml of a liquid laundry detergent composition comprising methyl ester ethoxylate,

[0422] And perform a wash cycle that draws a portion of the liquid detergent from the sump but leaves at least 20 ml in the sump.

[0423] Preferably, after the wash cycle, at least 30 ml, more preferably at least 100 ml, most preferably at least 200 ml remains in the reservoir.

[0424] In a fourth aspect, there is provided a method for cleaning a first fabric, comprising filling the tank of a washing machine with 80 ml to 3000 ml of a liquid laundry detergent composition comprising methyl ester ethoxylate,

[0425] and performing a first wash cycle by drawing a portion of the liquid detergent from the sump and combining it with water to form a first wash liquor, thereby forming a first wash liquor in the washing machine, and washing the first fabric;

[0426] optionally rinsing; and removing the first fabric from the washing machine; and

[0427] performing an additional wash cycle to clean additional fabrics by withdrawing a portion of the liquid detergent from the sump and combining with water to form additional wash liquor and washing additional fabrics;

[0428] optionally rinsing; and removing the additional fabric from the washing machine;

[0429] optionally repeating additional wash cycles; and

[0430] Add additional liquid detergent to the reservoir.

[0431] Preferably, the additional detergent comprises methyl ester ethoxylate.

[0432] But it can be a different liquid detergent. Example

[0433] Example 1

[0434] A liquid detergent formulation was prepared having the following composition:

[0435] Table 1

[0436] A Element weight% LAS 9.9 MEE C18 9EO 7.5 Lauryl Ether Sulfate 3EO 7.5 Triethanolamine 13.9 Polyester Soil Release Polymers 0.5 Monopropylene glycol 3.2 Polyamine Cleaning Polymers 1.0 / 2.2 HASE Thickening Polymer 0.5 fatty acid 1.4 Citric Acid 1.6 Dequest 2010 2.2 Fragrance 1.2 Total enzyme 1.5 Remaining water and trace substances to 100%

[0437] Example 2

[0438] The results of a stability study conducted on different compositions containing various surfactants are shown in Table 2. The study involved exposing the different formulations to ambient conditions for extended periods of time, similar to what the formulations would experience when stored in the tank of an automatic dosing washing machine between wash cycles.

[0439] The table shows the stability data for formulations (1) containing C12AE and formulations (2) containing MEE. All other ingredients in the compositions were identical.

[0440]

[0441] S = Stable

[0442] X = unstable

Claims

1. A washing machine comprising a detergent reservoir, the reservoir containing from 80 ml to 3000 ml of liquid detergent comprising methyl ester ethoxylate.

2. The washing machine according to claim 1, comprising 250 to 2500 ml of liquid detergent.

3. The washing machine according to claim 1, comprising 400 to 2000 ml of liquid detergent.

4. A washing machine according to any one of the preceding claims, wherein the liquid detergent comprises 0.01 to 2 wt% of benzoic acid or a salt thereof.

5. A washing machine according to any preceding claim, wherein the liquid detergent comprises from 0.1 to 3 wt% ethanol.

6. A washing machine according to any preceding claim, wherein the liquid detergent comprises from 0.1 to 5 wt% phenoxyethanol.

7. A washing machine according to any preceding claim, wherein the liquid detergent comprises from 5 to 30 wt% methyl ester ethoxylate.

8. A method for cleaning fabrics comprising filling the tank of a washing machine with 80 to 3000 ml of a liquid laundry detergent composition comprising methyl ester ethoxylate, and performing a wash cycle which draws a portion of the liquid detergent from the reservoir but leaves at least 20 ml in the reservoir.

9. A method for cleaning fabrics comprising filling the tank of a washing machine with 80 to 3000 ml of a liquid laundry detergent composition comprising methyl ester ethoxylate, and performing at least two wash cycles before adding additional liquid detergent to the sump.

10. A method for cleaning a first fabric comprising filling the tank of a washing machine with 80 ml to 3000 ml of a liquid detergent composition comprising methyl ester ethoxylate, and performing a first wash cycle in said washing machine by drawing a portion of said liquid detergent from said sump and combining with water to form a first wash liquor, and washing said first fabric; optionally rinse; and removing the first fabric from the washing machine; and performing an additional wash cycle to clean additional fabrics by withdrawing a portion of the liquid detergent from the sump and combining with water to form additional wash liquor, and washing additional fabrics; optionally rinse; and removing the additional fabric from the washing machine; optionally repeating the additional wash cycle; and Additional liquid detergent is added to the reservoir.

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