Washing machine and washing method

Abstract

The invention relates to a washing machine comprising a detergent storage tank. The storage tank comprises 80 ml to 3000 ml of ethanol-containing liquid detergent.

Description

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

[0002] Despite the prior art, there is still a need for improved liquid detergent compositions for automatic dosing washing machines.

[0003] Accordingly, in a first aspect, there is provided a washing machine comprising a detergent reservoir containing 80 ml to 3000 ml of an ethanol-containing liquid detergent.

[0004] In a second aspect, there is provided a method of cleaning fabrics, which comprises filling the reservoir of a washing machine with 80 to 3000 ml of an ethanol-containing liquid detergent composition, and performing at least two washing cycles before adding additional liquid detergent to the reservoir.

[0005] In a third aspect, there is provided a method of cleaning fabrics, which comprises filling the reservoir of a washing machine with 80 to 3000 ml of an ethanol-containing liquid laundry detergent composition, and performing a washing cycle that draws a portion of the liquid detergent from the reservoir but leaves at least 20 ml in the reservoir.

[0006] The amount of 80 to 3000 ml of liquid detergent characterizes more than one dose of washing dose. Preferably, the reservoir contains 250 to 2500 ml, more preferably 400 to 2000 ml of liquid detergent.

[0007] The washing machine preferably comprises a detergent reservoir capable of storing up to 3000 ml of detergent. Such a washing machine is known in the market as an automatic dosing washing machine and is capable of storing sufficient liquid detergent for more than one washing cycle, preferably for a plurality of washing cycles. Preferably, the washing machine is a front-loading automatic washing machine.

[0008] Preferably, the washing machine includes a housing; a washing tub disposed within the housing, the opening or mouth of which directly faces a laundry loading / unloading opening formed in the front wall of the housing; a detergent dispensing assembly configured to supply detergent to the washing tub; a main tap water supply circuit configured to be connected to a main water pipe and for selectively directing the tap water flow from the main water pipe to the detergent dispensing assembly and / or the washing tub; and an appliance control panel configured to allow a user to manually select a desired washing cycle.

[0009] The washing machine detergent dispensing assembly further includes an automatic metering detergent dispenser configured to automatically meter an appropriate amount of detergent for use during a selected wash cycle based on the selected wash cycle, and includes: one or more detergent reservoirs, each of which is configured to receive a quantity of detergent for performing a plurality of wash cycles; and for each detergent reservoir, a corresponding detergent supply pump configured to selectively draw from the corresponding detergent reservoir an amount of detergent for performing the selected wash cycle and pump / direct the specific amount of detergent into a detergent collection chamber in fluid communication with the wash tub.

[0010] With an automatic metering washing machine, the consumer can perform a plurality of wash cycles before needing to add additional liquid detergent to the reservoir. Typically, the reservoir is sufficient for five or more wash cycles and may be up to 20, depending on the size of the reservoir in the washing machine and the dosage for each wash cycle.

[0011] Each wash cycle includes drawing a certain volume of liquid laundry detergent from the reservoir, which is sufficient to form a suitable wash liquor to clean the fabric.

[0012] 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 surfactant and other cleaning agents in the liquid laundry composition.

[0013] After the first wash cycle is completed, the remaining liquid detergent remains in the washing machine until the next cycle begins, at which time another dose is pumped out of the reservoir and mixed with water to form the wash liquor.

[0014] We have surprisingly found that in such automatic metering washing machines, the liquid detergent is subject to significant physical stress, which means that some liquid detergents are more suitable for this form than others.

[0015] Typical physical stresses include temperature (where the temperature inside the washing machine near the reservoir can easily reach 50 °C or higher), agitation due to the wash cycle, and periods of non-use where the detergent may sit in the reservoir for long periods without any agitation at all.

[0016] A further feature of the liquid detergent in such washing machines is that they must flow freely when required (i.e., between wash cycles) and must not clog the additional pipes in the automatic metering device of the washing machine.

[0017] It is also necessary that the liquid detergent remains satisfactorily in the reservoir during maintenance.

[0018] Such a situation is unusual because it is normal for any liquid to be added to the reservoir at the start of the cycle only to be very rapidly flushed out by the wash water. Thus, it is rare for a washing machine to contain more than one dose of product.

[0019] Surfactant

[0020] The liquid detergent of the present invention preferably contains from 2 to 60% by weight, more preferably from 4 to 50% by weight, and most preferably from 10 to 30% by weight of total surfactants. Preferred are anionic and nonionic surfactants.

[0021] 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 known as alcohol ether sulfates.

[0022] C12-C14 alkyl ether sulfates are commonly used in laundry liquid compositions, which have a straight or branched alkyl (C12-14) containing 12 to 14 carbon atoms and contain on average 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which predominantly C12 lauryl alkyl is ethoxylated with on average 3 EO units per molecule.

[0023] The anionic surfactant is preferably added to the detergent composition in the form of a salt. Preferred cations are alkali metal ions such as sodium and potassium. However, the salt form of the anionic surfactant can be formed in situ by neutralizing the acid form of the surfactant with a base such as sodium hydroxide or an amine such as mono-ethanolamine, di-ethanolamine or tri-ethanolamine. The weight ratio is calculated for the protonated form of the surfactant.

[0024] Non-ionic surfactants are discussed in Non-ionic Surfactants: Organic Chemistry, edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press. Preferred non-ionic surfactants are alkoxylates, preferably ethoxylated. Preferred non-ionic surfactants are alcohol ethoxylates and methyl ester ethoxylates having a C10-C18 alkyl chain. C12-C15 alcohol ethoxylates are commonly used in laundry liquid compositions, which have a straight or branched alkyl group 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.

[0025] Among anionic and non-ionic surfactants, the ethoxy units can be partially replaced by propoxy units.

[0026] Further examples of suitable anionic surfactants are rhamnolipids, α-olefin sulfonates, olefin sulfonates, alkene sulfonates, alkane-2,3-diyl bis(sulfates), hydroxyalkane sulfonates and disulfonates, fatty alcohol sulfates (FAS), paraffin sulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates alkyl- or alkenyl-succinic, dodecenyl / tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEM’s, CITREM’s and diesters and monoesters of sulfosuccinic acid.

[0027] Further examples of suitable non-ionic 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, N-acyl N-alkyl derivatives of polyhydroxyalkyl fatty acid amides or glucosamines, polysorbates (Tweens).

[0028] 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.

[0029] Preferred non-ionic and anionic surfactants are further described below.

[0030] C16 / C18 alcohol ethoxylate

[0031] The preferred C16 / 18 alcohol ethoxylate has the following formula:

[0032] R1-O-(CH2CH2O) q -H

[0033] wherein R1 is selected from saturated, mono-unsaturated and poly-unsaturated straight-chain C16 and C18 alkyl chains, and wherein q is from 4 to 20, preferably from 5 to 14, more preferably from 8 to 12. The mono-unsaturation is preferably at the 9-position of the chain, where the carbon is counted from the chain end to which the ethoxylate is attached. The double bond can be in the cis or trans configuration (oleyl or elaidyl), preferably cis. The cis or trans alcohol ethoxylate 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 in the chain, where the carbon is counted from the chain end to which the OH is attached.

[0034] Preferably, R1 is selected from saturated C16, saturated C18 and mono-unsaturated C18. More preferably, the saturated C16 alcohol ethoxylate is at least 90 wt% of the total C16 straight-chain alcohol ethoxylates. With respect to the C18 alcohol ethoxylate content, it is preferred that the major C18 moiety is C18:1, more preferably C18:1(Δ9). The proportion of mono-unsaturated C18 alcohol ethoxylate is at least 50 wt% of the total C16 and C18 alcohol ethoxylate surfactants. Preferably, the proportion of mono-unsaturated C18 is at least 60 wt% of the total C16 and C18 alcohol ethoxylate surfactants, most preferably at least 75 wt%.

[0035] Preferably, the C16 alcohol ethoxylate surfactant is at least 2 wt% of the total C16 and C18 alcohol ethoxylate surfactants, more preferably 4 wt%.

[0036] Preferably, the saturated C18 alcohol ethoxylate surfactant is at most 20 wt% of the total C16 and C18 alcohol ethoxylate surfactants, and more preferably at most 11 wt%.

[0037] Preferably, the saturated C18 content is at least 2 wt% of the total C16 and C18 alcohol ethoxylate content.

[0038] Alcohol ethoxylates are discussed in Non-ionic Surfactants:Organic Chemistry, edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series, published by CRC Press. Alcohol ethoxylates are commonly referred to as alkyl ethoxylates.

[0039] Preferably, the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1, more preferably from 2 to 100, and 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.

[0040] Linear saturated or monounsaturated C20 and C22 alcohol ethoxylates may also be present. Preferably, the weight fraction of the sum of "C18 alcohol ethoxylate" / "C20 and C22 alcohol ethoxylate" is greater than 10.

[0041] Preferably, the C16 / 18 alcohol ethoxylate contains less than 15% by weight, more preferably less than 8% by weight, and most preferably less than 5% by weight of polyunsaturated alcohol ethoxylate of the alcohol ethoxylate. The polyunsaturated alcohol ethoxylate contains a hydrocarbon chain having two or more double bonds.

[0042] The C16 / 18 alcohol ethoxylate can be synthesized via reaction by ethoxylation of an alkyl alcohol:

[0043] R1-OH + q ethylene oxide → R1-O-(CH2CH2O) q -H

[0044] The alkyl alcohol can be produced by transesterifying triglycerides into methyl esters and then distilling and hydrogenating into an alcohol. This process is discussed in Journal of the American Oil Chemists' Society. 61(2):343 - 348 by Kreutzer, U.R. The preferred alkyl alcohol for this reaction is oleyl alcohol having an iodine value of 60 to 80, preferably 70 to 75, and such alcohol is available from BASF, Cognis, Ecogreen.

[0045] The production of fatty alcohols is further discussed in Sanchez M.A. et al J.Chem.Technol.Biotechnol 2017;92:27 - 92 and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th Edition, Vol.11, pages 436 ff.

[0046] 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.

[0047] 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.

[0048] C16 and / or C18 alcohol ether sulfate

[0049] Preferred ether sulfates have the formula:

[0050] R2-O-(CH2CH2O) p SO3H

[0051] 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.

[0052] Preferably, R2 is selected from saturated C16, saturated C18, and monounsaturated C18. More preferably, saturated C16 is a straight-chain alkyl group with at least 90 wt% C16 content. Regarding the C18 content, it is preferred that the major C18 moiety is C18:1, and 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.

[0053] More preferably, the proportion of monounsaturated C18 accounts for at least 60 wt% of the total C16 and C18 alkyl ether sulfate surfactants, and most preferably at least 75 wt%.

[0054] Preferably, the C16 alcohol ethoxylate surfactant accounts for at least 2 wt% of the total C16 and C18 alkyl ether sulfate surfactants, and more preferably 4 wt%.

[0055] Preferably, the saturated C18 alkyl ether sulfate surfactant accounts for 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.

[0056] In the case where the composition contains a mixture of materials for C16 / 18 sources for alkyl ether sulfates and more traditional C12 alkyl chain length materials, it is preferred that the total C16 / 18 alkyl ether sulfate content should account for at least 10 wt% of the total alkyl ether sulfates, more preferably at least 50 wt% of the alkyl ether sulfates in the composition, even more preferably at least 70 wt%, particularly preferably at least 90 wt%, and most preferably at least 95 wt%.

[0057] Ether sulfates are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, published by CRC Press.

[0058] Straight-chain saturated or monounsaturated C20 and C22 ether sulfates may also be present. Preferably, the weight fraction of "C18 ether sulfates" / "C20 and C22 ether sulfates" is greater than 10.

[0059] Preferably, the C16 and C18 ether sulfates contain less than 15 wt% of the ether sulfates, more preferably less than 8 wt%, most preferably less than 4 wt%, and most preferably less than 2 wt% of polyunsaturated ether sulfates. Polyunsaturated ether sulfates contain hydrocarbon chains with two or more double bonds.

[0060] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. Alcohol ethoxylates can be produced by ethoxylation of alkyl alcohols. The alkyl alcohols for preparing alcohol ethoxylates can be produced by transesterification of triglycerides into methyl esters followed by distillation and hydrogenation into alcohols. This process is discussed in Journal of the American Oil Chemists' Society by Kreutzer, U.R., 61(2):343 - 348. The preferred alkyl alcohol for this reaction is oleyl alcohol with an iodine value of 60 to 80, preferably 70 to 75, and this alcohol is available from BASF, Cognis, and Ecogreen.

[0061] As described in A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017), the poly - unsaturation in surfactants can be controlled by hydrogenation of triglycerides. Distillation and other purification techniques can be used.

[0062] The ethoxylation reaction is described in Non - Ionic Surfactant Organic Chemistry (N.M. van Os, ed.), Surfactant Science Series Volume 72, CRC Press.

[0063] Preferably, the ethoxylation reaction is base - catalyzed using NaOH, KOH, or NaOCH3. Even more preferably, a catalyst that provides a narrower ethoxylate distribution than NaOH, KOH, or NaOCH3 is used. Preferably, these catalysts with narrower distributions include Group II bases such as barium dodecanoate; Group II metal alkoxides; Group II hydrotalcites as described in WO2007 / 147866. Lanthanides can also be used. Such alcohol ethoxylates with narrower distributions are available from Azo Nobel and Sasol.

[0064] Preferably, the narrow ethoxylate distribution has more than 70 wt%, more preferably more than 80 wt% of the ether sulfate R2 - O - (CH2CH2O) z SO3H to R2 - O - (CH2CH2O) w SO3H in the range of ether sulfate R2 - O - (CH2CH2O) p SO3H, where q is the molar average degree of ethoxylation, x and y are absolute values, where z = p - p / 2, and w = p + p / 2. For example, when p = 6, more than 70 wt% of the ether sulfate should consist of ether sulfates with 3, 4, 5, 6, 7, 8, 9 ethoxylate groups.

[0065] The weight of the ether sulfate is calculated in the protonated form: R2-O-(CH2CH2O) p SO3H. In the formulation, it is present in ionic form R2-O-(CH2CH2O) p SO3- with the corresponding counterion. Preferred counterions are Group I and II metals, amines, and most preferably sodium.

[0066] Methyl ester ethoxylate (MEE)

[0067] Preferred methyl ester ethoxylate surfactants have the following form:

[0068] R3(-C=O)-O-(CH2CH2-O) n -CH3

[0069] 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 in the chain can be given in parentheses, oleic acid being 18:1(9), linoleic acid being 18:2(9,12), where 9 is the carbon number starting from the COOH end.

[0070] The integer n is the average molar number of the ethoxylate.

[0071] Methyl ester ethoxylates (MEEs) are described in Chapter 8, pages 287 - 301 of G.A. Smith's Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications (AOCS press 2019); J.Am.Oil.Chem.Soc. vol 74 (1997), pages 847 - 859 by Cox M.E. and Weerasooriva U; Tenside Surf.Det. Vol 28 (2001), pages 72 - 80 by Hreczuch et al.; Household and Personal Care Today (2012), pages 52 - 55 by C. Kolano; J.Am.Oil.Chem.Soc. vol 72 (1995), pages 781 - 784 by A. Hama et al. MEEs can be produced by the reaction of methyl esters with ethylene oxide using a calcium- or magnesium-based catalyst. The catalyst can be removed or left in the MEE.

[0072] Alternative preparation routes are the transesterification of methyl esters or the esterification of carboxylic acids with polyethylene glycol, where the polyethylene glycol is capped with a methyl group at one end of the chain.

[0073] 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) discussed the transesterification of triglycerides with fatty acid methyl esters and glycerol and is hereby incorporated by reference. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide, and sodium methoxide. Esterases and lipases can also be used. Triglycerides occur naturally 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 sunflower oil, high oleic sunflower oil, non-edible vegetable oil, tall oil, and any mixture thereof and any derivatives 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. Vegetable sources are preferred.

[0074] Distillation and fractionation processes can be used in the production of methyl esters or carboxylic acids to produce the desired carbon chain distribution. Preferred sources of triglycerides are those that contain less than 35 wt% polyunsaturated fatty acids in the oil before distillation, fractionation, or hydrogenation.

[0075] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, Unilever oleochemical Indonesia. Biodiesel is methyl ester, and these sources can be used.

[0076] When the ESB is MEE, it preferably has a molar average of 8 to 30 ethoxylate groups (EO), more preferably 10 to 20. The most preferred ethoxylates contain 12 to 18 EO.

[0077] 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, and 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 consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0078] Methyl ester ethoxylates preferably have 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.

[0079] 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.

[0080] In addition, it is preferred that the MEE component also contains some C16 MEE.

[0081] Thus, it is preferred that the total MEE component contains 5 to 50 wt% of C16 MEE of the total MEE. Preferably, the C16 MEE is greater than 90 wt%, more preferably greater than 95 wt% of C16:0.

[0082] In addition, it is preferred that the total MEE component contains less than 15 wt%, more preferably less than 10 wt%, most preferably less than 5 wt% of polyunsaturated C18, i.e., C18:2 and C18:3, of the total MEE. Preferably, C18:3 is present at less than 1 wt%, more preferably less than 0.5 wt%, and most preferably is substantially absent. The degree of polyunsaturation can be controlled by distillation, fractionation, or partial hydrogenation of the feedstock (triglyceride or methyl ester) or MEE.

[0083] In addition, it is preferred that the C18:0 component is less than 10 wt% of the total MEE present.

[0084] In addition, it is preferred that the components with a carbon chain of 15 or shorter account for less than 4 wt% of the total MEE weight present.

[0085] Particularly preferred MEE has 2 to 26 wt% of C16:0 chains, 1 to 10 wt% of C18:0 chains, 50 to 85 wt% of C18:1 chains, and 1 to 12 wt% of C18:2 chains of the MEE.

[0086] Preferred sources for the alkyl groups of the 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 low erucic acid rapeseed oil, methyl esters of high-oleic sunflower oil, methyl esters of high-oleic safflower oil, and methyl esters of high-oleic soybean oil.

[0087] 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.

[0088] Preferably, more than 80 wt% of the double bonds in the MEE are in the cis configuration.

[0089] Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0090] The methyl group of the methyl ester can be replaced by an ethyl or propyl group. The methyl group is most preferred.

[0091] Preferably, the methyl ester ethoxylate comprises from 0.1 to 95% by weight of the methyl ester ethoxylate of the composition. More preferably, the composition comprises from 2 to 40% MEE, most preferably from 4 to 30% by weight of MEE.

[0092] Preferably, the composition comprises at least 50% by weight of water, but this depends on the level of the total surfactant and is adjusted accordingly.

[0093] The composition may comprise further surfactants, and preferably other anionic and / or non-ionic 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% by weight of the total C18 surfactant is the methyl ester ethoxylate surfactant.

[0094] Preferably, the methyl ester ethoxylate surfactant is used in combination with an anionic surfactant. Preferably, the weight fraction of the methyl ester ethoxylate surfactant / total anionic surfactant is from 0.1 to 9, more preferably from 0.15 to 2, most preferably from 0.2 to 1. The 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.

[0095] The weight of the anionic surfactant is calculated in the protonated form.

[0096] Sodium alkyl sulfate

[0097] The composition preferably comprises sodium alkyl sulfate (SAS). The SAS comprises an alkyl chain having 10 to 18 carbon atoms, which may be straight-chain or branched-chain. As described below, the alkyl chain may be derived from renewable resources.

[0098] Preferably, the weight-average alkyl chain length is from 10 to 14, more preferably 12.

[0099] The SAS is present in the composition at from 0.1 to 25% by weight of the composition. In addition to SAS, the composition may also contain LAS, in which case it is preferred that the SAS accounts for 50% by weight (based on the protonated form) of the total LAS plus SAS, more preferably 70% of the total SAS plus LAS, most preferably 95%.

[0100] Source of alkyl chain

[0101] The alkyl chains of the C16 / 18 surfactants are preferably obtained from renewable sources, preferably from triglycerides. Renewable sources are sources in which the material is produced through the natural ecological cycle of living species, preferably by plants, algae, fungi, yeast or bacteria, more preferably by plants, algae or yeast.

[0102] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and trees. The oil from trees is called tall oil. Most preferably, the source is palm oil and rapeseed oil.

[0103] Algal oil is discussed in Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges by Saad M.G. et al. A method for producing triglycerides from biomass using yeast is described in Energy Environ. Sci., 2019, 12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents by Masri M.A. et al.

[0104] Non-edible vegetable oils can be used and are preferably selected from the fruits and seeds of the following plants: Jatropha curcas, Calophyllum inophyllum, Sterculia feotida, Madhuca indica (mahua), Pongamia glabra (koroch seeds), linseed, Pongamia pinnata (karanja), Hevea brasiliensis (rubber seeds), Azadirachta indica (neem), Camelina sativa, Lesquerella fendleri, Nicotiana tabacum (tobacco leaves), Deccan hemp, Ricinus communis L. (castor), Simmondsia chinensis (Jojoba), Eruca sativa.L., Cerbera odollam (Seamango), Coriandrum sativum L. (coriander seeds), Croton megalocarpus, Pilu, Crambe, syringa, Scheleichera triguga (kusum), Stillingia, Shorea robusta (sal), Terminalia belericaroxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, rice bran, Hingan (balanites), Desertdate, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, algae, Argemone mexicana L.)(Mexican prickly poppy), Putranjiva roxburghii (lucky bean tree), Sapindus mukorossi (Soapnut), Melia azedarach (syringe), Thevetia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, Brassica napus, Zanthoxylum bungeanum.

[0105] SLES and PAS

[0106] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are typically obtained by sulfating alcohol ethoxylates. These alcohol ethoxylates are typically obtained by ethoxylating linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating the linear alcohols. Thus, forming linear alcohols is a central step in obtaining both PAS and alkali metal alkyl ether sulfate surfactants.

[0107] Linear alcohols suitable as an intermediate step in manufacturing alcohol ethoxylates and thus anionic surfactants such as sodium lauryl ether sulfate can be obtained from many different sustainable sources. These include:

[0108] Primary sugar

[0109] Primary sugars are obtained from sources such as sucrose or sugar beets and can be fermented to form bioethanol. The bioethanol is then dehydrated to form bioethylene, which then undergoes olefin metathesis to form linear olefins. These linear olefins are then processed into linear alcohols by hydroformylation or oxidation.

[0110] An alternative method that also utilizes primary sugars to form linear alcohols can be used, in which the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed to form linear fatty acids, which are then reduced to form linear alcohols.

[0111] Biomass

[0112] Biomass, such as forest products, rice husks, and wheat straw, etc., can be processed into syngas by gasification. Through the Fischer-Tropsch reaction, these are processed into alkanes, which are dehydrogenated to form olefins. These olefins can be processed in the same manner as the linear olefins described above [primary sugars].[[]END]]

[0113] An alternative method 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 is in turn dehydrated to form bioethylene. This bioethylene is then processed into linear alcohols as described above [for primary sugars].

[0114] Waste plastics

[0115] Waste plastics are pyrolyzed to form pyrolysis oil. It is then fractionated to form linear alkanes, which are dehydrogenated to form olefins. These olefins are processed as described above [for primary sugars].

[0116] Alternatively, the pyrolysis oil is cracked to form ethylene, which is then processed by olefin metathesis to form the desired olefins. These are then processed into linear alcohols as described above [for primary sugars].

[0117] Municipal solid waste

[0118] MSW is converted into syngas by gasification. From the syngas, it can be processed as described above [for primary sugars], or it can be converted into ethanol through an enzymatic process before dehydrogenation into ethylene. The ethylene can then be converted into linear alcohols by the Ziegler process.

[0119] MSW can also be converted into pyrolysis oil by gasification, which is then fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins, and then into linear alcohols.

[0120] Marine carbon

[0121] There are various carbon sources from marine communities such as seaweeds and kelps. From such marine communities, triglycerides can be separated from the source, and it is then hydrolyzed to form fatty acids, which are reduced to linear alcohols in the usual way.

[0122] 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 [for primary sugars].

[0123] Waste oil

[0124] Waste oils such as used cooking oil can be physically separated into triglycerides, which are split as described above to form linear fatty acids and then linear alcohols.

[0125] Alternatively, used cooking oil can undergo the Neste process, whereby the oil is catalytically cracked to form bioethylene. It is then processed as described above.

[0126] Methane capture

[0127] The methane capture method captures methane from landfills or fossil fuel production. Methane can be converted to syngas by gasification. The syngas can be processed as described above, whereby the syngas is converted to methanol (Fischer Tropsch reaction) and then olefins before being converted to linear alcohols by hydroformylation oxidation.

[0128] Alternatively, the syngas can be converted to alkanes and then olefins by Fischer Tropsch and then dehydrogenation.

[0129] Carbon capture

[0130] Carbon dioxide can be captured by any of various well-known methods. Carbon dioxide can be converted to carbon monoxide by the reverse water gas shift reaction, and it can then be converted to syngas using hydrogen in an electrolysis reaction. The syngas is then processed as described above and converted to methanol and / or alkanes before reacting to form olefins.

[0131] Alternatively, the captured carbon dioxide is mixed with hydrogen before being enzymatically treated to form ethanol. This is a process developed by Lanzatech. Thereby, ethanol is converted to ethylene, and then processed into olefins and then linear alcohols as described above.

[0132] The above methods can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0133] Linear alkylbenzene sulfonate

[0134] LAS (linear alkylbenzene sulfonate) is the generally preferred anionic surfactant. However, considering that using SAS instead of LAS can improve performance, it is preferred to use SAS instead of LAS.

[0135] The key intermediate compound in LAS manufacture is the relevant olefin. These olefins (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, marine carbon, etc.

[0136] Whereas in the above methods the olefins are processed by hydroformylation and oxidation to form linear alcohols, the olefins react with benzene and then are sulfonated to form LAS.

[0137] Linear alkylbenzene sulfonates with an alkyl chain length of 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues of alkyl chains, each containing an aromatic ring sulfonated at the "para" position and attached to the linear alkyl chain at any position other than the terminal carbon. The linear alkyl chain preferably has a chain length of 11 to 15 carbon atoms, and the main material has a chain length of about C12. Each alkyl chain homologue consists of a mixture of all possible sulfophenyl isomers other than the 1-phenyl isomer. LAS is usually formulated into the composition in the acid form (i.e., HLAS) and then at least partially neutralized in situ. If used outside of SAS, the linear alkylbenzene sulfonate surfactant is present in the composition at 1 to 20% by weight, more preferably 2 to 15% by weight, and most preferably 8 to 12% by weight.

[0138] Surfactant ratio

[0139] Preferably, the weight ratio of the total nonionic surfactant to the total anionic surfactant (nonionic surfactant weight / anionic surfactant weight) is 0 to 2, preferably 0.2 to 1.5, and most preferably 0.3 to 1.

[0140] Preferably, the weight ratio of the total nonionic surfactant to the total alkyl ether sulfate surfactant (nonionic surfactant weight / alkyl ether sulfate weight) is 0.5 to 2, preferably 0.7 to 1.5, and most preferably 0.9 to 1.1.

[0141] Preferably, the weight ratio of the total C16 / 18 nonionic surfactant to the total alkyl ether sulfate surfactant (nonionic surfactant weight / alkyl ether sulfate weight) is 0.5 to 2, preferably 0.7 to 1.5, and most preferably 0.9 to 1.1.

[0142] Preferably, the weight ratio of the total nonionic surfactant to the total C16 / 18 alkyl ether sulfate surfactant (nonionic surfactant weight / alkyl ether sulfate weight) is 0.5 to 2, preferably 0.7 to 1.5, and most preferably 0.9 to 1.1.

[0143] Preferably, the weight ratio of the total C18:1 nonionic surfactant to the total C18:1 alkyl ether sulfate surfactant (nonionic surfactant weight / alkyl ether sulfate weight) is 0.5 to 2, preferably 0.7 to 1.5, and most preferably 0.9 to 1.1.

[0144] Preferably, the weight ratio of the total nonionic surfactant to the linear alkylbenzene sulfonate (if present) (nonionic surfactant weight / linear alkylbenzene sulfonate weight) is 0.1 to 2, preferably 0.3 to 1, and most preferably 0.45 to 0.85.

[0145] Preferably, the weight ratio of the total C16 / 18 nonionic surfactant to the linear alkylbenzene sulfonate (if present) (nonionic surfactant weight / linear alkylbenzene sulfonate weight) is from 0.1 to 2, preferably from 0.3 to 1, and most preferably from 0.45 to 0.85.

[0146] Preferably, the composition is visually clear.

[0147] Liquid laundry detergent

[0148] In the context of the present invention, the term "laundry detergent" refers to a formulated composition intended for and capable of wetting and cleaning household fabrics such as clothes, linens, and other household textiles. The object of the present invention is to provide a composition which, when diluted, is capable of forming a liquid laundry detergent composition in the manner now described.

[0149] In a preferred embodiment, the liquid composition is isotropic.

[0150] The term "linens" is commonly used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms. Textiles can include woven, non-woven, and knitted fabrics; and can include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends.

[0151] Examples of liquid laundry detergents include heavy-duty liquid laundry detergents for use in the wash cycles of automatic washing machines, as well as liquid delicates and liquid color care detergents, such as those suitable for hand washing or for washing delicate fabrics (e.g., fabrics made of silk or wool) in the wash cycles of automatic washing machines.

[0152] The term "liquid" in the context of the present invention means that the continuous phase or the major part of the composition is liquid and the composition is flowable at 15 °C and above. Thus, the term "liquid" can encompass emulsions, suspensions, and compositions with a flowable but stiffer consistency, called gels or pastes. The viscosity of the composition is preferably from 200 to about 10,000 mPa·s at a shear rate of 25 °C and 21 seconds -1 and a shear rate of 21 seconds. This shear rate is the shear rate typically applied to the liquid when pouring it out of the bottle. A pourable liquid detergent composition preferably has a viscosity of from 200 to 1,500 mPa·s, preferably from 200 to 700 mPa·s.

[0153] The composition according to the present invention may suitably have an aqueous continuous phase. "Aqueous continuous phase" means a water-based continuous phase. Preferably, the composition contains at least 50% by weight of water, more preferably at least 70% by weight of water.

[0154] Alkyl ether sulfates can be provided in the form of a single raw material component or as a mixture of components.

[0155] In cases where the composition comprises a mixture of C16 / 18 source materials for the alkyl ether sulfate and more conventional C12 alkyl chain length materials, it is preferred that the C16 / 18 alkyl ether sulfate in the composition should be at least 10% by weight of the total alkyl ether sulfate, more preferably at least 50% by weight, even more preferably at least 70% by weight, particularly preferably at least 90% by weight, and most preferably at least 95% by weight of the alkyl ether sulfate.

[0156] Alcohol ethoxylates can be provided in the form of a single raw material component or as a mixture of components.

[0157] In cases where the composition comprises a mixture of C16 / 18 source materials for the alcohol ethoxylate and more conventional C12 alkyl chain length materials, it is preferred that the C16 / 18 alcohol ethoxylate in the composition should be at least 10% by weight of the total alcohol ethoxylate, more preferably at least 50% by weight, even more preferably at least 70% by weight, particularly preferably at least 90% by weight, and most preferably at least 95% by weight of the alcohol ethoxylate.

[0158] Preferably, the surfactant is selected and is present in an amount such that the composition and the diluted mixture are isotropic in nature.

[0159] Ethanol

[0160] Preferably, ethanol is present at 0.1 to 5% by weight of the composition, more preferably at 0.5 to 3% by weight of the composition.

[0161] Alkoxylated polyamine

[0162] Preferably, the composition comprises an alkoxylated polyamine as an anti-redeposition polymer to stabilize the dirt in the washing solution and thus prevent the redeposition of dirt. Detergency polymers suitable for the present invention include alkoxylated polyamines, preferably alkoxylated polyethyleneimines. Polyethyleneimine is a material composed of ethyleneimine units -CH2CH2NH-, and in the case of branching, the hydrogen on the nitrogen is replaced by a chain of another ethyleneimine unit. The preferred alkoxylated polyethyleneimine for the present invention has a weight average molecular weight of about 300 to about 10000 (M w) of the polyethyleneimine backbone. 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 both. When the nitrogen atom is 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, where each ethoxylated nitrogen atom in the polyethyleneimine backbone has an average degree of ethoxylation of 10 to 30, preferably 15 to 25 ethoxy groups.

[0163] Mixtures of any of the above materials can also be used.

[0164] More preferably, the polyamine is an alkoxylated cationic or zwitterionic diamine or polyamine polymer, where the positive charge is provided by quaternization of the nitrogen atoms of the amine, and the anionic group (if present) is provided by sulfation or sulfonation of the alkoxylated group.

[0165] Preferably, the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0166] Preferably, greater than or equal to 50 mol% of the nitrogen amines are quaternized, preferably quaternized with methyl. Preferably, the polymer contains 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.

[0167] Preferably, the polymer contains ester (COO) or amide (CONH) groups in its structure. Preferably, these groups are arranged such that when all the ester or amide groups are hydrolyzed, at least one, preferably all of the hydrolysis fragments have a molecular weight less than 4000, preferably less than 2000, most preferably less than 1000.

[0168] Preferably, the polymer has the following form:

[0169]

[0170] where R1 is a C3 to C8 alkyl group, X is (C2H4O) n Y groups, where n is 15 to 30, where m is 2 to 10, preferably 2, 3, 4 or 5, and where Y is selected from OH and SO3 - , and preferably SO3 - group, and the number of SO3 groups is greater than the number of OH groups. Preferably, there are 0, 1 or 2 OH groups. X and R1 can contain ester groups therein. X can contain a carbonyl group, preferably an ester group. Preferably, there is 1 C2H4O unit that separates the ester group from N, such that the structural unit N - C2H4O - ester - (C2H4O) n-1 Y is preferred.

[0171] Such polymers are described in WO2021239547 (Unilever). Exemplary polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Amide and ester groups can be included by adding lactones or sodium chloroacetate (modified Williamson synthesis) to OH or NH groups respectively, followed by subsequent ethoxylation.

[0172] An exemplary reaction scheme for including ester groups is

[0173]

[0174] The addition of lactones is discussed in WO2021 / 165468.

[0175] The compositions of the present 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.

[0176] Aminocarboxylate chelating agent

[0177] Preferably, the composition comprises an aminocarboxylate chelating agent. Preferably, the aminocarboxylate chelating agent is selected from GLDA and MGDA.

[0178] Preferably, the aminocarboxylate is present in the composition in an amount of from 0.1 to 15% by weight, more preferably from 0.1 to 10% by weight, even more preferably from 0.3 to 5% by weight, more preferably from 0.8 to 3% by weight, and most preferably from 1 to 2.5% by weight (based on the weight of the composition).

[0179] Glutamic acid diacetic acid (GLDA)

[0180] GLDA can be present in the form of a mixture of GLDA and its salts. Preferred salt forms include the mono -, di -, tri - or tetra - alkali metal salts and mono -, di -, tri - or tetra - ammonium salts of GLDA. The alkali metal salts of glutamic acid diacetic acid GDLA are preferably selected from lithium salts, potassium salts, and more preferably the sodium salt of GLDA.

[0181] 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 with sodium. Most preferably, the composition comprises the tetrasodium salt of GLDA.

[0182] GLDA is at least partially neutralized with an alkali metal, more preferably with sodium or potassium, and most preferably with sodium.

[0183] The GLDA salt can be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA, or an enantiomerically enriched mixture of isomers.

[0184] Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or their respective mono-, di-, tri- or tetra-alkali metal salts or mono-, di-, tri- or tetra-ammonium salts or mixtures thereof, said mixture mainly comprising the respective L-isomers, with an enantiomeric excess ranging from 10 to 95%.

[0185] Preferably, the GLDA salt is substantially at least partially alkali metal-neutralized L-glutamic acid diacetic acid.

[0186] The sodium salt of GLDA is preferred.

[0187] A suitable commercial source of GLDA in the tetrasodium salt form is available from Nouryon as GL.

[0188] Preferably, the amount of GLDA present in the composition is from 0.1 to 15% by weight, more preferably from 0.1 to 10% by weight, even more preferably from 0.3 to 5% by weight, still more preferably from 0.8 to 3% by weight, and most preferably from 1 to 2.5% by weight (based on the weight of the composition).

[0189] Methylglycine diacetic acid (MGDA)

[0190] Preferred salt forms include the mono-, di-, tri- or tetra-alkali metal salts and mono-, di-, tri- or tetra-ammonium salts of MGDA. The alkali metal salts are preferably selected from lithium salts, potassium salts, and more preferably the sodium salt of MGDA.

[0191] The sodium salt of methylglycine diacetic acid is preferred. Particularly preferred is the trisodium salt of MGDA.

[0192] MGDA can be partially or preferably completely neutralized with the corresponding alkali metal. Preferably, on average 2.7 to 3 COOH groups per molecule of MGDA are neutralized with an alkali metal, preferably with sodium.

[0193] MGDA can be selected from the racemic mixtures of the alkali metal salts of MGDA and the pure enantiomers (such as the alkali metal salts of L-MGDA, D-MGDA), and enantiomerically enriched mixtures.

[0194] A suitable commercial source of MGDA in the trisodium salt form is available from BASF as M and from Nouryon as M-40.

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

[0196] A small amount of the aminocarboxylate may carry a cation other than an alkali metal. Thus, it is possible that a small amount, such as 0.01 to 5 mol%, carries an alkaline earth metal cation, such as Mg 2+ or Ca2 + , or Fe(II) or Fe(III) cations. GLDA may contain small amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. "Small amounts" in this context refers to a total amount of 0.1 to 1% by weight, which refers to the chelating agent aminocarboxylate.

[0197] In addition to the aminocarboxylate chelating agent, the detergent composition may optionally contain a relatively low content of an organic detergent builder or chelating agent substance. Examples include alkali metal citrates, succinates, malonates, carboxymethyl succinates, carboxylates, polycarboxylates, and polyacetyl carboxylates. Specific examples include the sodium, potassium, and lithium salts of oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid. Other examples are DEQUEST TM , the organic phosphonate type chelating agents and alkylene hydroxyphosphonates sold by Monsanto.

[0198] Other suitable organic builders include 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 sold by BASF under the name SOKALAN TM . If used, the organic builder material may 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 built laundry detergent formulation, i.e., it contains less than 1% by weight of phosphate. Most preferably, the laundry detergent formulation is non-built, i.e., it contains less than 1% by weight of builder. Typically in liquids, the preferred chelating agent is HEDP (1-hydroxyethylidene-1,1-diphosphonic acid), for example, sold as Dequest 2010. Also suitable but less preferred due to its poorer 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 is free of phosphonate-based chelating agents.

[0199] External structuring agent

[0200] The compositions of the present invention can be further modified in rheology by using one or more external structuring agents that form a structured network within the composition. Examples of such materials include crystallizable glycerol esters such as hydrogenated castor oil; microfibrillated cellulose and citrus pulp fiber. The presence of an external structuring agent can provide shear-thinning rheology and can also stably suspend materials such as encapsulates and visual cues in the liquid.

[0201] The composition preferably contains a crystallizable glycerol ester.

[0202] As described in WO2011 / 031940, crystallizable glycerol esters can be used to form an external structuring system, the content of which (particularly regarding the manufacture of ESS) is incorporated herein by reference. When ESS is present, it is preferred that the ESS of the present invention preferably comprises: (a) a crystallizable glycerol ester; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components will be discussed in detail below.

[0203] The crystallizable glycerol ester used herein preferably includes "hydrogenated castor oil" or "HCO". The HCO used herein can most commonly be any hydrogenated castor oil, provided that it is capable of crystallizing in the ESS premix. Castor oil can include glycerol esters, particularly triglycerides, which contain C10 to C22 alkyl or alkenyl moieties (which incorporate hydroxyl groups). The hydrogenation of castor oil to prepare HCO converts the double bonds (which may be present in the starting oil such as the castor oil moiety) to saturated hydroxyalkyl moieties (e.g., hydroxystearyl). In some embodiments, the HCO herein can be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. The HCO can be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. The level of HCO present in the ESS of the present invention is typically about 2 wt% to about 10 wt%, about 3 wt% to about 8 wt%, or about 4 wt% to about 6 wt% of the structuring 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 0.1% to 0.8%.

[0204] 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 castor oil source used for hydrogenation to form HCO can be any suitable origin source, 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.

[0205] 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 quite stable, but may vary. 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 consist essentially of triglycerides; or mainly contain or consist essentially of a mixture of diglycerides and triglycerides; or mainly contain or consist essentially 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 consist essentially 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.

[0206] The crystallizable glycerides used in the present invention may have a melting point of about 40 degrees Celsius to about 100 degrees Celsius.

[0207] Hydroxamic acid

[0208] Preferably, the composition comprises hydroxamic acid.

[0209] Whenever the term "hydroxamic acid" or "hydroxamate" is used, this encompasses hydroxamic acid and the corresponding hydroxamate salts (salts of hydroxamic acid), unless otherwise stated.

[0210] Hydroxamic acids are a class of compounds in which a hydroxylamine is inserted into a carboxylic acid. The general structure of a hydroxamic acid is as follows:

[0211]

[0212] where R 1 is an organic residue such as an alkyl or alkenyl group. Hydroxamic acids can exist as their corresponding alkali metal salts or hydroxamates. The preferred salt is the potassium salt.

[0213] Hydroxamates can be conveniently formed from the corresponding hydroxamic acid by replacing the acidic hydrogen atom with a cation:

[0214]

[0215] L + is a monovalent cation such as an alkali metal (e.g., potassium, sodium) or ammonium or substituted ammonium.

[0216] In the present invention, the hydroxamic acid or its corresponding hydroxamate has the following structure:

[0217]

[0218] where R 1 is

[0219] a straight-chain or branched C4-C 20 alkyl group, or

[0220] a straight-chain or branched substituted C4-C 20 alkyl group, or

[0221] a straight-chain or branched C4-C 20 alkenyl group, or

[0222] a straight-chain or branched substituted C4-C 20 alkenyl group, or

[0223] an alkyl ether group CH3(CH2) n (EO) m , where n is from 2 to 20 and m is from 1 to 12, or a substituted alkyl ether group CH3(CH2) n (EO) m , where n is from 2 to 20 and m is from 1 to 12, and the substitution types include one or more of NH2, OH, S, -O-, and COOH,

[0224] and R 2 is selected from hydrogen and a moiety forming part of a cyclic structure with the branched-chain R 1 group.

[0225] Preferred hydroxamic acids are those in which R 2 is hydrogen, R 1 is C8-C 14 alkyl, preferably normal alkyl, and most preferably those which are saturated.

[0226] In the context of the present invention, the general structure of the hydroxamic acid is indicated in Formula 3, and R 1 is defined as above. When R 1 is the alkyl ether group CH3(CH2) n (EO) m where n is from 2 to 20, and m is from 1 to 12, then the alkyl moiety caps the side group. Preferably, R 1 is selected from C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 and C 14 normal alkyl, and most preferably R 1 is at least C 8-14 normal alkyl. When a C8 material is used, this is called octyl hydroxamic acid. The potassium salt is particularly useful.

[0227]

[0228] However, other hydroxamic acids, although less preferred, are also suitable for use in the present invention. Such suitable compounds include, but are not limited to, the following compounds: such hydroxamic acids include lysine hydroxamic acid hydrochloride, methionine hydroxamate, and norvaline hydroxamate, and are commercially available.

[0229] Hydroxamic acids are thought to act by binding to metal ions present in the dirt on the fabric. This binding (which is actually the known chelating property of hydroxamic acids) by itself has no use for removing dirt from the fabric. The key is the "tail" of the hydroxamic acid, i.e., the group R 1 minus that through the group R 2Fold back any branches onto the hydroxamic acid nitrogen. The tail is selected to have an affinity for the surfactant system. This means that the detergency of the already optimized surfactant system is further enhanced by the use of hydroxamic acid, as it effectively labels 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 actually fixed to the particles by binding to the metal ions embedded in the clay-type particles. The non-soap detergency surfactant adheres to the hydroxamic acid, thus overall resulting in more surfactant interacting with the fabric and leading to better detergency. Thereby, hydroxamic acid is used as a linking molecule, thus facilitating the removal of particulate dirt from the fabric and suspension into the wash liquor, and thus enhancing the main detergency.

[0230] Hydroxamic acid has a higher affinity for transition metals (such as iron) than for alkaline earth metals (such as calcium and magnesium), so hydroxamic acid mainly acts to improve the removal of dirt on fabrics, especially particulate dirt, rather than as a builder for calcium and magnesium additionally.

[0231] The preferred hydroxamic acid is coconut hydroxamic acid of 80% solids, which can be obtained from Axis House under the trade name RK853. The corresponding potassium salt can be obtained from Axis House under the trade name RK852. Axis House also supplies coconut hydroxamic acid as 50% solids under the trade name RK858. 50% potassium coconut hydroxamate can be obtained as RK857. Another preferred material is RK842 from Axis House, an alkyl hydroxamic acid made from palm kernel oil.

[0232] Preferably, hydroxamic acid is present in the composition at 0.1 to 3% by weight. More preferably 0.2 to 2% by weight of the composition.

[0233] Preferably, the weight ratio of hydroxamic acid to surfactant is 0.05 to 0.3, more preferably 0.75 to 0.2, and most preferably 0.8 to 1.2. The weight is calculated based on the protonated form.

[0234] Alkoxylated cationic or zwitterionic polyamine polymer

[0235] Preferably, the composition contains an alkoxylated cationic or zwitterionic polyamine polymer. Preferably, the polyamine is an alkoxylated cationic or zwitterionic diamine or polyamine polymer, where the positive charge is provided by quaternization of the nitrogen atom of the amine, and the anionic group (if present) is provided by sulfation or sulfonation of the alkoxylated group.

[0236] Preferably, the alkoxylate is selected from propoxylate and ethoxylate, and most preferably ethoxylate.

[0237] Preferably, at least 50 mol% of the nitrogen amines are quaternized, preferably with methyl. Preferably, the polymer contains from 2 to 10, more preferably from 2 to 6, and most preferably from 3 to 5 quaternized nitrogen amines. Preferably, the alkoxylate groups are selected from ethoxy and propoxy, most preferably ethoxy.

[0238] Preferably, the polymer contains ester (COO) or amide (CONH) groups in its structure. Preferably, these groups are arranged such that when all the 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, and most preferably less than 1000.

[0239] Preferably, the polymer has the following form:

[0240]

[0241] wherein R1 is a C3 - C8 alkyl group, X is (C2H4O) n Y groups, where n is from 15 to 30, where m is from 2 to 10, preferably 2, 3, 4 or 5, and where Y is selected from OH and SO3 - and preferably SO3 - and the number of SO3 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 preferred structural unit is N - C2H4O - ester - (C2H4O) n-1 Y.

[0242] Such polymers are described in WO2021239547 (Unilever). Exemplary polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. The ester groups can be included by adding them to OH or NH groups using lactones or sodium chloroacetate (modified Williamson synthesis method), followed by subsequent ethoxylation.

[0243] Enzyme

[0244] The composition preferably contains an enzyme selected from the group consisting of cellulase, protease and amylase / mannanase mixtures.

[0245] In addition, further enzymes may be present, such as those described below.

[0246] 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, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malic enzyme, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tannase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase or mixtures thereof.

[0247] Preferably, the level of the enzyme is from 0.1 to 100 mg per 100 g of the finished laundry liquid composition, more preferably from 0.5 to 50 mg, and most preferably from 5 to 30 mg of active enzyme protein.

[0248] Examples of preferred enzymes are sold under the following trade names: Purafect (DuPont), Stainzyme (Novozymes), Biotouch (AB Enzymes), (BASF).

[0249] Detergent enzymes are discussed in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0250] A nuclease is an enzyme capable of cleaving the phosphodiester bond between the nucleotide subunits of nucleic acids, and is preferably deoxyribonuclease or ribonuclease. Preferably, the nuclease is deoxyribonuclease, preferably selected from any one of E.C.3.1.21.x (where x = 1, 2, 3, 4, 5, 6, 7, 8 or 9), E.C.3.1.22.y (where y = 1, 2, 4 or 5), E.C.3.1.30.Z (where z = 1 or 2) or E.C.3.1.31.1, and mixtures thereof.

[0251] Proteases hydrolyze the bonds within peptides and proteins, which, in the context 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 peptidases; serine proteases and threonine proteases. These protease families are described in the MEROPS peptidase database (http: / / merops.sanger.ac.uk / ). Serine proteases are preferred. Subtilisin-type serine proteases are more preferred. The term "subtilisin" 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 the substrate. Subtilisins can be divided into 6 subclasses, namely the subtilisin family, the thermitase family, the proteinase K family, the lantibiotic peptidase family, the kexin family and the pyrolysin family.

[0252] Examples of subtilisins are those derived from Bacillus species such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii as described in US 7262042 and WO09 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147 and subtilisin 168 as described in WO 89 / 06279, and proteinase PD138 as described in (WO 93 / 18140). Other useful proteases can be those described in WO 92 / 175177, WO 01 / 016285, WO 02 / 026024 and WO 02 / 016547. Examples of trypsin-like proteases are trypsin (e.g., of porcine or bovine origin) and Fusarium protease as described in WO 89 / 06270, WO 94 / 25583 and WO 05 / 040372, and chymotrypsin derived from Cellulomonas as described in WO 05 / 052161 and WO05 / 052146.

[0253] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0254] Examples of subtilisins are those derived from, for example, Bacillus species such as Bacillus lentus, Bacillus alcalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii as described in US 7,262,042 and WO 09 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147, and subtilisin 168 as described in WO 89 / 06279, and protease PD138 as described in (WO 93 / 18140). Preferably, the subtilisin is derived from a Bacillus species, preferably Bacillus lentus, Bacillus alcalophilus, 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, US 7,262,042, and WO 09 / 021867. Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0255] Suitable commercially available proteases include those sold under the following trade names: DuralaseTm, DurazymTm, Ultra, Ultra, Ultra, Ultra, and are all available as or (Novozymes A / S).

[0256] Suitable amylases (α and / or β) include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also included. Amylases include, for example, α-amylases obtained from Bacillus species, such as a particular strain of Bacillus licheniformis more particularly described in GB 1,296,839, or Bacillus species strains disclosed in WO 95 / 026397 or WO00 / 060060. Commercially available amylases are Duramyl TM 、Termamyl TM 、Termamyl Ultra TM 、Natalase TM 、Stainzyme TM 、Fungamyl TMand BAN TM (Novozymes A / S), Rapidase TM and Purastar TM (from Genencor International Inc.).

[0257] Suitable cellulases include those of bacterial or fungal origin. Chemically modified or protein engineered mutants are also included. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, e.g., the fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum as disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, WO 96 / 029397, and WO 98 / 012307. 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.

[0258] Lipase

[0259] Preferably, the composition contains lipase.

[0260] Lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously herein.

[0261] The composition preferably contains from 0.0005 to 0.5% by weight, preferably from 0.005 to 0.2% by weight of lipase.

[0262] Cleaning 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).

[0263] The lipid esterase can be selected from lipases in E.C. class 3.1 or 3.2 or a combination thereof.

[0264] Preferably, the cleaning lipid esterase is selected from:

[0265] (1) Triacylglycerol lipase (E.C. 3.1.1.3)

[0266] (2) Carboxylic ester hydrolase (E.C. 3.1.1.1)

[0267] (3) Cutinase (E.C. 3.1.1.74)

[0268] (4) Sterol esterase (E.C. 3.1.1.13)

[0269] (5) Wax-ester hydrolase (E.C. 3.1.1.50)

[0270] Triacylglycerol lipase (E.C. 3.1.1.3) is most preferred.

[0271] Suitable triacylglycerol lipases can be selected from variants of the lipase of Humicola lanuginosa (Thermomyces lanuginosus). Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, such as 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 lipases, such as from Bacillus subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), Bacillus stearothermophilus (JP 64 / 744992) or Bacillus pumilus (WO 91 / 16422).

[0272] Suitable carboxylesterases may be selected from wild-type carboxylesterases or variants endogenous to Burkholderia gladioli, Pseudomonas fluorescens, Pseudomonas putida, Bacillus acidocaldarius, Bacillus subtilis, Bacillus stearothermophilus, Streptomyces chrysomallus, Streptomyces diastatochromogenes, and Saccharomyces cerevisiae.

[0273] Suitable cutinases may be selected from wild-type cutinases or variants endogenous to strains of the genus Aspergillus, particularly Aspergillus oryzae; the genus Alternaria, particularly Alternaria brassiciola; the genus Fusarium, particularly Fusarium solani, Fusarium solani pisi, Fusarium oxysporum, Fusarium oxysporum cepa, Fusarium roseum or Fusarium roseum sambucium; the genus Helminthosporum, particularly Helminthosporum sativum; the genus Humicola, particularly Humicola insolens; the genus Pseudomonas, particularly Pseudomonas mendocina or Pseudomonas putida; the genus Rhizoctonia, particularly Rhizoctonia solani; the genus Streptomyces, particularly Streptomyces scabies; the genus Coprinus, particularly Coprinus cinereus; the genus Thermobifida, particularly Thermobifida fusca; the genus Magnaporthe, particularly Magnaporthe grisea; or the genus Ulocladium, particularly Ulocladium consortiale.

[0274] In a preferred embodiment, the cutinase is a variant of the Pseudomonas mendocina cutinase described in WO 2003 / 076580 (Genencor), such as the variant having three substitutions at I178M, F180V, and S205G.

[0275] In another preferred embodiment, the cutinase is the wild-type or a variant of six cutinases endogenous to Coprinus cinereus described in H. Kontkanen et al., App. Environ. Microbiology, 2009, p2148 - 2157.

[0276] In another preferred embodiment, the cutinase is the wild type or a variant of two endogenous cutinases of Trichoderma reesei described in WO2009007510 (VTT).

[0277] In a most preferred embodiment, the cutinase is derived from a strain of Humicola insolens, in particular the Humicola insolens DSM1800 strain. The Humicola insolens cutinase is described in WO 96 / 13580, which is incorporated herein by reference. The cutinase can be a variant, such as one of the variants disclosed in WO 00 / 34450 and WO 01 / 92502. Preferred cutinase variants include those listed in Example 2 of WO 01 / 92502. Preferred commercial cutinases include Novozym51032 (available from Novozymes, Bagsvaerd, Denmark).

[0278] Suitable sterol esterases can be derived from Ophiostoma, such as strains of Ophiostoma piceae; Pseudomonas, such as strains of Pseudomonas aeruginosa; or Melanocarpus, such as strains of Melanocarpus albomyces.

[0279] 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.

[0280] Suitable wax - ester hydrolases can be derived from Simmondsia chinensis.

[0281] The lipid esterase is preferably a lipase selected from E.C. class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably E.C. 3.1.1.3.

[0282] Examples of E.C. 3.1.1.3 lipases include those described in WIPO publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079 and US 5,869,438. Preferred lipases are produced by Absidia reflexa, Absidia corymbefera, Rhizomucor miehei, Rhizopus deleman, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum ( produced by Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzae, Penicilium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, especially Thermomyces lanoginosus. Certain preferred lipases are sold by Novozymes under the trade name Lipolase and (registered trademark of Novozymes); and LIPASE P is available from Areario Pharmaceutical Co., Ltd., Nagoya, Japan; is commercially available from Toyo Jozo Co., Tagata, Japan; and additional Chromobacter viscosum lipases from Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A 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 the "first cycle lipases" described in WO 00 / 60063 and U.S. Patent 6,939,702 B1, preferably variants of SEQ ID No. 2, more preferably SEQ ID No. 2 variants having at least 90% homology with SEQ ID No. 2, which contain a substitution of an electrically neutral or negatively charged amino acid at any of positions 3, 224, 229, 231 and 233 with R or K, and most preferably variants containing the T231R and N233R mutations, and such most preferred variants are sold under the trade name (Novozymes).

[0283] 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, U.S.A.; Diosynth Co., Oss, Netherlands, and / or prepared according to the examples included herein.

[0284] As described in WO 2007 / 087243, lipid esterases with reduced odor generation potential and good relative performance are particularly preferred. These include (Novozyme).

[0285] Preferred commercially available lipases include Lipolase TM and Lipolase Ultra TM 、Lipex TM and Lipoclean TM (Novozymes A / S).

[0286] Fragrance

[0287] Preferably, the fragrance contains components selected from: ethyl 2-methylvalerate (chrysanthemum ester), limonene, (4Z)-cyclopentadecen-4-en-1-one, dihydromyrcenol, dimethyl benzyl carbinyl acetate, benzyl acetate, spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)], benzyl acetate, rose oxide, geraniol, methyl nonyl acetaldehyde, tricyclodecenyl acetate (tricyclodecene acetate), cyclamen aldehyde (cyclamal), β-ionone, hexyl salicylate, tonalide, [2-(cyclohexyloxy)ethyl]benzene (phenafleur), octahydrotetramethylacetophenone (OTNE), benzene, toluene, xylene (BTX) raw materials such as 2-phenylethanol, phenoxanol and their mixtures, cyclododecanone raw materials such as habolonolide, phenolic raw materials such as hexyl salicylate, C5 block or oxygen-containing heterocyclic moiety raw materials such as γ-decalactone, methyl dihydrojasmonate and their mixtures, terpene raw materials such as dihydromyrcenol, linalool, terpinolene, camphor, citronellol and their mixtures, alkyl alcohol raw materials such as ethyl-2-methylbutyrate, diacid raw materials such as ethylene glycol brassylate, and mixtures of these components.

[0288] 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 the fragrance ethyl-2-methylvalerate (chrysanthemum ester).

[0289] 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 the fragrance (4Z)-cyclopentadecen-4-en-1-one.

[0290] 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 the fragrance dimethyl benzyl carbinyl acetate.

[0291] 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 the fragrance dihydromyrcenol.

[0292] 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 the fragrance rose oxide.

[0293] 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 the fragrance tricyclodecenyl acetate.

[0294] 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 the fragrance benzyl acetate.

[0295] 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 the fragrance spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

[0296] 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 the fragrance geraniol.

[0297] 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 the fragrance methyl nonyl acetaldehyde.

[0298] 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 the fragrance tricyclodecenyl acetate (tricyclodecene acetate).

[0299] 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 the fragrance cyclamen aldehyde.

[0300] 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 the fragrance β-ionone.

[0301] 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 the fragrance hexyl salicylate.

[0302] 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 the fragrance tonalide.

[0303] 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 the fragrance [2-(cyclohexyloxy)ethyl]benzene.

[0304] Preferably, the fragrance contains components selected from benzene, toluene, xylene (BTX) raw material classes. More preferably, the fragrance components are selected from 2-phenylethanol, benzoin pentanol and mixtures thereof.

[0305] Preferably, the fragrance contains components selected from cyclododecanone raw material classes. More preferably, the fragrance component is habolonolide.

[0306] Preferably, the fragrance contains components selected from phenolic raw material classes. More preferably, the fragrance component is hexyl salicylate.

[0307] Preferably, the fragrance contains components selected from C5 block or oxygen-containing heterocyclic moiety raw material classes. More preferably, the fragrance components are selected from γ-decalactone, methyl dihydrojasmonate and mixtures thereof.

[0308] Preferably, the fragrance contains components selected from terpene raw material classes. More preferably, the fragrance components are selected from linalool, terpinolene, camphor, citronellol and mixtures thereof.

[0309] Preferably, the fragrance contains components selected from alkyl alcohol raw material classes. More preferably, the fragrance component is ethyl-2-methylbutyrate.

[0310] Preferably, the fragrance contains components selected from diacid raw material classes. More preferably, the fragrance component is ethylene glycol brassylate.

[0311] 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 a fragrance material 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:

[0312] · 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 54464-57-2)

[0313] · 1-(1,2,3,5,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 68155-66-8)

[0314] · 1-(1,2,3,4,6,7,8,8a-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethan-1-one (CAS 68155-67-9)

[0315] This OTNE and its method of manufacture are fully described in US3907321 (IFF).

[0316] The fragrance Molecule 01 is a specific isomer of OTNE and is available from IFF. Another commercially available fragrance, Escentric 01, contains OTNE but also contains ambroxan, pink pepper, lime with a balsamic note such as benzoin, frankincense and incense.

[0317] Generally, commercially available fragrance raw materials contain 1 to 8% by weight of the fragrance raw material OTNE.

[0318] Preferably, the fragrance components listed above are present in the final detergent composition at 0.0001 to 1% by weight of the composition.

[0319] Fluorescent agent

[0320] Preferably, the composition contains a fluorescent agent. More preferably, the fluorescent agent comprises a sulfonated stilbenylbiphenyl fluorescent agent such as those discussed in Chapter 7 of Industrial Dyes (edited by K. Hunger, Wiley VCH 2003).

[0321] Sulfonated stilbenylbiphenyl fluorescent agents are discussed in US5145991 (Ciba Geigy). 4,4'-stilbenylbiphenyl is preferred. Preferably, the fluorescent agent contains 2 SO3 -Group.

[0322] Most preferably, the fluorescent agent has the following structure:

[0323]

[0324] Wherein X is a suitable counterion, preferably selected from metal ions, ammonium ions or amine salt ions, more preferably alkali metal ions, ammonium ions or amine salt ions, and most preferably Na or K.

[0325] Preferably, the fluorescent agent is present at a level of 0.01% to 1% by weight of the composition, more preferably 0.05 to 0.4% by weight, and most preferably 0.11 to 0.3% by weight.

[0326] Surfactants based on C16 and / or C18 alkyl groups, whether alcohol ethoxylates or alkyl ether sulfates, are usually obtained as a mixture with C16 and C18 alkyl chain length raw materials.

[0327] Defoamer

[0328] The composition may also contain an antifoaming agent, but preferably it does not contain an antifoaming agent. Antifoaming agent materials are well known in the art and include siloxanes and fatty acids.

[0329] Preferably, the fatty acid soap is present at 0 to 0.5% by weight of the composition (measured as the acid added to the composition), more preferably 0 to 0.1% by weight, and most preferably zero.

[0330] In the case of the present invention, suitable fatty acids include aliphatic carboxylic acids of the formula RCOOH, where R is a straight-chain or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, and most preferably 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can generally be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or beef tallow).

[0331] The fatty acid can exist in the form of its sodium salt, potassium salt or ammonium salt, and / or in the form of a soluble salt of an organic base (such as monoethanolamine, diethanolamine or triethanolamine).

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

[0333] For the purpose of formulation calculations, in the formulation, fatty acids and / or their salts (as defined above) are not included in the surfactant content or the builder content.

[0334] Preferably, the composition comprises 0.2 to 10% by weight of a cleaning polymer, based on the composition. Preferably, the cleaning polymer is selected from alkoxylated polyethyleneimines, polyester soil-release polymers and copolymers of PEG / vinyl acetate.

[0335] Preservative

[0336] Food preservatives are discussed in Food Chemistry (Belitz H.-D., Grosch W., Schieberle), 4th Edition, Springer.

[0337] The formulation contains a preservative or a mixture of preservatives selected from benzoic acid and its salts, alkyl esters of p-hydroxybenzoic acid and their salts, sorbic acid, diethyl pyrocarbonate, dimethyl pyrocarbonate, preferably benzoic acid and its salts, and most preferably sodium benzoate.

[0338] Optional preferred preservatives are selected from sodium benzoate, phenoxyethanol, dehydroacetic acid and mixtures thereof.

[0339] The preservative is present in an amount of 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight. Where appropriate, the weight is calculated for the protonated form.

[0340] Preferably, the composition comprises 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight, of sodium benzoate, based on the composition.

[0341] Preferably, the composition comprises 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight, of phenoxyethanol, based on the composition.

[0342] Preferably, the composition comprises 0.1 to 3% by weight, preferably 0.3 to 1.5% by weight, of dehydroacetic acid, based on the composition.

[0343] Preferably, the composition comprises less than 0.1% by weight of an isothiazolinone-based preservative, more preferably less than 0.05% by weight.

[0344] Detergent polymer

[0345] The soil-release polymer helps to improve the release of soil from the fabric by modifying the fabric surface during the washing process. The affinity between the chemical structure of the SRP and the target fiber promotes the adsorption of the SRP on the fabric surface.

[0346] The SRPs for use in the present invention can include a variety of charged (e.g., anionic) as well as uncharged monomer units, and the structure can be linear, branched, or star-shaped. The SRP structure can also include end groups to control the molecular weight or alter polymer properties such as surface activity. The weight-average molecular weight (M w ) of the SRP can suitably be in the range of from about 1,000 to about 20,000, preferably in the range of from about 1,500 to about 10,000.

[0347] The SRPs for use in the present invention can suitably be 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 low polyesters produced by transesterification / oligomerization of poly(ethylene glycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”), and poly(ethylene glycol) (“PEG”); partially and fully anionic end-capped low polyesters such as oligomers from ethylene glycol (“EG”), PG, DMT, and sodium 3,6-dioxaoctane sulfonate; non-ionic end-capped block polyester oligomeric compounds such as those produced from a combination of DMT, Me-capped PEG, and EG and / or PG, or DMT, EG and / or PG, Me-capped PEG, and sodium dimethyl-5-sulfoisophthalate, and those produced by copolymeric block of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate.

[0348] Other types of SRPs for use 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 ester), e.g., C1-C6 vinyl esters (such as poly(vinyl acetate)) grafted onto a polyalkylene oxide backbone; poly(vinylcaprolactam) and related copolymers with monomers such as vinylpyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

[0349] Preferred SRPs for use in the present invention include copolyesters formed by the condensation of terephthalates and diols, preferably 1,2-propanediol, and further comprising end-caps formed from alkylene oxide repeat units capped with alkyl groups. Examples of such materials have a structure corresponding to the general formula (I):

[0350]

[0351] wherein R 1 and R 2Each independently is X-(OC2H4) n -(OC3H6) m ;

[0352] wherein X is C 1-4 alkyl, preferably methyl;

[0353] n is a number from 12 to 120, preferably from 40 to 50;

[0354] m is a number from 1 to 10, preferably from 1 to 7; and

[0355] a is a number from 4 to 9.

[0356] Since they are average values, m, n and a are not necessarily integers for the overall polymer.

[0357] Mixtures of any of the above materials can also be used.

[0358] When including SRP, the total content of SRP can range from 0.1 to 10%, depending on the content of the polymer intended for use in the final diluted composition, and it is desirably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the diluted composition).

[0359] Suitable soil-release polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850 and WO2016 / 005271. If used, the soil-release polymer is typically incorporated into the liquid laundry detergent composition herein at a concentration in the range of 0.01% to 10%, more preferably 0.1% to 5% by weight of the composition.

[0360] Hydrotrope

[0361] The compositions of the present invention can incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers. Such materials are typically low molecular weight, water-soluble or water-miscible organic liquids such as C1 to C5 monohydric alcohols (such as ethanol and n-propanol or isopropanol); C2 to C6 diols (such as monopropylene glycol and dipropylene glycol); C3 to C9 triols (such as glycerol); polyethylene glycols with a weight average molecular weight (M w ) in the range of about 200 to 600; C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylaryl sulfonates having at most 3 carbon atoms in the lower alkyl group (such as sodium and potassium xylene, toluene, ethylbenzene and cumene (isopropylbenzene) sulfonates).

[0362] Mixtures of any of the above materials can also be used.

[0363] When a non-aqueous carrier is included, its amount may be in the range of 0.1 to 3%, preferably 0.5 to 1% (by weight based on the total weight of the composition). The content of the hydrotrope used is related to the content of the surfactant, and it is desirable to use the content of the hydrotrope to control the viscosity of this composition. Preferred hydrotropes are monopropylene glycol and glycerol.

[0364] Cosurfactant

[0365] In addition to the above non-soap anionic and / or non-ionic detergent surfactants, the compositions of the present invention may include one or more co-surfactants (such as amphoteric (zwitterionic) and / or cationic surfactants).

[0366] Specific cationic surfactants include C8 to C18 alkyldimethylammonium halides and their derivatives (where one or two hydroxyethyl groups replace one or two methyl groups), and mixtures thereof. When a cationic surfactant is included, its amount may be in the range of 0.1 to 5% (by weight based on the total weight of the composition).

[0367] Specific amphoteric (zwitterionic) surfactants include alkylamine oxides, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines (sulfobetaines), alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates, alkylamphopropionates, alkylamphoglycinates, alkylamidopropylhydroxysulfobetaines, acyltaurates and acylglutamates, which have an alkyl group containing about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18 and C18:1, and the term "alkyl" is used to include the alkyl moiety of the higher acyl group. When an amphoteric (zwitterionic) surfactant is included, its amount may be in the range of 0.1 to 5% (by weight based on the total weight of the composition).

[0368] Mixtures of any of the above materials may also be used.

[0369] Polymer thickener

[0370] The compositions of the present invention can comprise 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 means a monomer having an ethylenically unsaturated segment (for addition polymerization with other monomers in the mixture) and a hydrophobic segment. Preferred types of associative monomers include 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 associative monomer selected from straight-chain or branched C8-C 40 alkyls (preferably straight-chain C 12 -C 22 alkyl) polyethoxylated (meth)acrylate; and (ii) at least one further monomer selected from C1-C4 alkyl (meth)acrylates, polyacid vinyl monomers such as maleic acid, maleic anhydride and / or its salts, and mixtures thereof. The polyethoxylated portion of the associative monomer (i) typically comprises from about 5 to about 100, preferably from about 10 to about 80, more preferably from about 15 to about 60 oxyethylene repeat units.

[0371] Mixtures of any of the above materials can also be used.

[0372] When included, the compositions of the present invention preferably comprise from 0.01 to 5% by weight of the composition, but depending on the amount intended to be used in the final diluted product, it is desirably from 0.1 to 3% by weight based on the total weight of the diluted composition.

[0373] Colorant dye

[0374] Toning dyes can be used to improve the performance of the compositions. Preferred dyes are purple or blue. It is believed that deposition of low levels of dyes of these hues on the fabric masks the yellowing of the fabric. Another advantage of toning dyes is that they can be used to mask any yellow hue of the composition itself.

[0375] Toning dyes are well known in the field of liquid laundry detergent formulations.

[0376] 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 polyethyleneimine as described in WO2011 / 047987 and WO 2012 / 119859, alkoxylated monoazo thiophenes, the dye of CAS-No 72749-80-5, Acid Blue 59, and phenazine dyes selected from:

[0377]

[0378] wherein:

[0379] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5;

[0380] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and -OC2H5;

[0381] Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0382] Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and WO2008 / 087497.

[0383] The color-toning dye is preferably present in the composition in the range of 0.0001 to 0.1% by weight. Depending on the nature of the color-toning dye, there is a preferred range depending on the potency of the color-toning dye, which depends on the class and the specific potency within any particular class.

[0384] Microcapsule

[0385] One type of microparticle suitable for the present invention is microcapsules. Microencapsulation can be defined as the process of surrounding or encapsulating a substance within another substance on a very small scale, resulting in capsules ranging in size from less than one micron to several hundred microns. The material being encapsulated can be referred to as the core, active ingredient or agent, filler, payload, nucleus, or inner phase. The material encapsulating the core can be referred to as the coating, membrane, shell, or wall material.

[0386] Microcapsules generally have at least one continuous shell that is generally spherical and surrounds the core. Depending on the materials and encapsulation techniques employed, the shell can contain pores, voids, or interstitial openings. Multiple shells can be made of the same or different encapsulating materials and can be arranged in layers of different thicknesses around the core. Alternatively, the microcapsules can be asymmetrically and variably shaped, with a certain amount of smaller core material droplets embedded throughout the microcapsule.

[0387] The shell can have a barrier function to protect the core material from the external environment of the microcapsule, but it can also be used as a means to regulate the release of core materials such as fragrances. Thus, the shell can be water-soluble or water-swellable and can initiate fragrance release in response to the microcapsule being exposed to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule can release the fragrance in response to an increase in temperature. The microcapsule can also release the fragrance in response to shear forces applied to the surface of the microcapsule.

[0388] A preferred type of polymer microparticle suitable for 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 formulation (f2). Based on the total weight of the microcapsule, the shell typically accounts for at most 20% by weight. Based on the total weight of the microcapsule, the fragrance formulation (f2) typically accounts for about 10 to about 60% by weight, preferably about 20 to about 40% by weight. The amount of the fragrance (f2) can be measured by obtaining a slurry of the microcapsule, extracting it into ethanol and measuring by liquid chromatography.

[0389] Further optional ingredients

[0390] The compositions of the present invention can include further optional ingredients to enhance performance and / or consumer acceptability. Examples of these ingredients include foam boosters, preservatives (e.g., bactericides), polyelectrolytes, anti-shrinkage agents, anti-wrinkle agents, antioxidants, sunscreens, corrosion inhibitors, drape imparting agents, antistatic agents, ironing aids, colorants, pearlescent agents and / or opacifying agents and shading dyes. The amount of each of these ingredients is present in an amount effective to achieve its purpose. Generally, these optional ingredients are individually included in an amount of up to 5% (by weight based on the total weight of the diluted composition) and are thus adjusted according to the dilution ratio with water.

[0391] In a second aspect, there is provided a method for cleaning fabrics, comprising filling the detergent reservoir of a washing machine with 80 to 2000 ml of a liquid laundry detergent composition containing ethanol,

[0392] and performing at least two washing cycles before adding additional liquid detergent to the reservoir.

[0393] Preferably, the method includes adding at least 5 ml of liquid laundry detergent to the wash liquor during the washing cycle. More preferably, the method includes metering in at least 10 ml and most preferably at least 15 ml of liquid laundry detergent.

[0394] The additional liquid detergent can be the same or different from the initial liquid laundry composition, but preferably it is the same or substantially similar.

[0395] Preferably, the additional liquid laundry composition contains ethanol.

[0396] Preferably, the method includes performing at least five wash cycles before adding said additional liquid detergent to the reservoir.

[0397] Preferably, each wash cycle includes withdrawing a volume of liquid laundry detergent from the reservoir sufficient to form a suitable wash liquor and clean the fabric. Preferably, the volume is from 10 to 75 milliliters, although this may depend on the amount of fabric, the stains to be cleaned, and the amount of surfactant and other cleaning agents in the liquid laundry composition.

[0398] After the first wash cycle is completed, the remaining liquid detergent remains in the washing machine until the next cycle begins, at which point an additional dose is pumped from the reservoir and mixed with water to form the wash liquor.

[0399] In a third aspect, there is provided a method for cleaning fabric, the method comprising filling the reservoir of a washing machine with 80 to 3000 milliliters of an ethanol-containing liquid laundry detergent composition and performing a wash cycle that withdraws a portion of the liquid detergent from the reservoir but leaves at least 20 milliliters in the reservoir.

[0400] Preferably, after the wash cycle, at least 30 milliliters, more preferably at least 100 milliliters, and most preferably at least 200 milliliters are left in the reservoir.

[0401] In a fourth aspect, there is provided a method for cleaning a first fabric, comprising filling the reservoir of a washing machine with 80 milliliters to 3000 milliliters of an ethanol-containing liquid detergent composition and forming a first wash liquor in the washing machine by withdrawing a portion of the liquid detergent from the reservoir and combining it with water to form a first wash liquor, and performing a first wash cycle by washing said first fabric;

[0402] Optionally rinsing; and removing said first fabric from the washing machine; and

[0403] Performing an additional wash cycle to clean said additional fabric by withdrawing a portion of the liquid detergent from the reservoir and combining it with water to form an additional wash liquor, and washing the additional fabric;

[0404] Optionally rinsing; and removing said additional fabric from the washing machine;

[0405] Optionally repeating the additional wash cycle; and

[0406] Adding additional liquid detergent to the reservoir.

[0407] Preferably, the additional detergent contains ethanol.

[0408] However, it can be a different liquid detergent. Examples

[0409] Example 1

[0410] Prepare a liquid detergent formulation having the following composition:

[0411] Table 1

[0412]

[0413]

[0414] Example 2

[0415] The data in Table 2 show that the composition containing ethanol loses less water over time than the composition containing the equivalent preservatives sodium benzoate and phenoxyethanol.

[0416] This means that the composition containing ethanol rather than sodium benzoate or phenoxyethanol as a preservative is more suitable for an automatic metering environment where the composition is exposed for an extended period between wash cycles.

[0417] Table 2

[0418] Formulation 1 contains sodium benzoate

[0419] Formulation 2 contains phenoxyethanol

[0420] Formulation 3 contains ethanol

[0421]

Claims

1. A washing machine comprising a detergent reservoir containing 80 to 3000 ml of an ethanol-containing liquid detergent.

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

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

4. The washing machine according to any one of the preceding claims, wherein the liquid detergent comprises 0.01 to 2% by weight of benzoic acid or its salt.

5. The washing machine according to any one of the preceding claims, wherein the liquid detergent comprises 0.1 to 3% by weight of ethanol.

6. The washing machine according to any one of the preceding claims, wherein the liquid detergent comprises 0.1 to 5% by weight of phenoxyethanol.

7. The washing machine according to any one of the preceding claims, wherein the liquid detergent comprises 5 to 30% by weight of methyl ester ethoxylate.

8. A method for cleaning fabrics, comprising filling the reservoir of a washing machine with 80 to 3000 ml of an ethanol-containing liquid laundry detergent composition and performing a wash cycle that withdraws 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 reservoir of a washing machine with 80 to 3000 ml of an ethanol-containing liquid laundry detergent composition and performing at least two wash cycles before adding additional liquid detergent to the reservoir.

10. A method for cleaning a first fabric, comprising filling the reservoir of a washing machine with 80 ml to 3000 ml of an ethanol-containing liquid detergent composition and forming a first wash liquor in the washing machine by withdrawing a portion of the liquid detergent from the reservoir and combining it with water to form a first wash liquor, and performing a first wash cycle by washing the first fabric; Optionally rinse; and removing the first fabric from the washing machine; and performing an additional wash cycle to clean an additional fabric by withdrawing a portion of the liquid detergent from the reservoir and combining it with water to form an additional wash liquor, and washing the additional fabric; optionally rinsing; and removing the additional fabric from the washing machine; optionally repeating the additional wash cycle; and adding additional liquid detergent to the reservoir.

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