Composition

Abstract

A unit dose product comprising from 8 to 15 g of a detergent composition contained within a pouch formed from a water-soluble film, the composition comprising water and a non-aqueous solvent and a surfactant, where the detergent composition comprises from 5 to 8 g of a surfactant, and where the weight ratio of the total surfactant to the total water and non-aqueous solvent is at least 1.6.

Description

[0001] The present invention relates to an improved unit dose product comprising a detergent liquid laundry composition.

[0002] EP-A-1 059 350 (Greither) discloses capsules containing detergents for releasing detergents during the cleaning process. The capsules contain at least one surfactant having a given chemical formula, which is selected from the monoalkanolammonium salts, dialkanolammonium salts or trialkanolammonium salts of alkyl ether sulfuric acid, having a molecular weight of at least 200 g / mol, preferably at least 300 g / mol. In the chemical formula, R1 represents a hydrocarbon group containing at least 6 carbon atoms; n represents an integer from 1 to 8; L represents -SO3; R2 is a straight-chain or branched-chain alcohol group containing 1 to 10 carbons and at least one hydroxyl group; R3 and R4 are the same or different and are selected from hydrogen, straight-chain and / or branched-chain alcohol groups containing 1 to 10 carbon atoms and at least one hydroxyl group, and straight-chain and / or branched-chain alkyl groups having 1 to 10 carbon atoms. The surfactant can be present in the capsule shell or the capsule filling material, or in both. The capsules of this invention have a high proportion of detergent substances. The capsule shell material is preferably a macromolecular native natural substance and / or is chemically and / or physically modified, preferably gelatin.

[0003] US2021 / 163860 (Meier) discloses a detergent product for treating, cleaning and / or washing textiles, which comprises a membrane bag having a plurality of compartments, wherein each compartment is surrounded by at least one water-soluble membrane. The compartments are formed by water-soluble membranes, which are interconnected in a sealing plane and separated from each other by a sealing portion located in the sealing plane, and the compartments are filled with a detergent formulation. A plurality of compartments with a number n greater than or equal to 2 are provided, and the compartments are arranged in a cross-sectional plane around a common n-fold rotation axis perpendicular to at least one cross-sectional plane, and at least one central compartment, which is arranged in the middle region of the membrane bag and filled with a detergent formulation. The compartments are arranged around the central compartment, and the detergent formulation filled in the central compartment is transparent and achromatic.

[0004] WO 2015 / 164515 (Sun) discloses a unit dose detergent composition, which comprises a water-soluble container formed from a water-soluble film material, and the water-soluble film material encapsulates a liquid composition having a relatively high water content. In one embodiment, the unit dose detergent composition comprises a water-soluble container formed from a water-soluble film material encapsulating a liquid composition, wherein the liquid composition comprises (a) at least one surfactant, (b) at least one humectant selected from polyols having 3 to 9 carbon atoms, and (c) about 15% to about 35% by weight of water.

[0005] Despite the existing technology, there is still a need for improved unit dose detergent compositions. In particular, there is a need for unit dose detergent compositions that are compact, concentrated and yet capable of delivering sufficient cleaning power.

[0006] Accordingly, in a first aspect, there is provided a unit dose product comprising from 8 to 15 g of a detergent composition contained within a sachet formed from a water-soluble film, said composition comprising water and a non-aqueous solvent as well as a surfactant, wherein said detergent composition comprises from 5 to 8 g of surfactant, and wherein the weight ratio of total surfactant to total water and non-aqueous solvent is at least 1.6.

[0007] We have surprisingly found that unit dose products containing a liquid laundry detergent composition in which the weight ratio between the surfactant level and the non-aqueous solvent is higher than 1.6 result in a more stable product. This is particularly relevant for formulations in which the total dose is less than 15 g of detergent composition. Typical prior art unit dose compositions contain much higher levels of detergent composition and thus do not have the same stability conditions.

[0008] More preferably, the weight ratio of total surfactant to total water and non-aqueous solvent is at least 2.0, most preferably at least 2.5.

[0009] Preferably, the surfactant comprises linear alkylbenzene sulfonate and a non-ionic surfactant.

[0010] Preferably, the product contains from 8 to 15 g of detergent composition. Such low dose compositions present formulation challenges as proportionally increased surfactant levels are required to deliver a dose sufficient to clean an average load but yet remain stable when becoming more concentrated.

[0011] Preferably, the composition comprises from 5 to 10 wt% water of the composition.

[0012] Preferably, the product comprises one, two or three chambers, and wherein at least one chamber contains said detergent composition.

[0013] Water-soluble film composition

[0014] The liquid detergent composition is contained within a water-soluble capsule.

[0015] Preferably, the capsule has from one to four compartments. Preferably, the capsule is a unit dose product and can be from 8 to 15 g in weight to represent a unit dose.

[0016] Water-soluble film compositions, optional ingredients therefor and methods for their preparation are well known in the art, whether for preparing relatively thin water-soluble films (e.g., as capsule materials) or others.

[0017] PVA is a synthetic resin usually prepared by the alcoholysis (commonly referred to as hydrolysis or saponification) of polyvinyl acetate. Fully hydrolyzed PVA, in which almost all acetate groups are converted to alcohol groups, is a highly crystalline polymer with strong hydrogen bonding that dissolves only in hot water above approximately 140 degrees Fahrenheit (60 °C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, the PVA polymer is considered to be partially hydrolyzed, with weaker hydrogen bonding and lower crystallinity, and is soluble in cold water below approximately 10 °C. Intermediate cold- or hot-water-soluble films can include, for example, PVA that is partially hydrolyzed in the middle (e.g., a degree of hydrolysis of approximately 94% to approximately 98%), and is only soluble in warm water - for example, dissolving rapidly at temperatures of approximately 40 °C and higher. The fully and partially hydrolyzed types of PVA are generally referred to as PVA homopolymers, although the partially hydrolyzed type is technically a vinyl alcohol - vinyl acetate copolymer.

[0018] In addition to PVA polymers and PVA copolymers, other water-soluble polymers used in blends can include, but are not limited to, modified polyvinyl alcohol, polyacrylates, water-soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine, amylose, water-soluble natural polymers (including, but not limited to, guar gum, gum arabic, xanthan gum, carrageenan, and starch), water-soluble polymer derivatives (including, but not limited to, modified starch, ethoxylated starch, and hydroxypropylated starch), copolymers of the foregoing, and any combination of the foregoing. Other water-soluble polymers can also include polyalkylene oxides, polyacrylamides, polyacrylic acid and its salts, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetate, polycarboxylic acids and their salts, polyamino acids, polyamides, gelatin, methylcellulose, carboxymethylcellulose and its salts, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, and polymethacrylates. Such water-soluble polymers, whether PVOH or others, are commercially available from a variety of sources.

[0019] Any of the foregoing water-soluble polymers are generally suitable for use as film-forming polymers. Generally speaking, water-soluble films can include copolymers and / or blends of the foregoing resins.

[0020] The weight ratio of the amount of all water-soluble polymers to the combined amount of all plasticizers, compatibilizers, and secondary additives can be in the range of, for example, from about 0.5 to about 18, from about 0.5 to about 15, from about 0.5 to about 9, from about 0.5 to about 5, from about 1 to 3, or from about 1 to 2. The specific amounts of plasticizers and other non-polymer components can be selected in a particular embodiment based on the intended application of the water-soluble film to adjust film flexibility and confer processing benefits while considering the desired mechanical film properties. It is well known in the art that the viscosity of a water-soluble polymer (PVA or others) is related to the weight-average molecular weight (W) of the same polymer, and viscosity is typically used as a representative of Mw. Thus, the weight-average molecular weight of the water-soluble polymers (including the first PVA copolymer and the second PVA polymer) can be in the range of, for example, from about 30,000 to about 175,000, or from about 30,000 to about 100,000, or from about 55,000 to about 80,000.

[0021] The water-soluble film can contain other auxiliaries and processing agents, such as but not limited to plasticizers, plasticizing compatibilizers, surfactants, lubricants, mold release agents, fillers, extenders, crosslinking agents, anti-caking agents, antioxidants, anti-sticking agents, defoaming agents, nanoparticles such as layered silicate-type nanoclays (e.g., sodium montmorillonite), bleaching agents (e.g., sodium metabisulfite, sodium bisulfite, etc.), aversion agents such as bittering agents (e.g., denatonium salts such as denatonium benzoate, denatonium saccharide, and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringin; and quassinoids such as quassin and brucine) and pungent agents (e.g., capsaicin, piperine, allyl isothiocyanate, and resiniferatoxin), as well as other functional components, in amounts suitable for their intended purposes. Embodiments including plasticizers are preferred. The amounts of these reagents can be, individually or jointly, up to about 50 wt%, 20 wt%, 15 wt%, 10 wt%, 5 wt%, 4 wt% and / or at least 0.01 wt%, 0.1 wt%, 1 wt% or 5 wt%.

[0022] Plasticizers can include, but are not limited to, glycerol, diglycerol, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol up to 400 MW, neopentyl glycol, trimethylolpropane, polyether polyols, sorbitol, 2-methyl-1,3-propanediol, ethanolamine, and mixtures thereof. Preferred plasticizers are glycerol, sorbitol, triethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, or combinations thereof. Based on the total film weight, the total amount of plasticizer can be in the range of about 10 wt% to about 40 wt%, or about 15 wt% to about 35 wt%, or about 20 wt% to about 30 wt%, for example about 25 wt%. Combinations of glycerol, dipropylene glycol, and sorbitol can be used. Optionally, glycerol can be used in an amount of about 5 wt% to about 30 wt%, or 5 wt% to about 20 wt%, for example about 13 wt%.

[0023] Optionally, dipropylene glycol can be used in an amount of about 1 wt% to about 20 wt%, or about 3 wt% to about 10 wt%, for example 6 wt%. Optionally, sorbitol can be used in an amount of about 1 wt% to about 20 wt%, or about 2 wt% to about 10 wt%, for example about 5 wt%. In certain embodiments, the specific amount of plasticizer can be selected based on the desired film flexibility and processability characteristics of the water-soluble film. At low plasticizer contents, the film may become brittle, difficult to process, or prone to cracking. At elevated plasticizer levels, the film may be too soft, weak, or difficult to process for the desired use.

[0024] In preferred embodiments, the composition contains a taste aversion agent, such as denatonium benzoate, and / or a pungent agent, such as capsaicin.

[0025] Maleic acid-modified polyvinyl alcohol is well known in the art and is commercially available from many water-soluble film manufacturers.

[0026] Preferably, the maleic acid-modified PVA accounts for 10 to 70 wt% of the water-soluble film, more preferably 30 to 60 wt%.

[0027] Preferably, the film contains a phthalocyanine-based pigment.

[0028] Preferably, the film contains less than 10 wt% of acrylic acid-modified PVA.

[0029] The liquid unit dose composition is preferably a laundry composition and contains a detergent (surfactant) and other ingredients as described below to contribute to cleaning performance.

[0030] Surfactant

[0031] The liquid detergent of the present invention preferably contains from 2 to 60% by weight, more preferably from 20 to 60% by weight, and most preferably from 40 to 60% by weight of total surfactants. Preferred are anionic and nonionic surfactants.

[0032] 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.

[0033] Typically used in laundry liquid compositions is C12-C14 alkyl ether sulfate, which has a straight-chain or branched alkyl group containing 12 to 14 carbon atoms (C12-14) and contains an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which mainly the C12 lauryl alkyl group is ethoxylated with an average of 3 EO units per molecule.

[0034] 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 monoethanolamine, diethanolamine or triethanolamine. The weight ratio is calculated for the protonated form of the surfactant.

[0035] Preferably, the composition contains an alkyl ether sulfate as mono-isopropanolamine (MIPA) AES, more preferably MIPA LES.

[0036] Preferably, the alkyl ether sulfate, more preferably, MIPA AES is present in the detergent composition in an amount of 1-10% by weight.

[0037] Other 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 acids, dodecenyl / tetradecenyl succinic acid (DTSA), fatty acid derivatives of amino acids, DATEM's, CITREM's, and diesters and monoesters of sulfosuccinic acid.

[0038] 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 ethoxylates. Preferred non-ionic surfactants are alcohol ethoxylates and methyl ester ethoxylates having C10-C18 alkyl chains. C12-C15 alcohol ethoxylates are commonly used in laundry liquid compositions, which have straight-chain or branched-chain alkyl groups containing 12 to 15 carbon atoms and contain an average of 5 to 12 EO units per molecule. A preferred example is C12-C15 alcohol ethoxylate having a molar average of 7 to 9 ethoxylate units.

[0039] In anionic and non-ionic surfactants, the ethoxy units can be partially replaced by propoxy units.

[0040] The non-ionic surfactant fraction is preferably greater than 50% by weight, more preferably greater than 80% by weight, and most preferably greater than 95% by weight of alcohol ethoxylate. More preferably, the non-ionic surfactant fraction is preferably greater than 50% by weight, more preferably greater than 80% by weight, and most preferably greater than 95% by weight of alcohol ethoxylate.

[0041] Other examples of suitable non-ionic surfactants include alkoxylated fatty acid alkyl esters, alkyl polyglycosides, alkoxylated amines, ethoxylated glycerol esters, 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, and polysorbates (Tweens). The formulation may contain soaps 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.

[0042] Preferred non-ionic surfactants include narrow-range ethoxylates. Preferably, the detergent composition comprises an alcohol ethoxylate of the formula R-O-(CH2CH2O) q -H, where q is the molar average degree of ethoxylation, and the alcohol ethoxylate comprises greater than 70% by weight of R-O-(CH2CH2O) x -H to R-O-(CH2CH2O) y -H within the range of alcohol ethoxylates, and x and y are absolute numbers, where x = q - q / 2 and y = q + q / 2, and R is a C12-C15 alkyl group.

[0043] Preferably, R is a straight-chain or branched-chain alkyl group and preferably has 12 to 14 carbon atoms. In the most preferred embodiment, R is C12 and / or C14. Most preferably, greater than 50% of the total alcohol ethoxylate is C12 or C14.

[0044] Preferably, q is 7, 8, 9, 10, 11, 12, 13 or 14 and mixtures thereof. More preferably, q is 8, 9, 10 or 11 and mixtures thereof, and most preferably 9 and 10.

[0045] Alcohol ethoxylate nonionic 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. C12-C15 alcohol ethoxylates are commonly used in laundry liquid compositions, which have a straight-chain or branched-chain alkyl group containing 12 to 15 carbon atoms and contain an average of 5 to 12 EO units per molecule.

[0046] Preferably, the alcohol ethoxylate is present in the composition at 1 wt% to 35 wt%, preferably 5 wt% to 25 wt%.

[0047] Typically, the ethoxylation reaction to form alcohol ethoxylate is base-catalyzed using NaOH, KOH or NaOCH3. This reaction produces a distribution of ethoxy chain lengths in the alcohol ethoxylate. Narrow-range ethoxylation provides a narrower distribution of ethoxy chain lengths than NaOH, KOH or NaOCH3. Preferably, the narrow ethoxy distribution has greater than 70 wt%, more preferably greater than 80 wt% of the alcohol ethoxylate in the range of X R-O-(CH2CH2O) y -H to R-O-(CH2CH2O) q -H, where q is the molar average degree of ethoxylation and x and y are absolute numbers, where x = q - q / 2 and y = q + q / 2. For example, when q = 10, then greater than 70 wt% of the alcohol ethoxylate should consist of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 ethoxylate groups.

[0048] Narrow range ethoxylation catalysts are described in EP3289790 (Procter & Gamble), EP1747183 (Hacros); Santacesatia et al., Ind. Eng. Chem. Res. 1992, 31, 2419 - 2421; US4239917 (Conoco); Li et al., ACS Omega. November 9, 2021; 6(44):29774 - 29780; Hreczuch et al., J. Am. Oil Chem. Soc. 1996, 73, 73 - 78 and WO2022 / 129374 (Unilever). Ca or Ba based catalysts are preferred, most preferably in combination with sulfuric acid.

[0049] Preferably, the non - ionic surfactant is present in the liquid detergent in an amount of 1 to 22 wt% of the composition, more preferably 2 to 12 wt% of the composition.

[0050] C16 and / or C18 alcohol ether sulfate

[0051] Preferred ether sulfates have the following formula:

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

[0053] wherein R2 is selected from saturated, mono - unsaturated and poly - unsaturated straight - chain C16 and C18 alkyl chains, and wherein p is from 3 to 20, preferably from 4 to 12, more preferably from 5 to 10. The mono - unsaturation is preferably at the 9 - position of the chain, where the carbon is counted from the end of the chain to which the ethoxylate is attached. The double bond can be in the cis or trans configuration (oleyl or elaidyl), but is preferably cis. The cis or trans ether sulfate CH3(CH2)7 - CH=CH - (CH2)8O - (OCH2CH2) 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, where the carbon is counted from the end of the chain to which the OH is attached.

[0054] Preferably, R2 is selected from saturated C16, saturated C18 and mono - unsaturated C18. More preferably, the saturated C16 is a straight - chain alkyl with at least 90 wt% C16 content. Regarding the C18 content, it is preferred that the major C18 portion is C18:1, more preferably C18:1(Δ9). Preferably, the proportion of mono - unsaturated C18 constitutes at least 50 wt% of the total C16 and C18 alkyl ether sulfate surfactants.

[0055] More preferably, the proportion of monounsaturated C18 constitutes at least 60% by weight, and most preferably at least 75% by weight, of the total C16 and C18 alkyl ether sulfate surfactants.

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

[0057] Preferably, the saturated C18 alkyl ether sulfate surfactant constitutes at most 20% by weight, and more preferably at most 11% by weight, of the total C16 and C18 alkyl ether sulfate surfactants.

[0058] Preferably, the saturated C18 content is at least 2% by weight of the total C16 and C18 alkyl ether sulfate content.

[0059] In cases where the composition comprises a mixture of C16 / 18 source materials 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 be at least 10% by weight, 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 total alkyl ether sulfates in the composition.

[0060] Ether sulfates are discussed in the table published by CRC Press, Anionic Surfactants: Organic Chemistry (Marcel Dekker 1995), Surfactant Science Series, edited by Helmut W. Stache.

[0061] Linear saturated or monounsaturated C20 and C22 ether sulfates may also be present.

[0062] Preferably, the sum of "C18 ether sulfates" / the weight fraction of "C20 and C22 ether sulfates" is greater than 10.

[0063] Preferably, the C16 and C18 ether sulfates contain less than 15% by weight, more preferably less than 8% by weight, most preferably less than 4% by weight and most preferably less than 2% by weight of polyunsaturated ether sulfates. Polyunsaturated ether sulfates contain hydrocarbon chains with two or more double bonds.

[0064] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. The alcohol ethoxylates can be produced by ethoxylation of alkyl alcohols. The alkyl alcohols used to produce the alcohol ethoxylates can be produced by transesterification of triglycerides to methyl esters followed by distillation and hydrogenation to alcohols. This process is discussed in 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 such alcohols are available from BASF, Cognis, Ecogreen.

[0065] The degree of polyunsaturation in the surfactant can be controlled by hydrogenation of triglycerides as described in A Practical Guide to Vegetable Oil Processing (Gupta M.K. Academic Press 2017). Distillation and other purification techniques can be used. The ethoxylation reaction is described in Non - Ionic Surfactant Organic Chemistry (edited by N.M. van), Surfactant Science Series Volume 72, CRC Press.

[0066] Preferably, the ethoxylation reaction is base - catalyzed using NaOH, KOH, or NaOCH3. More preferably, catalysts that provide a narrower ethoxylate distribution than NaOH, KOH, or NaOCH3 are used. Preferably, these narrower - distribution catalysts involve Group II bases such as barium laurate; Group II metal alkoxides; Group II hydrotalcites described in WO2007 / 147866. Lanthanides can also be used. Such narrower - distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0067] Preferably, the narrow ethoxylate distribution has greater than 70% by weight, more preferably greater than 80% by weight, of the ether sulfate in the range of R2 - O - (CH2CH2O) z SO3H to R2 - O - (CH2CH2O) w SO3H of the ether sulfate R2 - O - (CH2CH2O) q SO3H, where q is the molar average degree of ethoxylation, and x and y are absolute numbers, where z = p - p / 2 and w = p + p / 2. For example, when p = 6, greater than 70% by weight of the ether sulfate should consist of ether sulfates having 5, 6, 7, 8, 9 ethoxy groups.

[0068] The weight of the ether sulfate is calculated in the protonated form: R2 - O - (CH2CH2O) pSO3H. In the formulation, it is present in ionic form R2 - O - (CH2CH2O) p SO3− together with the corresponding counterion, and the preferred counterions are metals of groups I and II, amines, most preferably sodium.

[0069] The preferred anionic surfactants are further described below.

[0070] C16 / C18 alcohol ethoxylate

[0071] The preferred alcohol ethoxylates have the formula:

[0072] R1 - O - (CH2CH2O) q -H

[0073] 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 cis or trans configuration (oleyl or elaidyl), but is preferably cis. The cis or trans alcohol ethoxylate CH3(CH2)7 - CH=CH - (CH2)8O - (OCH2CH2) n OH is described as a C18:1(Δ9) ether ethoxylate. This follows the nomenclature CX:Y(ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds, and ΔZ is the position of the double bond on the chain, where the carbon is counted from the chain end to which the OH is attached.

[0074] Preferably, R1 is selected from saturated C16, saturated C18, and mono - unsaturated C18. More preferably, the saturated C16 alcohol ethoxylate is a straight - chain alcohol ethoxylate with at least 90 wt% C16 content. Regarding the C18 alcohol ethoxylate content, it is preferred that the major C18 portion is C18:1, more preferably C18:1(Δ9). The proportion of mono - unsaturated C18 alcohol ethoxylate constitutes at least 50 wt% of the total C16 and C18 alcohol ethoxylate surfactants. Preferably, the proportion of mono - unsaturated C18 constitutes at least 60 wt% of the total C16 and C18 alcohol ethoxylate surfactants, most preferably at least 75 wt%.

[0075] Preferably, the C16 alcohol ethoxylate surfactant constitutes at least 2 wt% of the total C16 and C18 alcohol ethoxylate surfactants, and more preferably 4 wt%.

[0076] Preferably, the saturated C18 alcohol ethoxylate surfactant constitutes at most 20 wt% of the total C16 and C18 alcohol ethoxylate surfactants, more preferably at most 11 wt%.

[0077] Preferably, the saturated C18 content is at least 2 wt% of the total C16 and C18 alcohol ethoxylate content.

[0078] Alcohol ethoxylates are discussed in Non-ionic Surfactants: Organic Chemistry (Marcel Dekker 1998), Surfactant Science Series, edited by Nico M. van Os and published by CRC Press. Alcohol ethoxylates are commonly referred to as alkyl ethoxylates.

[0079] 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 fractions in the alcohol ethoxylate, and "C16 alcohol ethoxylate" is the sum of all C16 fractions in the alcohol ethoxylate.

[0080] 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.

[0081] Preferably, the C16 / 18 alcohol ethoxylate contains less than 15 wt%, more preferably less than 8 wt%, and most preferably less than 5 wt% of polyunsaturated alcohol ethoxylate. Polyunsaturated alcohol ethoxylates contain hydrocarbon chains with two or more double bonds.

[0082] The C16 / 18 alcohol ethoxylate can be synthesized by ethoxylation of an alkyl alcohol via the following reaction:

[0083] R1-OH + q ethylene oxide → R1-O-(CH2CH2O) q -H

[0084] The alkyl alcohol can be produced by transesterifying a triglyceride to a methyl ester and then distilling and hydrogenating it to an alcohol. This method is discussed in Journal of the American Oil Chemists’ Society 61(2): 343-348 by Kreutzer, U.R. The preferred alkyl alcohol for the reaction has an iodine value of 60 - 80, preferably 70 - 75, and such alcohols are available from BASF, Cognis, Ecogreen.

[0085] The production of fatty alcohols is further discussed in Sanchez M.A. J. Chem. Technol. Biotechnol 2017; 92: 27 - 92 and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th Edition, Volume 11, pages 436 ff.

[0086] Preferably, the ethoxylation reaction is base - catalyzed using NaOH, KOH or NaOCH3. Even more preferably, a catalyst is provided that gives a narrower ethoxy distribution than NaOH, KOH or NaOCH3. Preferably, these catalysts with a narrower distribution relate to Group II bases such as barium laurate; Group II metal alkoxides; Group II hydrotalcites as described in WO2007 / 147866. Lanthanides can also be used. Such alcohol ethoxylates with a narrower distribution are available from Azo Nobel and Sasol.

[0087] Preferably, the narrow ethoxy distribution has more than 70 wt%, more preferably more than 80 wt%, of the alcohol ethoxylate R - O-(CH2CH2O) x -H to R - O-(CH2CH2O) y -H in the range of R - O-(CH2CH2O) q -H, where q is the molar average degree of ethoxylation, and x and y are absolute numbers, where x = q - q / 2 and y = q + q / 2. For example, when q = 10, then more than 70 wt% of the alcohol ethoxylate should consist of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15 ethoxylate groups.

[0088] Methyl ester ethoxylate (MEE)

[0089] Preferred methyl ester ethoxylate surfactants have the following form:

[0090] R3(-C = O)-O-(CH2CH2 - O) n -CH3

[0091] where R3COO is the fatty acid moiety, such as oleic acid, stearic acid, palmitic acid. Fatty acid nomenclature describes a fatty acid by 2 numbers A:B, where A is the number of carbon atoms in the fatty acid and B is the number of double bonds it contains. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bond on the chain can be given in parentheses, oleic acid is 18:1(9), linoleic acid is 18:2(9,12), where 9 is the carbon number starting from the COOH end.

[0092] The integer n is the molar average of the ethoxylate.

[0093] Methyl ester ethoxylates (MEEs) are described in Chapter 8, Synthesis, Properties, and Applications, pp. 287 - 301 of Biobased Surfactants (2nd Edition) by G.A. Smith (AOCS press 2019); J. Am. Oil Chem. Soc. vol 74 (1997) by Cox M.E. and Weerasooriva U, pp. 847 - 859; Tenside Surf. Det. Vol. 28 (2001) by Hreczuch et al., pp. 72 - 80; Household and Personal Care Today (2012) by C. Kolano, pp. 52 - 55; J. Am. Oil Chem. Soc. Vol. 72 (1995) by A. Hama et al., pp. 781 - 784. MEEs can be produced by the reaction of methyl esters with ethylene oxide using calcium - or magnesium - based catalysts. The catalyst can be removed or left in the MEE.

[0094] Alternative preparation routes are the transesterification of methyl esters or the esterification of carboxylic acids with polyethylene glycols capped with a methyl group at one end of the chain.

[0095] Methyl esters can be prepared by the transesterification of methanol with triglycerides or the esterification of methanol with fatty acids. The transesterification of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol. 8, Chapter 101) and references therein. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide, and sodium methoxide. Esterases and lipases can also be used. Triglycerides occur naturally in vegetable fats or oils. Preferred sources are rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high stearic acid / high oleic sunflower oil, high oleic sunflower oil, inedible vegetable oils, tall oil, and any mixtures thereof, and any derivatives thereof. Oils from trees are called tall oil. Used food cooking oils can be used. Triglycerides can also be obtained from algae, fungi, yeast, or bacteria. Plant sources are preferred.

[0096] Distillation and fractionation processes can be used to produce methyl esters or carboxylic acids to yield 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.

[0097] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, and Unilever oleochemical Indonesia. Biodiesel is methyl ester and can use these sources.

[0098] When the ESB is MEE, it preferably has a molar average of 8 to 30, more preferably 10 to 20 ethoxylate groups (EO). The most preferred ethoxylates contain 12 to 18 EO.

[0099] Preferably, at least 10% by weight, more preferably at least 30% by weight of the total C18:1 MEE in the composition has 9 to 11 EO, and even more preferably at least 10% by weight is exactly 10 EO. For example, when the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0100] 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, and even more preferably 10 EO. When the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0101] In the case of a wider MEE contribution, it is preferred that at least 40% by weight of the total MEE in the composition is C18:1.

[0102] In addition, it is preferred that the MEE component also contains some C16 MEE.

[0103] Therefore, it is preferred that the total MEE component contains 5 to 50% by weight of C16 MEE based on the total MEE. Preferably, the C16 MEE is greater than 90% by weight, more preferably greater than 95% by weight of C16:0.

[0104] In addition, it is preferred that the total MEE component contains less than 15% by weight, more preferably less than 10% by weight, and most preferably less than 5% by weight of polyunsaturated C18, i.e., C18:2 and C18:3. Preferably, C18:3 is present at less than 1% by weight, more preferably less than 0.5% by weight, and most preferably is substantially absent. The polyunsaturated level can be controlled by distillation, fractionation, or partial hydrogenation of the raw material (triglyceride or methyl ester) or MEE.

[0105] In addition, it is preferred that the C18:0 component is less than 10% by weight of the total MEE weight present.

[0106] In addition, it is preferred that the components having a carbon chain of 15 or shorter account for less than 4% by weight of the total MEE present.

[0107] Particularly preferred MEEs have C16:0 chains at 2 to 26 wt% of the MEE, C18:0 chains at 1 to 10 wt% of the MEE, C18:1 chains at 50 to 85 wt% of the MEE, and C18:2 chains at 1 to 12 wt% of the MEE.

[0108] Preferred sources of the alkyl groups of 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.

[0109] High oleic oils are available from DuPont (Plenish high oleic soybean oil), Monsanto (Visitive Gold soybean oil), Dow (ω-9 rapeseed oil, ω-9 sunflower oil), National Sunflower Association, and Oilseeds International.

[0110] Preferably, greater than 80 wt% of the double bonds in the MEE are in the cis configuration.

[0111] Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0112] The methyl group of the methyl ester can be replaced by an ethyl or propyl group. The methyl group is most preferred.

[0113] Preferably, the methyl ester ethoxylate constitutes 0.1 to 95 wt% of the methyl ester ethoxylate in the composition. More preferably the composition comprises 2 to 40 wt% of MEE, and most preferably 4 to 30 wt% of MEE.

[0114] Preferably, the methyl ester ethoxylate surfactant is used in combination with an anionic surfactant. Preferably, the weight fraction of methyl ester ethoxylate surfactant / total anionic surfactant is 0.1 to 9, more preferably 0.15 to 2, and most preferably 0.2 to 1. The total anionic surfactant refers to the total content of any type of anionic surfactant, and the anionic surfactant is preferably ether sulfate, linear alkylbenzene sulfonate, alkyl ether carboxylate, alkyl sulfate, rhamnolipid, and mixtures thereof.

[0115] Source of alkyl chain

[0116] The alkyl chains of the C16 / 18 surfactant are preferably obtained from renewable sources, preferably from triglycerides. A renewable source is a source in which the material is produced through the natural ecological cycle of living species, preferably through plants, algae, fungi, yeast, or bacteria, more preferably plants, algae, or yeast.

[0117] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil, and trees. Oil from trees is known as tall oil. Most preferably, palm oil and rapeseed oil are the sources.

[0118] Algal oils are discussed in Energies 2019, 12, 1920 by Saad M.G. et al. titled Algal Biofuels: Current Status and Key Challenges. A method for producing triglycerides from biomass using yeast is described in Energy Environ. Sci., 2019, 12, 2717. Masri M.A. et al. describe a sustainable and high-performance economic production method for waste-free microbial oil as an alternative to plant-based equivalents.

[0119] Inedible vegetable oils can be used, and fruits and seeds are preferably selected from the following: 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 (Sea mango), Coriandrum sativum L. (coriander seeds), Croton megalocarpus, Pilu, Crambe, syringa, Scheleichera triguga (kusum), Stillingia, Shorearobusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var.vestita, algae, Argemone mexicana L.)(Mexican prickly poppy), Putranjiva roxburghii (lucky bean tree), Sapindus mukorossi (Soapnut), Melia azedarach (clove), Thevetia peruviana (yellow oleander), Copaiba, Milk bush, Laurel, Cumaru, Andiroba, Piqui, Brassica napus, Zanthoxylum bungeanum.

[0120] SLES and PAS

[0121] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are generally obtainable by sulfating alcohol ethoxylates. These alcohol ethoxylates are generally obtainable by ethoxylating linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating linear alcohols.

[0122] Therefore, forming linear alcohols is a central step in obtaining PAS and alkali metal alkyl ether sulfate surfactants.

[0123] Linear alcohols suitable as an intermediate step in the manufacture of alcohol ethoxylates and thus anionic surfactants such as sodium dodecyl ether sulfate can be obtained from many different sustainable sources. These include:

[0124] Primary sugar

[0125] 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.

[0126] Alternative methods that also utilize primary sugars to form linear alcohols can be used, and in which the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed into linear fatty acids, which are then reduced to form linear alcohols.

[0127] Biomass

[0128] Biomass, such as forestry products, rice husks, and rice straw, can be gasified to produce syngas. Through the Fischer-Tropsch reaction, these materials are processed into alkanes, which are then dehydrogenated to produce olefins. These olefins can be processed in the same manner as the olefins described above [primary sugars].

[0129] An alternative method is to convert the same biomass into polysaccharides by steam explosion, which can be enzymatically degraded to secondary sugars. These secondary sugars are then fermented to form bioethanol, which is subsequently dehydrated to form bioethylene. This bioethylene is then processed into linear alcohols as described above [primary sugars].

[0130] Waste plastic

[0131] Waste plastics are pyrolyzed to form pyrolysis oil. This is then fractionated to form linear alkanes, which are dehydrogenated to produce olefins. These olefins are processed as described above [primary sugars].

[0132] Alternatively, the pyrolysis oil is cracked to form ethylene, which is then processed by olefin metathesis to form the desired olefins. These are then processed into linear alcohols as described above [primary sugars].

[0133] Municipal solid waste

[0134] MSW is converted to syngas by gasification. From the syngas, it can be processed as described above [primary sugars], or it can be converted to ethanol by an enzymatic process before dehydrogenation to ethylene. The ethylene can then be converted to linear alcohols by the Ziegler process.

[0135] MSW can also be converted to pyrolysis oil by gasification, which is then fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins, and then linear alcohols.

[0136] Marine carbon

[0137] There are various carbon sources from marine communities such as seagrasses and seaweeds. From such marine communities, triglycerides can be separated from the source and subsequently hydrolyzed to form fatty acids, which are reduced to linear alcohols in the usual manner.

[0138] Alternatively, the feedstock can be separated into polysaccharides, which are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol, and then processed as described above [primary sugars].

[0139] Waste oil

[0140] Waste oil (such as used cooking oil) can be physically separated into triglycerides, which are split to form linear fatty acids, and then linear alcohols as described above.

[0141] Alternatively, used cooking oil can undergo the Neste process, whereby the oil is catalytically cracked to form bio-ethylene. It is then processed as described above.

[0142] Methane capture

[0143] Methane capture methods capture methane from landfills or fossil fuel production. Methane can be formed into syngas by gasification. The syngas can be processed as described above, whereby the syngas is converted to methanol (Fischer Tropsch reaction), and then to olefins before being converted to linear alcohols by hydroformylation oxidation.

[0144] Alternatively, the syngas can be converted to alkanes and then to olefins by Fischer Tropsch and subsequent dehydrogenation.

[0145] Carbon capture

[0146] Carbon dioxide can be captured by any of a variety of well-known methods. Carbon dioxide can be converted to carbon monoxide by the reverse water gas shift reaction, which 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 to alkanes before reacting to form olefins.

[0147] Alternatively, the captured carbon dioxide is mixed with hydrogen before being enzymatically treated to form ethanol. This is a method developed by Lanzatech. Thereby, the ethanol is converted to ethylene, then processed to olefins and then processed to linear alcohols as described above.

[0148] The methods described above can also be used to obtain the C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0149] Linear alkylbenzene sulfonate

[0150] LAS (linear alkylbenzene sulfonate) is the preferred anionic surfactant.

[0151] The key intermediate compound in LAS production is the relevant chain olefin. These chain olefins (olefins) can be produced by any of the methods described above and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, marine carbon, etc.

[0152] Whereas in the methods described above the olefins are processed by hydroformylation and oxidation to form linear alcohols, the olefins react with benzene and then are sulfonated to form LAS.

[0153] Linear alkylbenzene sulfonates having 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 in 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, with the main material having a chain length of about C12. Each alkyl chain homologue consists of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is usually formulated into the composition in acid form (i.e., HLAS) and then at least partially neutralized in situ.

[0154] Preferably, the linear alkylbenzene sulfonate surfactant is present in the detergent composition in an amount of 10 to 30% by weight, more preferably 15 to 25% by weight, and most preferably 18 to 23% by weight.

[0155] Surfactant ratio

[0156] Preferably, the weight ratio of total nonionic surfactant to total anionic surfactant (weight of nonionic surfactant / weight of anionic surfactant) is 0 to 2, preferably 0.2 to 1.5, and most preferably 0.3 to 1.

[0157] Preferably, the weight ratio of total nonionic surfactant to total alkyl ether sulfate surfactant (weight of nonionic surfactant / weight of alkyl ether sulfate surfactant) is 0.5 to 2, preferably 0.7 to 1.5, and most preferably 0.9 to 1.1.

[0158] Preferably, the composition contains less than 12% by weight of water, but this depends on the total surfactant content and is adjusted accordingly. More preferably, the composition contains less than 10% by weight of water.

[0159] Preferably, the composition is visually transparent.

[0160] Aminocarboxylate

[0161] Preferably, the composition contains an aminocarboxylate chelating agent. Preferably, the aminocarboxylate chelating agent is selected from GLDA and MGDA.

[0162] Preferably, the aminocarboxylate is present in the composition in an amount of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, still more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

[0163] Glutamic acid diacetic acid (GLDA)

[0164] GLDA can be present as a salt of GDLA or as a mixture of GDLA and GDLA salts. Preferred salt forms include the mono-, di-, tri- or tetra-alkali metal salts of GLDA and the mono-, di-, tri- or tetra-ammonium salts. The alkali metal salts of glutamic acid diacetic acid GDLA are preferably selected from the lithium salt, potassium salt of GLDA, and more preferably the sodium salt.

[0165] Glutamic acid diacetic acid can be partially or preferably completely neutralized with the corresponding base. Preferably, on average 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.

[0166] GLDA is at least partially neutralized with an alkali metal, more preferably with sodium or potassium, and most preferably with sodium.

[0167] The GLDA salt can be an alkali metal salt of L-GLDA, an alkali metal salt of D-GLDA or a mixture of enantiomerically enriched isomers.

[0168] Preferably, the composition comprises a mixture of the L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or their corresponding mono-, di-, tri- or tetra-alkali metal salts or mono-, di-, tri- or tetra-ammonium salts or mixtures thereof, said mixture mainly containing the corresponding L-isomer with an enantiomeric excess (ee) in the range of 10 to 95%.

[0169] Preferably, the GLDA salt is substantially L-glutamic acid diacetic acid at least partially neutralized with an alkali metal.

[0170] The sodium salt of GLDA is preferred.

[0171] A commercial source of GLDA in the form of the suitable tetrasodium salt is GL purchased from Nouryon GL.

[0172] Preferably, GLDA is present in the composition in an amount of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, still more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

[0173] Methylglycine diacetic acid (MGDA)

[0174] Preferred salt forms include the mono-, di-, tri- or tetra-alkali metal and mono-, di-, tri- or tetra-ammonium salts of MGDA. The alkali metal salts are preferably selected from the lithium salt, potassium salt of MGDA, and more preferably the sodium salt.

[0175] The sodium salt of methylglycine diacetic acid is preferred. Particularly preferred is the trisodium salt of MGDA.

[0176] MGDA can be partially or preferably completely neutralized with the corresponding alkali metal. Preferably, 2.7 to 3 COOH groups per molecule of MGDA are neutralized with an alkali metal, preferably with sodium.

[0177] MGDA can be selected from the racemic mixtures of the alkali metal salts of MGDA and the pure enantiomers, and the pure enantiomers such as the alkali metal salts of L-MGDA, the alkali metal salts of D-MGDA, and the mixtures of enantiomerically enriched isomers.

[0178] A suitable commercial source of the trisodium form of MGDA is M purchased from BASF and M-40 purchased from Nouryon.

[0179] Preferably, MGDA is present in the composition in an amount of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.3 to 5% by weight, still more preferably 0.8 to 3% by weight, and most preferably 1 to 2.5% by weight (based on the weight of the composition).

[0180] A small amount of the aminocarboxylate may carry cations other than alkali metals. Thus, a small amount (such as 0.01 to 5 mol%) may carry alkaline earth metal cations, such as Mg 2+ or Ca 2+ , or Fe(II) or Fe(III) cations are possible. GLDA may contain small amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. In such cases, "a small amount" means a total of 0.1 to 1% by weight, referring to the chelating agent aminocarboxylate.

[0181] Organic acid

[0182] The composition preferably contains an organic acid. Preferably, the organic acid has the general formula structure R-CH(OH)-COOH, where R is a straight-chain C1-C5, more preferably C2-C4, and most preferably C4 alkyl.

[0183] Preferably, at least two, more preferably all, of the carbon atoms in the straight-chain C1-4 are substituted with OH groups. Preferably, R contains a terminal COOH group.

[0184] Preferred examples are lactic acid, tartaric acid, gluconic acid, mucic acid, glucoheptonic acid. Most preferably, the organic acid is gluconic acid.

[0185] The organic acid can be in its D or L form.

[0186] Gluconic acid can be selected from the racemic mixtures of the salts (gluconates) of gluconic acid and the pure enantiomers (such as the alkali metal salts of L-gluconic acid, the alkali metal salts of D-gluconic acid) and the mixtures of enantiomerically enriched isomers. The D-isomer form is preferred.

[0187] Preferably, the organic acid is present in the range of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.2 to 4% by weight, still more preferably 0.5 to 3% by weight, and most preferably 0.8 to 2% by weight (based on the weight of the composition). Measurement is made for its protonated form.

[0188] In the most preferred embodiment, the composition comprises GLDA and / or MGDA and gluconic acid, more preferably GLDA and gluconic acid.

[0189] Crystallizable glyceride

[0190] The composition preferably comprises a crystallizable glyceride.

[0191] The crystallizable glyceride can be used to form an external structuring system as described in WO2011 / 031940, the content of which (especially regarding the manufacture of ESS) is incorporated herein by reference. In the case where ESS is present, it is preferred that the ESS of the present invention preferably comprises: (a) a crystallizable glyceride; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

[0192] The crystallizable glyceride 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 glycerides, especially triglycerides, which contain C10 to C22 alkyl or alkenyl moieties (which incorporate hydroxyl groups). Hydrogenation of the castor oil for preparing HCO can convert the double bonds present in the feed oil as ricinoleoyl moieties and convert the ricinoleoyl moieties to saturated hydroxyalkyl moieties, such as 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 HCO is generally present in the ESS of the present invention at a level of about 2% to about 10%, about 3% to about 8%, or about 4% to about 6% of the weight 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%.

[0193] Useful HCO may have the following properties: a melting point of about 40 °C to about 100 °C, or about 65 °C to about 95 °C; and / or an iodine value in the range of 0 to about 5, 0 to about 4, or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: differential scanning calorimetry. The HCO used in the present invention includes those commercially available. Non-limiting examples of commercially available HCO for use in the present invention include: THIXCIN(R) from Rheox, Inc. Other examples of useful HCO can be found in U.S. Patent 5,340,390. The castor oil source used for hydrogenation to form HCO can have any suitable origin, such as from Brazil or India. In a suitable embodiment, the 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.

[0194] The present invention is not intended to be limited solely to the use of hydrogenated castor oil. Any other suitable crystallizable glyceride can be used. In one example, the structurant is a triglyceride of substantially pure 12-hydroxy stearic acid. This molecule represents the pure form of the fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is rather stable, but it may vary slightly. Similarly, the hydrogenation process can vary. Any other suitable equivalent materials can be used, such as a mixture of triglycerides, where at least 80 wt% is derived from castor oil. Exemplary equivalent materials mainly contain triglycerides or consist essentially of triglycerides; or mainly contain a mixture of diglycerides and triglycerides or consist essentially of a mixture of diglycerides and triglycerides; or mainly contain a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20 wt% of the glyceride mixture) of monoglycerides or consist essentially of a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20 wt% of the glyceride mixture) of monoglycerides; or mainly contain any of the foregoing glycerides with a limited amount (e.g., less than about 20 wt%) of the corresponding acid hydrolysis products of any of the said glycerides or consist essentially of any of the foregoing glycerides with a limited amount (e.g., less than about 20 wt%) of the corresponding acid hydrolysis products of any of the said glycerides. The foregoing is provided that the major portion (usually at least 80 wt%) of any of the said glycerides is chemically identical to the glyceride of fully hydrogenated ricinoleic acid, i.e., the glyceride of 12-hydroxy stearic acid. For example, it is well known in the art to modify hydrogenated castor oil such that in a given triglyceride, there are two 12-hydroxy stearic acid moieties and one stearic acid moiety. Similarly, it is expected that hydrogenated castor oil may not be fully hydrogenated. Instead, when it does not meet the melting criteria, the present invention does not include poly(alkoxylated) castor oil.

[0195] The melting point of the crystallizable glycerol esters useful in the present invention can be from about 40 degrees Celsius to about 100 degrees Celsius.

[0196] Fatty acid

[0197] Preferably, the fatty acid is present in the composition at 1 to 6% by weight (measured relative to the acid added to the composition), more preferably 2 to 5% by weight.

[0198] In the context 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 from 6 to 24, more preferably from 10 to 22, and most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% by weight (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 tallow).

[0199] The fatty acid can be present in the form of its sodium, potassium or ammonium salts and / or in the form of soluble salts of organic bases such as mono-, di- or triethanolamine.

[0200] Mixtures of any of the above materials can also be used.

[0201] For the purposes of formulation description, in the formulation, the fatty acid and / or their salts (as defined above) are not included at surfactant levels or builder levels.

[0202] Chelating agent

[0203] Preferably, the detergent composition can also contain chelating materials. 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 , a chelating agent of the organic phosphonate type sold by Monsanto, and alkane hydroxyphosphonates.

[0204] A preferred chelating agent is Dequest(R) 2066 (diethylenetriamine penta(methylenephosphonic acid) or DTPMP heptasodium). Preferably, HEDP (1-hydroxyethylidene-1,1-diphosphonic acid) is absent.

[0205] In a preferred embodiment, the composition contains a fatty acid and a chelating agent.

[0206] The composition according to the invention is a low-water composition. Preferably, the composition comprises less than 15% by weight of water, more preferably less than 10% by weight of water.

[0207] Alkoxylated cationic or zwitterionic polyamine polymer

[0208] Preferably, the composition comprises an alkoxylated cationic or zwitterionic diamine or polyamine polymer, wherein a positive charge is provided by quaternization of the nitrogen atom of the amine, and an anionic group (if present) is provided by sulfation or sulfonation of the alkoxylated group.

[0209] Preferably, the alkoxylate is selected from propoxy and ethoxy, most preferably ethoxy.

[0210] Preferably, greater than or equal to 50 mol% of the nitrogen amines are quaternized, preferably quaternized with methyl. Preferably, the polymer contains 3 to 10, more preferably 3 to 6, most preferably 3 to 5 quaternized nitrogen amines. Preferably, the alkoxylate groups are selected from ethoxy and propoxy, most preferably ethoxy.

[0211] Preferably, the polymer contains ester (COO) or amide (CONH) groups within its structure, and 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 of less than 4000, preferably less than 2000, most preferably less than 1000.

[0212] Preferably, the polymer has the following form:

[0213]

[0214] wherein R1 is a C3 to C8 alkyl group, X is a (C2H4O)nY group, 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 - The number of groups is greater than the number of OH groups. Preferably, 0, 1 or 2 OH groups are present. X and R1 may contain 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, such that the structural unit is N-C2H4O-ester-(C2H4O) n-1 Y is preferred.

[0215] Such polymers are described in WO2021239547 (Unilever). Example polymers are sulfated ethoxylated hexamethylenediamine and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. Lactones or sodium chloroacetate (modified Williamson synthesis) can be used, added to OH or NH groups, and then subsequent ethoxylation to incorporate ester groups.

[0216] Exemplary reaction schemes for inclusion of ester groups are

[0217]

[0218] The addition of lactones is discussed in WO2021 / 165468.

[0219] Detergent polymer

[0220] Detergent polymers contribute to improved soil release from fabrics by modifying the fabric surface during washing. Adsorption of SRP on the fabric surface is facilitated by the affinity between the chemical structure of the SRP and the target fiber.

[0221] The SRP for use in the present invention may include a variety of charged (e.g., anionic) as well as uncharged monomer units, and the structure may be linear, branched, or star-shaped. The SRP structure may also include end-capping groups to control the molecular weight or to alter polymer properties such as surface activity. The weight-average molecular weight (M w ) of the SRP may suitably range from about 1000 to about 20,000, preferably from about 1500 to about 10,000.

[0222] The SRP for use in the present invention may 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 may also include monomer units substituted with anionic groups, such as 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-anion-capped low polyesters, such as oligomers from ethylene glycol (“EG”), PG, DMT, and Na-3,6-dioxaoctane-8-sulfonic acid; non-ionic-capped block polyester oligomeric compounds, such as those produced by combinations of DMT, Me-capped PEG, and EG and / or PG, or DMT, EG and / or PG, Me-capped PEG, and Na-dimethyl-5-sulfoisophthalic acid, and copolymers of ethylene terephthalate or propylene terephthalate with polyethylene terephthalate or polypropylene terephthalate.

[0223] 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 esters), for example 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.

[0224] 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 capping with repeating units of alkylene oxides capped with alkyl groups. An example of such a material has a structure corresponding to the general formula (I):

[0225]

[0226] wherein R 1 and R 2 are independently of each other X-(OC2H4) n -(OC3H6) m ;

[0227] wherein X is a C 1-4 alkyl and preferably methyl;

[0228] n is a number from 12 to 120, preferably from 40 to 50;

[0229] m is a number from 1 to 10, preferably from 1 to 7; and

[0230] a is a number from 4 to 9.

[0231] Since it is an average value, m, n, and a are not necessarily integers for the overall polymer.

[0232] Mixtures of any of the above materials may also be used.

[0233] The total content of SRP (when included) can range from 0.1 to 10 wt%, depending on the content of the polymer intended for use in the final dilution composition, and it is desirably from 0.3 to 7 wt%, more preferably from 0.5 to 5 wt% (by weight based on the total weight of the dilution composition).

[0234] 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 polymers are generally incorporated into the liquid laundry detergent compositions herein at a concentration ranging from 0.01% to 10% by weight of the composition, more preferably from 0.1% to 5% by weight.

[0235] Non-aqueous solvent

[0236] The detergent compositions of the present invention can incorporate such non-aqueous carriers, also known as hydrotropes or phase stabilizers. Such materials are generally 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 ) ranging from about 200 to 600; C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkyl aryl sulfonates having at most 3 carbon atoms in the lower alkyl group (e.g., sodium and potassium xylene, toluene, ethylbenzene and isopropylbenzene (cumene) sulfonates).

[0237] Mixtures of any of the above materials can also be used.

[0238] The amount of the non-aqueous solvent preferably included can range from 1 to 50%, preferably from 10 to 30%, and more preferably from 15 to 25% (by weight based on the total weight of the composition). The level of the hydrotrope used is associated with the level of the surfactant, and it is desirable to use the hydrotrope level to control the viscosity of these compositions. Preferred hydrotropes are monopropylene glycol and glycerol.

[0239] Cosurfactant

[0240] In addition to the non-soap anionic and / or nonionic soil release surfactants described above, the compositions of the present invention can contain one or more co-surfactants (such as amphoteric (zwitterionic) and / or cationic surfactants).

[0241] Specific cationic surfactants include C8-C18 alkyldimethyl ammonium halides and their derivatives, in which one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof. When a cationic surfactant is included, its amount can range from 0.1 - 5% (by weight based on the total weight of the composition).

[0242] Specific zwitterionic surfactants include alkyldimethylamine oxides, alkylbetaines, alkylamidopropylbetaines, alkylsulfobetaines (sulfobetaines), alkylglycinates, alkylcarboxyglycinates, alkylamphoacetates, alkylamphopropionates, alkylamphoglycinates, alkylamidopropylhydroxysulfobetaines, acyltaurates, and acylglutamates, which have an alkyl group containing from 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 portion of the higher acyl groups. When zwitterionic surfactants are included, their amount may be in the range of 0.1 - 5% (by weight based on the total weight of the composition).

[0243] Mixtures of any of the above materials may also be used.

[0244] Fluorescent agent

[0245] It may be advantageous to include fluorescent agents in the composition. Generally, these fluorescent agents are provided and used in the form of their alkali metal salts (e.g., sodium salts). The total amount of one or more fluorescent agents used in the composition is typically from 0.005 to 2% by weight of the composition, more preferably from 0.01 to 0.5% by weight.

[0246] Preferred classes of fluorescent agents are: stilbenylbiphenyl compounds, such as CBS-X, diamine stilbene disulfonic acid compounds, such as Tinopal DMS pure Xtra, Tinopal 5BMGX, and HRH, and pyrazoline compounds, such as Blankophor SN.

[0247] Preferred fluorescent agents are: sodium 2(4-styryl-3-sulfophenyl)-2H-naphtho[1,2-d]triazole, disodium 4,4'-bis{[(4-anilino-6-(N-methyl-N-2-hydroxyethyl)amino-1,3,5-triazin-2-yl)]amino}stilbene-2,2'-disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1,3,5-triazin-2-yl)]amino}stilbene-2,2'-disulfonate, and disodium 4,4'-bis(2-sulfostyryl)biphenyl.

[0248] Most preferably, the fluorescent agent is a stilbenylbiphenyl compound, preferably sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzene sulfonate (CAS-No 27344-41-8).

[0249] Color-toning dye

[0250] The color - correcting dyes can be used to improve the properties of the composition. Preferred dyes are purple or blue. It is believed that depositing low levels of dyes of these hues on the fabric masks the yellowing of the fabric. A further advantage of the color - correcting dyes is that they can be used to mask any yellow hues in the composition itself.

[0251] Color - correcting dyes are known in the field of liquid laundry detergent formulations.

[0252] Suitable and preferred classes of dyes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes, and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bound to ethoxylated or propoxylated polyethyleneimine as described in WO2011 / 047987 and WO2012 / 119859, alkoxylated mono - azo thiophenes, dyes with CAS - No 72749 - 80 - 5, Acid Blue 59, and phenazine dyes selected from:

[0253]

[0254] wherein:

[0255] X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and -OC2H5;

[0256] X4 is selected from: -H; -CH3; -C2H5; -OCH3; and -OC2H5;

[0257] Y2 is selected from: -OH; -OCH2CH2OH; -CH(OH)CH2OH; -OC(O)CH3; and C(O)OCH3.

[0258] Alkoxylated thiophene dyes are described in WO2013 / 142495 and WO2008 / 087497.

[0259] The color - correcting dyes are preferably present in the composition in the range of 0.0001 - 0.1% by weight. Depending on the nature of the color - correcting dye, there is a preferred range that depends on the efficacy of the color - correcting dye, and the efficacy of the color - correcting dye depends on the class and the specific efficacy within any particular class.

[0260] External structuring agent

[0261] 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, micro - fibrillar cellulose, and citrus pulp fiber. The presence of the external structuring agent can provide shear - thinning rheology and can also stably suspend materials such as encapsulates and visual cues in the liquid.

[0262] The composition preferably comprises a crystallizable glyceride.

[0263] The crystallizable glyceride can be used to form an external structuring system, as described in WO2011 / 031940, the content of which (particularly regarding the manufacture of ESS) is incorporated by reference. In the presence of an ESS, it is preferred that the ESS of the present invention preferably comprises: (a) a crystallizable glyceride; (b) an alkanolamine; (c) an anionic surfactant; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

[0264] The crystallizable glyceride used herein preferably includes "hydrogenated castor oil" or "HCO". As used herein, HCO can most commonly be any hydrogenated castor oil, provided that it can crystallize in the ESS premix. Castor oil can include glycerides, particularly triglycerides, which contain C10 to C22 alkyl or alkenyl moieties incorporating hydroxyl groups. The hydrogenation of the castor oil used to prepare HCO converts the double bonds (which may be present in the alkenyl moiety of the starting oil such as castor oil) to convert the alkenyl moiety to a saturated hydroxyalkyl moiety, for example, 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 amount of HCO present in the ESS of the present invention is typically about 2% to about 10%, about 3% to about 8% or about 4% to about 6% by weight 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%.

[0265] Useful HCO can have the following characteristics: a melting point of about 40°C to about 100°C, or about 65°C to about 95°C; and / or an iodine value range of 0 to about 5, 0 to about 4 or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests use DSC: differential scanning calorimetry. The HCO used in the present invention includes those 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 5,340,390. The source of castor oil used for hydrogenation to form HCO can be any suitable source, such as from Brazil or India. In a suitable embodiment, the castor oil is hydrogenated using a noble metal, such as a palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds in the original castor oil while avoiding unacceptable levels of dehydroxylation.

[0266] The present invention is not intended to relate only to the use of hydrogenated castor oil. Any other suitable crystallizable glycerides can be used. In one example, the structuring agent is a triglyceride of substantially pure 12-hydroxy stearic acid. This molecule represents the pure form of the fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid. In nature, the composition of castor oil is rather stable, but there can also be some variations. Similarly, the hydrogenation process can vary. Any other suitable equivalent materials can also be used, such as a mixture of triglycerides where at least 80% by weight is derived from castor oil. Exemplary equivalent materials mainly comprise triglycerides or consist essentially of them; or mainly comprise a mixture of diglycerides and triglycerides or consist essentially of them; or mainly comprise a mixture of triglycerides with diglycerides and a limited amount (e.g., less than about 20% by weight of the glyceride mixture) of monoglycerides or consist essentially of them; or mainly comprise any of the above glycerides with a limited amount (e.g., less than about 20% by weight) of the corresponding acid hydrolysis products of any of the said glycerides or consist essentially of them. The prerequisite in the above is that the major proportion (usually at least 80% by weight) of any of the said glycerides is chemically identical to the glyceride of fully hydrogenated ricinoleic acid (i.e., the glyceride of 12-hydroxy stearic acid). For example, it is well known in the art to modify hydrogenated castor oil such that in a given triglyceride, there are two 12-hydroxy stearic acid moieties and one stearic acid moiety. Similarly, it is contemplated that hydrogenated castor oil may not be fully hydrogenated. On the contrary, if poly(oxyalkylated) castor oil does not meet the melting criteria, the present invention excludes it.

[0267] The crystallizable glycerides used in the present invention can have a melting point of about 40 °C to about 100 °C.

[0268] Enzyme

[0269] The composition preferably comprises an enzyme selected from the group consisting of cellulase, protease, and an amylase / mannanase mixture.

[0270] In addition, other enzymes may also be present, such as those described below.

[0271] Preferably, the composition may comprise an effective amount of one or more enzymes, preferably selected from the group consisting of lipase, hemicellulase, peroxidase, hemicellulase, xylanase, xanthanase, lipase, phospholipase, esterase, cutinase, pectinase, carrageenase, pectate lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanases, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, tannase, nuclease (such as deoxyribonuclease and / or ribonuclease), phosphodiesterase, or a mixture thereof.

[0272] Preferably, the enzyme content is from 0.1 to 100, more preferably from 0.5 to 50, and most preferably from 5 to 30 mg of active enzyme protein per 100 g of the finished laundry liquid composition.

[0273] Preferred examples of enzymes are sold under the following trade names: Purafect (DuPont), Stainzyme (Novozymes), Biotouch (AB Enzymes), (BASF).

[0274] Detergent enzymes are described in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF) and WO2020 / 259949 (Unilever).

[0275] A nuclease is an enzyme capable of cleaving the phosphodiester bonds between the nucleotide subunits of a nucleic acid, and is preferably a deoxyribonuclease or a ribonuclease. Preferably, the nuclease is a deoxyribonuclease, preferably selected from the group consisting 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, and any one of the species of E.C. 3.1.31.1, and mixtures thereof.

[0276] Proteases hydrolyze the bonds in peptides and proteins, which results in enhanced removal of protein- or peptide-containing stains during the laundry process. Examples of suitable protease families include aspartic proteases, cysteine proteases, glutamic proteases; asparaginyl peptide lyases, 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.

[0277] Examples of subtilisins are those derived from: Bacillus spp., such as Bacillus lentus, Bacillus alkalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii, as described in US 7262042 and WO 09 / 021867, and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147, and subtilisin 168 described in WO 89 / 06279 and protease PD138 described in (WO 93 / 18140). Other useful proteases can be those described in WO 92 / 175177, WO01 / 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 (described in WO 89 / 06270, WO 94 / 25583, and WO 05 / 040372) and chymotrypsin derived from Cellulomonas (described in WO05 / 052161 and WO 05 / 052146).

[0278] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0279] Examples of subtilisins are those derived from Bacillus species such as Bacillus lentus, Bacillus alcalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii (described in US7262042 and WO09 / 021867), and subtilisin lentus, subtilisin Novo, subtilisin Carlsberg, Bacillus licheniformis, subtilisin BPN', subtilisin 309, subtilisin 147, and subtilisin 168 (described in WO89 / 06279) and protease PD138 (described in WO93 / 18140). Preferably, the subtilisin is derived from Bacillus species, preferably Bacillus lentus, Bacillus alcalophilus, Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus pumilus, and Bacillus gibsonii (as described in US 6,312,936 B1, US5,679,630, US 4,760,025, US7,262,042, and WO 09 / 021867). Most preferably, the subtilisin is derived from Bacillus gibsonii or Bacillus lentus.

[0280] Suitable commercially available proteases include those sold under the following trade names: DuralaseTm, DurazymTm, Ultra, Ultra, Ultra, Ultra, and all available as or (Novozymes A / S).

[0281] Suitable amylases (α and / or β) include those of bacterial or fungal origin. This includes chemically modified or protein engineered mutants. Amylases include, for example, α-amylases obtained from Bacillus species such as specific strains of Bacillus licheniformis (more particularly described in GB 1,296,839), or Bacillus 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 TM and BANTM (Novozymes A / S), Rapidase TM and Purastar TM (from Genencor International Inc.).

[0282] Suitable cellulases include those of bacterial or fungal origin. This includes chemically modified or protein engineered mutants. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, such as fungal cellulases produced by Humicola insolens, Thielavia terrestris, Myceliophthora thermophila, and Fusarium oxysporum (disclosed in US 4,435,307, US 5,648,263, US 5,691,178, US 5,776,757, WO 89 / 09259, 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.

[0283] Lipase

[0284] The lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously herein.

[0285] The composition preferably contains 0.0005 to 0.5% by weight, preferably 0.005 to 0.2% by weight of lipase.

[0286] 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).

[0287] The lipid esterase can be selected from lipases of E.C. class 3.1 or 3.2 or a combination thereof.

[0288] Preferably, the cleaning lipase is selected from:

[0289] (1) Triacylglycerol lipase (E.C. 3.1.1.3)

[0290] (2) Carboxylic ester hydrolase (E.C. 3.1.1.1)

[0291] (3) Cutinase (E.C. 3.1.1.74)

[0292] (4) Sterol esterase (E.C. 3.1.1.13)

[0293] (5) Wax-ester hydrolase (E.C. 3.1.1.50)

[0294] Triacylglycerol lipase (E.C. 3.1.1.3) is most preferred.

[0295] Suitable triacylglycerol lipases may be selected from variants of the lipase of Humicola lanuginosa (Thermomyces lanuginosus). Other suitable triacylglycerol lipases may be selected from variants of Pseudomonas lipases, such as from Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes (EP 218 272), Pseudomonas cepacia (EP 331376), Pseudomonas stutzeri (GB 1,372,034), Pseudomonas fluorescens, Pseudomonas strain SD705 (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).

[0296] 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.

[0297] 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.

[0298] In a preferred embodiment, the cutinase is selected from variants of Pseudomonas mendocina cutinase, described in WO2003 / 076580 (Genencor), such as the variant having three substitutions at I178M, F180V, and S205G.

[0299] In another preferred embodiment, the cutinase is the wild-type or a variant of six cutinases endogenous to Coprinus cinereus, described by H. Kontkanen et al., App. Environ. Microbiology, 2009, pp. 2148-2157.

[0300] In another preferred embodiment, the cutinase is the wild type or a variant of two cutinases endogenous to Trichoderma reesei as described in WO2009007510 (VTT).

[0301] In a most preferred embodiment, the cutinase is derived from a strain of Humicola insolens, in particular Humicola insolens strain DSM 1800. The Humicola insolens cutinase is described in WO96 / 13580, which is incorporated herein by reference. The cutinase can be a variant, such as one of the variants disclosed in WO00 / 34450 and WO01 / 92502. Preferred cutinase variants include those listed in Example 2 of WO01 / 92502. A preferred commercial cutinase is Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0302] Suitable sterol esterases can be derived from Ophiostoma, such as a strain of Ophiostoma piceae; Pseudomonas, such as a strain of Pseudomonas aeruginosa; or Melanocarpus, such as a strain of Melanocarpus albomyces.

[0303] 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.

[0304] Suitable wax-ester hydrolases can be derived from Simmondsia chinensis.

[0305] The lipid esterase is preferably selected from lipases of E.C. class 3.1.1.1 or 3.1.1.3 or a combination thereof, most preferably E.C. 3.1.1.3.

[0306] Examples of EC 3.1.1.3 lipases include those described in WIPO publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079 and US 5,869,438. Preferred lipases are from 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 (a 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 a 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).

[0307] The above lipases can be used in combination (any mixture of lipases can be used). Suitable lipases are commercially available from Novozymes, Bagsvaerd, Denmark; Areario Pharmaceutical Co., Ltd., Nagoya, Japan; ToyoJozo Co., Tagata, Japan; Amersham Pharmacia Biotech., Piscataway, New Jersey, U.S.A.; Diosynth Co., Oss, Netherlands, and / or can be prepared according to the examples included herein.

[0308] Lipid esterases with reduced potential for odor generation and good relative performance are particularly preferred, as described in WO 2007 / 087243. These include (Novozyme).

[0309] Preferred commercially available lipase enzymes include Lipolase TM and Lipolase Ultra TM , Lipex TM and LipocleanTM (Novozymes A / S).

[0310] Fragrance

[0311] The composition contains an aroma agent, and preferably the aroma agent is present in the composition in an amount of 0.01 to 5% by weight, more preferably 0.1 to 1% by weight.

[0312] Preferably, the fragrance contains components selected from the following: ethyl-2-methylvalerate (chrysanthemum ester), limonene, (4Z)-cyclopentadec-4-en-1-one, dihydromyrcenol, dimethylbenzyl carboacetate, 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, decanal, octanal, undecanal, tricyclodecenyl acetate, tert-butylcyclohexyl acetate, cyclamen aldehyde, β-ionone, hexyl salicylate, tonalide, [2-(cyclohexyloxy)ethyl]benzene (phenafleur), octahydrotetramethylacetophenone (OTNE), benzene, toluene, xylene (BTX) raw materials such as 2-phenylethanol, phenoxanol and mixtures thereof, cyclododecanone raw materials such as habolonolide, phenolic raw materials such as hexyl salicylate, C5 module or oxygen-containing heterocyclic moiety raw materials such as γ-decalactone, methyl dihydrojasmonate and mixtures thereof, terpene raw materials such as dihydromyrcenol, linalool, terpinolene, camphor, citronellol and mixtures thereof, alkyl alcohol raw materials such as ethyl-2-methylbutyrate, diacid raw materials such as ethylene glycol brassylate, and mixtures of these components.

[0313] 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 component ethyl-2-methylvalerate (chrysanthemum ester).

[0314] 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 component limonene.

[0315] 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 component (4Z)-cyclopentadec-4-en-1-one.

[0316] 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 component dimethylbenzyl carboacetate.

[0317] 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 component dihydromyrcenol.

[0318] 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 component rose oxide.

[0319] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component tert-butylcyclohexyl acetate.

[0320] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component tricyclodecenyl acetate.

[0321] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component benzyl acetate.

[0322] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component spiro[1,3-dioxolane-2,5'-(4',4',8',8'-tetramethyl-hexahydro-3',9'-methylenenaphthalene)].

[0323] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component geraniol.

[0324] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component methyl nonyl acetaldehyde.

[0325] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component cyclamen aldehyde.

[0326] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component β-ionone.

[0327] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component hexyl salicylate.

[0328] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component tonalide.

[0329] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and particularly preferably from 6 to 10% by weight of the fragrance component [2-(cyclohexyloxy)ethyl]benzene.

[0330] Preferably, the fragrance comprises components selected from benzene, toluene, xylene (BTX) raw material classes. More preferably, the fragrance components are selected from 2-phenylethanol, benzo amyl alcohol, and mixtures thereof.

[0331] Preferably, the fragrance comprises components selected from cyclododecanone raw material classes. More preferably, the fragrance component is habolonolide.

[0332] Preferably, the fragrance comprises components selected from phenolic raw material classes. More preferably, the fragrance component is the ingredient of hexyl salicylate.

[0333] Preferably, the fragrance comprises components selected from C5 modules or oxygen-containing heterocyclic moiety raw material classes. More preferably, the fragrance components are selected from γ-decalactone, methyl dihydrojasmonate, and mixtures thereof.

[0334] Preferably, the fragrance comprises components selected from terpene raw material classes. More preferably, the fragrance components are selected from linalool, terpinolene, camphor, citronellol, and mixtures thereof.

[0335] Preferably, the fragrance comprises components selected from alkyl alcohol raw material classes. More preferably, the fragrance component is ethyl-2-methylbutyrate.

[0336] Preferably, the fragrance comprises components selected from diacid raw material classes. More preferably, the fragrance component is ethylene glycol brazileinate.

[0337] Preferably, the above-listed fragrance components are present in the final detergent composition in an amount of 0.0001 to 1% by weight of the composition.

[0338] Microcapsule

[0339] One type of particle suitable for the present invention is a microcapsule. Microencapsulation can be defined as the process of surrounding or encapsulating a substance within another substance on a very small scale, resulting in capsules with sizes in the range of less than 1 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.

[0340] Microcapsules typically have at least one continuous, generally spherical shell surrounding 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 droplets of core material embedded throughout the microcapsule.

[0341] 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 fragrance release can be initiated in response to the microcapsule being exposed to a humid environment. Similarly, if the shell is temperature-sensitive, the microcapsule may release the fragrance in response to an elevated temperature. The microcapsule can also release the fragrance in response to a shear force applied to the surface of the microcapsule.

[0342] A preferred type of polymer microparticle suitable for the present invention is a polymer core-shell microcapsule in which at least one generally spherical continuous shell of polymer material surrounds a core containing a fragrance formulation (f2). Based on the total weight of the microcapsule, the shell generally accounts for at most 20% by weight. The fragrance formulation (f2) generally accounts for about 10 - about 60% by weight, preferably about 20 - about 40% by weight, based on the total weight of the microcapsule. The amount of the fragrance (f2) can be determined by obtaining a slurry of the microcapsules, extracting into ethanol, and measuring by liquid chromatography.

[0343] The polymer core-shell microcapsules for the present invention can be prepared using methods known to those skilled in the art, such as coacervation, interfacial polymerization, and polycondensation.

[0344] The coacervation method generally involves encapsulating a generally water-insoluble core material by precipitating a colloidal material onto the surface of the material droplets. Coacervation can be simple, for example, using a single colloid such as gelatin, or complex, where two or possibly more oppositely charged colloids such as gelatin and gum arabic or gelatin and carboxymethyl cellulose are used under carefully controlled conditions of pH, temperature, and concentration.

[0345] Interfacial polymerization is generally carried out by forming a fine dispersion of oil droplets (oil droplets containing the core material) in an aqueous continuous phase. The dispersed droplets form the core of the future microcapsules, and the size of the dispersed droplets directly determines the size of the subsequent microcapsules. The microcapsule shell-forming materials (monomers or oligomers) are contained in both the dispersed phase (oil droplets) and the aqueous continuous phase, and they react together at the phase interface to build a polymer wall around the oil droplets, thereby encapsulating the droplets and forming core-shell microcapsules. An example of a core-shell microcapsule produced by this method is a polyurea microcapsule having a shell formed by the reaction of a diisocyanate or polyisocyanate with a diamine or polyamine.

[0346] Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of a precondensate of the polymeric material under suitable stirring conditions to produce capsules of the desired size, and adjusting the reaction conditions to cause condensation of the precondensate by acid catalysis, resulting in separation of the condensate from the solution and deposition around the dispersed core material to produce a coacervate film and the desired microcapsules. Examples of core-shell microcapsules produced by this method are aminoplast microcapsules having a shell formed from the polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde. Suitable crosslinking agents (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) can also be used, and, where appropriate, secondary wall polymers such as acid anhydrides and their derivatives, especially polymers and copolymers of maleic anhydride, can also be used.

[0347] An example of a preferred polymeric core-shell microcapsule for use in the present invention is an aminoplast microcapsule in which the aminoplast shell surrounds a core containing an aroma formulation (f2). More preferably, such an aminoplast shell is formed from the polycondensation product of melamine with formaldehyde.

[0348] Polymeric microparticles suitable for use in the present invention typically have an average particle size in the range of 100 nanometers to 50 micrometers. Particles larger than this size range enter the visible range. Examples of particles in the sub-micron range include latexes and microemulsions having a typical size range of 100 - 600 nanometers. A preferred particle size range is in the micron range. Examples of particles in the micron range include polymeric core-shell microcapsules (such as those further described above) having a typical size range of 1 to 50 micrometers, preferably 5 to 30 micrometers. The average particle size can be determined by light scattering using a Malvern Mastersizer, where the average particle size is taken as the median particle size D(0.5) value. The particle size distribution can be narrow, wide, or multimodal. If desired, the initially produced microcapsules can be filtered or screened to produce a product with greater size uniformity.

[0349] Polymeric microparticles suitable for use in the present invention can have a deposition aid at the outer surface of the microparticle. The deposition aid is used to modify the properties of the exterior of the microparticle, such as making the microparticle more affinity for a desired substrate. Desired substrates include cellulosics (including cotton) and polyesters (including those used in the manufacture of polyester fabrics).

[0350] The deposition aid can be suitably provided at the outer surface of the microparticle by covalent bonding, entanglement, or strong adsorption. Examples include polymeric core-shell microcapsules (such as those further described above), where the deposition aid is preferably attached to the exterior of the shell by covalent bonding. While it is preferred that the deposition aid is directly attached to the exterior of the shell, it can also be attached via a linking substance.

[0351] The deposition aids for use in the present invention may suitably be selected from polysaccharides having an affinity for cellulose. Such polysaccharides may be naturally occurring or synthetic and may have an intrinsic affinity for cellulose or may be derivatized or otherwise modified to have an affinity for cellulose. Suitable polysaccharides have a 1-4 linked β-glycan (broad sense sugar) backbone structure having at least 4, preferably at least 10 β1-4 linked backbone residues, such as a glucan backbone (composed of β1-4 linked glucose residues), a mannan backbone (composed of β1-4 linked mannose residues) or a xylan backbone (composed of β1-4 linked xylose residues). Examples of such β1-4 linked polysaccharides include xyloglucan, glucomannan, mannan, galactomannan, β(1-3),β(1-4) glucan and xylan families containing glucuronyl-, arabinose- and glucuronoarabinoxylan. Preferred β1-4 linked polysaccharides for use in the present invention may be selected from xyloglucans of plant origin, such as pea xyloglucan and tamarind xyloglucan (TXG) (which has a β1-4 linked glucan backbone with side chains of α-D-xylopyranose and β-D-galactopyranosyl-(1-2)-α-D-xylopyranose, both 1-6 linked to the backbone); and galactomannans of plant origin, such as locust bean gum (LBG) (which has a mannan backbone of β1-4 linked mannose residues, where single unit galactose side chains are α1-6 linked to the backbone).

[0352] Also suitable are polysaccharides that can acquire an affinity for cellulose upon hydrolysis, such as cellulose monoacetate; or modified polysaccharides having an affinity for cellulose, such as hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl guar gum, hydroxyethyl ethyl cellulose and methyl cellulose.

[0353] The deposition aids for use in the present invention may also be selected from phthalate-containing polymers having an affinity for polyester. Such phthalate-containing polymers may have one or more non-ionic hydrophilic segments containing oxyalkylene groups (such as oxyethylene, polyoxyethylene, oxypropylene or polyoxypropylene groups), and one or more hydrophobic segments containing terephthalate groups. Generally, the degree of polymerization of the oxyalkylene groups is from 1 to about 400, preferably from 100 to about 350, more preferably from 200 to about 300. Suitable examples of this type of phthalate-containing polymer are copolymers having random blocks of ethylene glycol terephthalate and polyethylene oxide terephthalate.

[0354] Mixtures of any of the above materials may also be suitable.

[0355] The weight average molecular weight (M w)Typically in the range of about 5 kDa to about 500 kDa, preferably about 10 kDa to about 500 kDa, more preferably about 20 kDa to about 300 kDa.

[0356] An example of a particularly preferred polymer core - shell microcapsule for use in the present invention is an aminoplast microcapsule having a shell formed by the polycondensation of melamine and formaldehyde; which surrounds a core containing an aroma formulation (f2); wherein the deposition aid is attached to the exterior of the shell by covalent bonding. Preferred deposition aids are selected from β1 - 4 linked polysaccharides and in particular xyloglucan of plant origin as further described above.

[0357] The inventors have surprisingly observed that it is possible to reduce the total content of the aroma contained in the compositions of the present invention without sacrificing the overall aroma experience provided to the consumer at the critical stages of the laundry process. Reducing the total content of the aroma is advantageous for cost and environmental reasons.

[0358] Accordingly, the total amount of aroma formulation (f1) and aroma formulation (f2) in the compositions of the present invention is suitably in the range of 0.5 - 1.4%, preferably 0.5 - 1.2%, more preferably 0.5 - 1%, most preferably 0.6 - 0.9% (by weight based on the total weight of the composition).

[0359] The weight ratio range of aroma formulation (f1) to aroma formulation (f2) in the compositions of the present invention is preferably from 60:40 to 45:55. Particularly good results are obtained when the weight ratio of aroma formulation (f1) to aroma formulation (f2) is about 50:50.

[0360] Aroma (f1) and aroma (f2) are typically incorporated at different stages of the formation of the compositions of the present invention. Typically, discrete polymer microparticles (such as microcapsules) encapsulating aroma formulation (f2) are added in the form of a slurry to a warm base formulation containing the other components of the composition (such as surfactants and solvents). Subsequently, aroma (f1) is typically post - added after the base formulation has cooled.

[0361] Further optional ingredients

[0362] The compositions of the present invention may comprise further optional ingredients to enhance performance and / or consumer acceptability. Examples of such ingredients include foam boosters, preservatives (such as bactericides), polyelectrolytes, anti - shrinkage agents, anti - wrinkle agents, antioxidants, sunscreens, anti - corrosion agents, drape - imparting agents, antistatic agents, ironing aids, colorants, pearlescents and / or opacifiers, as well as color - correcting dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Typically, these optional ingredients are individually included in amounts 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.

[0363] Many of the ingredients used in the embodiments of the present invention can be obtained from so-called black carbon sources or more sustainable green sources. A list of alternative sources for several of these ingredients and how they can be made into the starting materials described herein is provided below.

[0364] Preferably, the unit dose detergent is packaged in a container such as a plastic pail. Such plastic pails are typically hermetically sealable and include child-resistant closures.

[0365] More preferably, the liquid unit dose detergent is packaged in a container comprising at least 80 wt% of a biodegradable material. Suitable biodegradable materials include cardboard and other pulp-based materials. Such biodegradable materials can be virgin or recycled materials, but preferably they are recycled.

[0366] Preferably, the container comprises at least 90 wt% of a biodegradable material.

[0367] Preferred pulps include cardboard, especially corrugated cardboard. Examples

[0368] The following are unit dose formulations.

[0369]

[0370] Formulations A and B cannot be concentrated to form a detergent product containing less than 15 g because they are unstable. Compositions C and D are stable at low dose levels but do not contain enough detergent to effectively clean in a challenge load.

[0371] Composition 1 is stable at lower doses but can still clean a soiled load.

Claims

1. A unit dose product comprising from 8 to 15 g of a detergent composition contained within a sachet formed from a water-soluble film, said composition comprising water and a non-aqueous solvent and a surfactant, wherein said detergent composition comprises from 5 to 8 g of surfactant and wherein the weight ratio of total surfactant to total water and non-aqueous solvent is at least 1.

6.

2. The product according to claim 1, wherein said surfactant comprises linear alkylbenzene sulfonate and a non-ionic surfactant.

3. The product according to any one of the preceding claims, wherein said composition comprises from 5 to 10% by weight of water of the composition.

4. The product according to any one of the preceding claims, wherein said composition comprises an alkyl ether sulfate.

5. The product according to claim 5, wherein the alkyl ether sulfate comprised by said composition is MIPA LES.

6. The product according to any one of the preceding claims, wherein said composition comprises less than 5% by weight of fatty acids.

7. The product according to any one of the preceding claims, which comprises one, two or three chambers, each chamber containing a detergent composition.

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