Composition

Abstract

A liquid unit dose composition comprising from 5% to 15% water and a dye wherein the composition is contained within a capsule comprising a water-soluble film wherein the film comprises a maleic acid modified polyvinyl alcohol and wherein the absorbance of the total dye in the washing liquid of the capsule in the range of from 400 to 700 nm measured at 1 cm is less than 1.

Description

[0001] The present invention relates to an improved liquid laundry composition.

[0002] WO 2016 / 061053 (Procter and Gamble) discloses an article comprising a water-soluble film and a home care composition, wherein the film comprises a polyvinyl alcohol (PVOH) resin blend and optionally one or more additional components such as plasticizers, fillers, surfactants, and other additives. The PVOH resin blend comprises: a PVOH copolymer (such as a PVOH terpolymer) comprising one or more types of anionic monomer units and a PVOH polymer (such as another PVOH anionic copolymer, or a partially or fully hydrolyzed PVOH homopolymer). When the PVOH copolymer and the PVOH polymer are blended in a specific ratio and / or selected according to various criteria related to physical and chemical film properties, the resulting water-soluble film formed from the PVOH resin blend exhibits significantly improved water solubility performance, tensile strength performance, and tensile modulus performance.

[0003] US 2016 / 280869 (Monosol LLC) discloses a water-soluble film comprising a polyvinyl alcohol copolymer resin, a plasticizer, an anti-caking filler, and a release regulator. Also disclosed are related packages comprising the film, and related methods of making and using the film and the packages.

[0004] Despite the prior art, there is a need for improved unit-dose laundry compositions.

[0005] Accordingly, in a first aspect, there is provided a liquid unit-dose composition comprising 5 to 15% water and a dye, wherein the composition is contained within a water-soluble film capsule, wherein the film comprises maleic acid-modified polyvinyl alcohol, and wherein the total dye in the capsule wash liquor has an absorbance at 1 cm in the range of 400 to 700 nm of less than 1.

[0006] We have surprisingly found that a water-soluble film having maleic acid-modified polyvinyl alcohol and a low level of dye is aesthetically more appealing. In particular, it exhibits a more glossy appearance.

[0007] Preferably, the maleic acid modification comprises copolymerization with PVA.

[0008] Water-soluble film composition

[0009] The liquid unit-dose composition is preferably contained within a water-soluble capsule.

[0010] Preferably, the capsule has one to four compartments. Preferably, the capsule is a unit-dose product and can be 10 to 50 g in weight to represent a unit dose.

[0011] Water-soluble film compositions, optional ingredients used in the present invention, 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 for other uses.

[0012] PVA is a synthetic resin generally prepared by the alcoholysis (commonly referred to as hydrolysis or saponification) of polyvinyl acetate. Fully hydrolyzed PVA in which almost all of the acetate groups are converted to alcohol groups is a highly crystalline polymer with strong hydrogen bonding, and it dissolves only in hot water at temperatures greater than about 140°F (about 60°C). If a sufficient number of acetate groups are allowed to remain after the hydrolysis of polyvinyl acetate, the PVA polymer is called partially hydrolyzed, which is weakly hydrogen-bonded and less crystalline, and is generally soluble in cold water at temperatures below about 10°C. Intermediate cold- or hot-water-soluble films can include, for example, intermediate partially hydrolyzed PVA (e.g., having a degree of hydrolysis of about 94% to about 98%), and are soluble only in warm water, e.g., dissolving rapidly at about 40°C and higher temperatures. The fully and partially hydrolyzed types of PVA are generally referred to as PVA homopolymers, although the partially hydrolyzed type is technically an ethylene alcohol-vinyl acetate copolymer.

[0013] Other water-soluble polymers used in addition to PVA polymers and PVA copolymers 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 combinations of any of the foregoing polymers. Still other water-soluble polymers can 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.

[0014] Any of the above 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.

[0015] For example, the weight ratio of the amount of all water-soluble polymers to the combined amount of all plasticizers, compatibilizers, and minor additives can be in the range of 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. In certain embodiments, the specific amounts of plasticizers and other non-polymer components can be selected based on the intended application of the water-soluble film to adjust the flexibility of the film and impart processing benefits according to the desired mechanical film properties.

[0016] It is well known in the art that the viscosity of a water-soluble polymer (PVA or otherwise) is related to the weight-average molecular weight (Mw) of the same polymer, and generally viscosity is used as a proxy for Mw. Thus, for example, the weight-average molecular weight of a water-soluble polymer (including the first PVA copolymer and the second PVA polymer) can be in the range of 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.

[0017] 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, cross-linking 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, or others), aversion agents such as bittering agents (e.g., denatonium salts such as denatonium benzoate, denatonium saccharin, 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) and other functional ingredients, in amounts suitable for their intended use. Embodiments including plasticizers are preferred. The amounts of such reagents, individually or in combination, can be 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%.

[0018] 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 with up to 400 MW, neopentyl glycol, trimethylolpropane, polyether polyol, sorbitan, 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. The total amount of plasticizer can range from about 10 wt% to about 40 wt%, or about 15 wt% to about 35 wt%, or about 20 wt% to about 30 wt% based on the total film weight, such as 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%.

[0019] 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 content, the film may become brittle, difficult to process, or prone to cracking. At high plasticizer content, the film may be too soft, weak, or difficult to process for the desired use.

[0020] In a preferred embodiment, the composition contains a taste aversion agent such as denatonium benzoate and / or a pungent agent such as capsaicin.

[0021] Maleic acid-modified polyvinyl alcohol is well known in the art and is commercially available from many water-soluble film manufacturers.

[0022] Preferably, maleic acid-modified PVA accounts for 10 to 70 wt% of the water-soluble film, and more preferably 30 to 60 wt%. Maleic acid modification means copolymerization with PVA, and this is described in Moritani T et al.: "Functional modification of poly(vinyl alcohol) by copolymerisation: 1. Modification with carboxylic monomers, POLYMER, ELSEVIER, AMSTERDAM, NL, vol. 38, no. 12, 1 June 1997 (1997-06-01), pages 2933-2945. The degree of copolymerization is well known from this literature and in the art and can be adjusted to suit specific needs.

[0023] Preferably, the film contains a phthalocyanine-based pigment.

[0024] Preferably, the film comprises less than 10% by weight of acrylic acid-modified PVA.

[0025] Preferably, the composition comprises less than 3% by weight of propylene glycol.

[0026] Preferably, the composition comprises at least 5% by weight of glycerol.

[0027] Preferably, the pH of the composition is from 6.1 to 8.2. More preferably, the pH of the composition is from 6.5 to 7.5.

[0028] The liquid unit dose composition is preferably a laundry composition and comprises a detergent (surfactant) and other ingredients as described below to assist cleaning performance.

[0029] Dye

[0030] The color depth of the dye in solution can be determined by the absorbance measured by UV-VIS spectroscopy. The absorbance A is defined as:

[0031] A = Log10(I 0 / I)

[0032] where I 0 is the intensity of the incident light, and I is the intensity of the light after passing through the sample.

[0033] The maximum absorbance of the dye in the wash liquor of the capsule in the range of 400 to 700 nm measured at a path length of 1 cm is less than 1, preferably from 0.05 to 1, more preferably from 0.1 to 0.6, and most preferably from 0.2 to 0.4.

[0034] The dyes are described in Industrial Dyes, edited by K. Hunger, 2003 Wiley-VCH ISBN 3-527-30426-6.

[0035] Dyes are colored organic chemicals that are soluble in the application medium. Dyes can be cationic, anionic or non-ionic.

[0036] The dyes can be of any color. Preferably, the dyes are blue, purple, yellow, green or red. Most preferably, the dyes are yellow, green or red.

[0037] Many dyes are listed in the Color Index (Society of Dyers and Colourists and American Association of Textile Chemists and Colorists). Examples of dyes are Acid Blue 80, Acid Blue 62, Acid Violet 43, Acid Green 25, Direct Blue 86, Acid Blue 59, Acid Blue 98, Direct Violet 9, Direct Violet 99, Direct Violet 35, Direct Violet 51, Acid Violet 50, Acid Yellow 3, Acid Red 94, Acid Red 51, Acid Red 95, Acid Red 92, Acid Red 98, Acid Red 87, Acid Yellow 73, Acid Red 50, Acid Violet 9, Acid Red 52, Food Black 1, Food Black 2, Acid Red 163, Acid Black 1, Acid Orange 24, Acid Yellow 23, Acid Yellow 40, Acid Yellow 11, Acid Red 180, Acid Red 155, Acid Red 1, Acid Red 33, Acid Red 41, Acid Red 19, Acid Orange 10, Acid Red 27, Acid Red 26, Acid Orange 20, Acid Orange 6, sulfonated aluminum and zinc phthalocyanines, Solvent Violet 13, Disperse Violet 26, Disperse Violet 28, Solvent Green 3, Solvent Blue 63, Disperse Blue 56, Disperse Violet 27, Solvent Yellow 33, Disperse Blue 79:1.

[0038] The dye is preferably selected from dyes containing a chromophore selected from anthraquinone, monoazo or triphenylmethane.

[0039] The dye of the present invention preferably has a maximum extinction coefficient greater than 5000 L / mol / cm, preferably greater than 10000 L / mol / cm, in the range of 400 to 700 nm.

[0040] Preferably the dye is an alkoxylated dye. The alkoxylated dye contains at least one poly-alkoxy group covalently bonded to the chromophore. The poly-alkoxy group can be directly bonded to the aromatic ring of the chromophore or more preferably indirectly bonded, such as through the N-atom of an amine or amide group. The polyalkoxy group can contain a linker moiety and has the structure:

[0041] -linker-(alkoxy) n

[0042] The alkoxy monomer preferably has 2 to 4 carbon atoms and can form a mixed poly-alkoxylate, such as a poly-alkoxylate containing ethoxylate, propoxylate and butoxylate monomers. Dyes having alkoxy monomers of the same type are preferred. Dyes having ethoxy monomers are preferred.

[0043] The alkoxylated dyes are described in WO2022056205 (Milliken).

[0044] The blue dye is preferably selected from:

[0045]

[0046] and its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0047] The green dye is preferably selected from:

[0048]

[0049] and its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0050] The red dye is preferably selected from:

[0051]

[0052] and its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0053] The yellow dye is preferably selected from:

[0054]

[0055] and its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0056] The purple dye is preferably selected from:

[0057]

[0058]

[0059] and its equivalent molecules with different degrees of ethoxylation, preferably each ethoxy chain having a molar average of 2 to 15 ethoxy units.

[0060] In the -[ethoxy] n portion, "n" generally refers to the average number of alkoxy - monomers, where "n" can thus represent the average of the distribution. In this case, it is advantageous that -[ethoxy] nPartial distribution, where the most prevalent molecular species has an ethoxy group number corresponding to the distribution average "n". Further preferred are those distributions in which the molecular species with a degree of alkoxylation corresponding to the average number "n" are present in a higher molar percentage. For example, if "n" is 4, a distribution of 25% with n = 2, 50% with n = 4, and 25% with n = 6 is more preferred than a distribution of 30% with n = 2, 40% with n = 4, and 30% with n = 6. This is advantageously applied to the average number of alkoxy - monomers in the overall alkoxylated dye and / or the average number of alkoxy monomers in an individual polyalkoxy - containing group.

[0061] Surfactant

[0062] The liquid detergent of the present invention preferably contains 2 to 60% by weight, most preferably 4 to 30% by weight of total surfactants. Anionic and non - ionic surfactants are preferred.

[0063] 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.

[0064] Typically used in laundry liquid compositions is C12 - C14 alkyl ether sulfate, which contains a straight - chain or branched - chain alkyl (C12 - 14) having 12 to 14 carbon atoms and contains an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), where mainly the C12 lauryl alkyl is ethoxylated with an average of 3 EO units per molecule.

[0065] The anionic surfactant is preferably added to the washing composition in the form of a salt. Preferred cations are alkali metal ions such as sodium and potassium. However, the salt form of the anionic surfactant can be formed in situ by neutralizing the acid form of the surfactant with a base (such as sodium hydroxide) or an amine (such as mono -, di -, or tri - ethanolamine). The weight ratio is calculated for the protonated form of the surfactant.

[0066] Non-ionic surfactants are discussed in Non-ionic Surfactants: Organic Chemistry, edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series, published by CRC press. Preferred non-ionic surfactants are alkoxylates, preferably ethoxylated. Preferred non-ionic surfactants are alcohol ethoxylates and methyl ester ethoxylates having 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. Preferred examples are C12-C15 alcohol ethoxylates having a molar average of 7 to 9 ethoxylate units.

[0067] In anionic and non-ionic surfactants, the ethoxy units can be partially replaced by propoxy units.

[0068] Further examples of suitable anionic surfactants are rhamnolipids, α-olefin sulfonates, olefin sulfonates, chain olefin sulfonates, alkane-2,3-diyl bis(sulfates), hydroxyalkane sulfonates and disulfonates, fatty alcohol sulfates (FAS), alkane 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.

[0069] The non-ionic surfactant portion is preferably greater than 50% by weight, more preferably greater than 80% by weight, and most preferably greater than 95% by weight of alcohol ethoxylates. More preferably, the non-ionic surfactant portion is preferably greater than 50% by weight, more preferably greater than 80% by weight, and most preferably greater than 95% by weight of alcohol ethoxylates.

[0070] Further 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, polyhydroxyalkyl fatty acid amides or glucamine N-acyl N-alkyl derivatives, polysorbates (Tweens).

[0071] 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.

[0072] Preferred nonionic surfactants include narrow range ethoxylates. Preferably, the detergent composition comprises an alcohol ethoxylate of the formula R-O-(CH 2 CH 2 O) q -H, where q is the molar average degree of ethoxylation, the alcohol ethoxylate comprising greater than 70% by weight of alcohol ethoxylate in the range from R-O-(CH 2 CH 2 O) X -H to R-O-(CH 2 CH 2 O) y -H, and x and y are absolute numbers, where x = q - q / 2 and y = q + q / 2, and R is a C12-15 alkyl group.

[0073] Preferably, R is a straight or branched chain alkyl group, preferably having 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.

[0074] 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.

[0075] 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, which have a straight or branched chain alkyl group containing 12 to 15 carbon atoms and contain an average of 5 to 12 EO units per molecule, are commonly used in laundry liquid compositions.

[0076] Preferably, the alcohol ethoxylate is present in the composition at 1 to 35% by weight, preferably 5 to 25% by weight.

[0077] Typically, the ethoxylation reaction to form the alcohol ethoxylate is base-catalyzed using NaOH, KOH or NaOCH 3 . The 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 NaOCH 3 . Preferably, the narrow ethoxy distribution has greater than 70% by weight, more preferably greater than 80% by weight, of R-O-(CH 2 CH 2 O) X -H to R-O-(CH2 CH 2 O) y -H within the range of alcohol ethoxylates R-O-(CH 2 CH 2 O) 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.

[0078] Narrow range ethoxylation catalysts are described in EP3289790 (Procter & Gamble), EP1747183 (Hacros); Santacesatia et al., Ind. Eng. Chem. Res. 1992, 31, 2419 - 2421; US4239917 (Conoco); Li et al., ACS Omega. 2021 Nov 9; 6(44):29774 - 29780; Hreczuch et al., J. Am. Oil Chem. Soc. 1996, 73, 73 - 78, and WO2022 / 129374 (Unilever). Catalysts based on Ca or Ba are preferred, most preferably in combination with sulfuric acid.

[0079] The preferred anionic surfactants are further described below.

[0080] C16 / C18 alcohol ethoxylate

[0081] The preferred C16 / 18 alcohol ethoxylate has the following formula:

[0082] R 1 -O-(CH 2 CH 2 O) q -H

[0083] where R 1 is selected from saturated, monounsaturated, and polyunsaturated straight-chain C16 and C18 alkyl chains, and where q is from 4 to 20, preferably from 5 to 14, more preferably from 8 to 12. Monounsaturation is preferably at the 9-position of the chain, where the carbon is counted from the chain end to which the ethoxylate is attached. The double bond can be in the cis or trans configuration (oleyl or elaidyl), preferably cis. Cis or trans alcohol ethoxylate CH 3 (CH 2 ) 7 -CH=CH-(CH 2 ) 8 O-(OCH 2 CH2 ) n The OH is described as C18:1(Δ9) alcohol ethoxylate. This follows the nomenclature CX:Y(ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds and ΔZ is the position of the double bond in the chain, with the carbons being counted from the end of the chain to which the OH is attached.

[0084] Preferably, R1 is selected from saturated C16, saturated C18 and monounsaturated C18. More preferably, the saturated C16 alcohol ethoxylate is at least 90% by weight of the total C16 straight-chain alcohol ethoxylate. As regards the C18 alcohol ethoxylate content, it is preferred that the major C18 moiety is C18:1, more preferably C18:1(Δ9). The proportion of the monounsaturated C18 alcohol ethoxylate is at least 50% by weight of the total C16 and C18 alcohol ethoxylate surfactants. Preferably, the proportion of the monounsaturated C18 is at least 60% by weight, most preferably at least 75% by weight of the total C16 and C18 alcohol ethoxylate surfactants.

[0085] Preferably, the C16 alcohol ethoxylate surfactant is at least 2% by weight, and more preferably 4% by weight, of the total C16 and C18 alcohol ethoxylate surfactants.

[0086] Preferably, the saturated C18 alcohol ethoxylate surfactant is at most 20% by weight, and more preferably at most 11% by weight, of the total C16 and C18 alcohol ethoxylate surfactants.

[0087] Preferably the saturated C18 content is at least 2% by weight of the total C16 and C18 alcohol ethoxylate content.

[0088] Alcohol ethoxylates are discussed in Non-ionic Surfactants: Organic Chemistry, edited by Nico M. van Os (Marcel Dekker 1998), Surfactant Science Series, published by CRC press. Alcohol ethoxylates are commonly referred to as alkyl ethoxylates.

[0089] Preferably the weight fraction of C18 alcohol ethoxylate / C16 alcohol ethoxylate is greater than 1, more preferably from 2 to 100, most preferably from 3 to 30. "C18 alcohol ethoxylate" is the sum of all C18 moieties in the alcohol ethoxylate, and "C16 alcohol ethoxylate" is the sum of all C16 moieties in the alcohol ethoxylate.

[0090] 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.

[0091] Preferably, the C16 / 18 alcohol ethoxylate contains less than 15% by weight, more preferably less than 8% by weight, and most preferably less than 5% by weight of polyunsaturated alcohol ethoxylate. The polyunsaturated alcohol ethoxylate contains a hydrocarbon chain having two or more double bonds.

[0092] The C16 / 18 alcohol ethoxylate can be synthesized by ethoxylation of an alkyl alcohol via the following reaction:

[0093] R 1 -OH + q ethylene oxide → R 1 -O-(CH 2 CH 2 O) q -H

[0094] The alkyl alcohol can be produced by transesterification of triglycerides to methyl esters, followed by distillation and hydrogenation to the alcohol. This method is discussed in Journal of the American Oil Chemists' Society by Kreutzer, U.R. 61(2): 343 - 348. The preferred alkyl alcohol for the reaction is oleyl alcohol having an iodine value of 60 to 80, preferably 70 to 75, and such alcohols are available from BASF, Cognis, Ecogreen.

[0095] The production of fatty alcohols is further discussed in Sanchez M.A. et al J.Chem.Technol.Biotechnol 2017;92:27 - 92 and Ullmann's Enzyclopaedie der technischen Chemie, Verlag Chemie, Weinheim, 4th edition, Vol.11, p436 et seq.

[0096] Preferably, the ethoxylation reaction is base - catalyzed using NaOH, KOH or NaOCH 3 Even more preferably, a catalyst that provides a narrower ethoxy distribution than NaOH, KOH or NaOCH 3 is used. Preferably, these catalysts with narrower distributions involve 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 narrower distributions are available from Azo Nobel and Sasol.

[0097] Preferably, the narrow ethoxy distribution has greater than 70% by weight, more preferably greater than 80% by weight of R - O-(CH 2 CH 2 O) x -H to R - O-(CH 2 CH2 O) y -H within the range of the alcohol ethoxylate R-O-(CH 2 CH 2 O) 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% by weight of the alcohol ethoxylate should consist of ethoxylates having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15 ethoxylate groups.

[0098] C16 and / or C18 alcohol ether sulfate

[0099] The preferred ether sulfate has the following formula:

[0100] R 2 -O-(CH 2 CH 2 O) p SO 3 H

[0101] where R 2 is selected from saturated, monounsaturated, and polyunsaturated straight-chain C16 and C18 alkyl chains, and where p is from 3 to 20, preferably from 4 to 12, more preferably from 5 to 10. Monounsaturation is preferably at the 9-position of the chain, where carbon is counted from the chain end to which the ethoxylate is attached. The double bond can be in the cis or trans configuration (oleyl or elaidyl), but is preferably cis. The cis or trans ether sulfate CH 3 (CH 2 ) 7 -CH=CH-(CH 2 ) 8 O-(CH 2 CH 2 O) n SO 3 H 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 in the chain, where carbon is counted from the chain end to which the OH is attached.

[0102] Preferably, R2 is selected from saturated C16, saturated C18, and monounsaturated C18. More preferably, saturated C16 is a straight-chain alkyl having at least 90% by weight of C16 content. As for the C18 content, it is preferred that the major C18 portion is C18:1, more preferably C18:1(Δ9). Preferably, the proportion of monounsaturated C18 accounts for at least 50% by weight of the total C16 and C18 alkyl ether sulfate surfactants.

[0103] More preferably, the proportion of monounsaturated C18 is at least 60% by weight of the total C16 and C18 alkyl ether sulfate surfactants, and most preferably at least 75% by weight.

[0104] Preferably, the C16 alcohol ethoxylate surfactant is at least 2% by weight of the total C16 and C18 alkyl ether sulfate surfactants, and more preferably 4% by weight.

[0105] Preferably, the saturated C18 alkyl ether sulfate surfactant is at most 20% by weight of the total C16 and C18 alkyl ether sulfate surfactants, and more preferably at most 11% by weight.

[0106] Preferably, the saturated C18 content is at least 2% by weight of the total C16 and C18 alkyl ether sulfate content.

[0107] In cases where the composition comprises a mixture of C16 / 18 source materials for alkyl ether sulfates and more conventional C12 alkyl chain length materials, it is preferred that the total C16 / 18 alkyl ether sulfate content should be at least 10% by weight of the total alkyl ether sulfates, more preferably at least 50% by weight, even more preferably at least 70% by weight, particularly preferably at least 90% by weight, and most preferably at least 95% by weight of the alkyl ether sulfates in the composition.

[0108] Ether sulfates are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, published by CRC press.

[0109] Linear saturated or monounsaturated C20 and C22 ether sulfates may also be present.

[0110] Preferably, the weight fraction of the sum of "C18 ether sulfates" / "C20 and C22 ether sulfates" is greater than 10.

[0111] Preferably, the C16 and C18 ether sulfates contain less than 15% by weight of the ether sulfates, 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 having two or more double bonds.

[0112] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. Alcohol ethoxylates can be produced by ethoxylation of alkyl alcohols. The alkyl alcohols used to produce alcohol ethoxylates can be produced by transesterification of triglycerides to methyl esters, followed by distillation and hydrogenation to alcohols. This method is discussed in Journal of the American Oil Chemists' Society by Kreutzer, U.R., 61(2): 343 - 348. The preferred alkyl alcohol for the reaction is oleyl alcohol with an iodine value of 60 to 80, preferably 70 to 75, and such alcohol can be obtained from BASF, Cognis, Ecogreen.

[0113] The poly - unsaturation in surfactants 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 also be used.

[0114] The ethoxylation reaction is described in Non - Ionic Surfactant Organic Chemistry (N.M. van Os), Surfactant Science Series, Volume 72, CRC Press.

[0115] Preferably, the ethoxylation reaction is base - catalyzed using NaOH, KOH or NaOCH 3 Even more preferably, a catalyst that provides a narrower ethoxylate distribution than NaOH, KOH or NaOCH 3 is used. Preferably, these catalysts with narrower distributions involve 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 narrower distributions can be obtained from Azo Nobel and Sasol.

[0116] Preferably, the narrow ethoxylate distribution has more than 70 wt%, more preferably more than 80 wt% of ether sulfates in the range of R 2 -O-(CH 2 CH 2 O) z SO 3 H to R 2 -O-(CH 2 CH 2 O) w SO 3 H range of R 2 -O-(CH 2 CH 2O) p SO 3 H, 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, then more than 70% by weight of the ether sulfate should consist of ether sulfates having 3, 4, 5, 6, 7, 8, 9 ethoxylate groups.

[0117] The weight of the ether sulfate is calculated in protonated form: R 2 -O-(CH 2 CH 2 O) p SO 3 H. In the formulation, it exists in ionic form R 2 -O-(CH 2 CH 2 O) p SO 3 - together with the corresponding counterion, and the preferred counterions are metals of Groups I and II, amines, and most preferably sodium.

[0118] Methyl ester ethoxylate (MEE)

[0119] Preferred methyl ester ethoxylate surfactants are of the following form:

[0120] R 3 (-C=O)-O-(CH 2 CH 2 -O) n -CH 3

[0121] where R 3 COO is the fatty acid moiety, such as oleic acid, stearic acid, palmitic acid. Fatty acid nomenclature is used to describe fatty acids by two 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 in 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.

[0122] The integer n is the molar average of the ethoxylate.

[0123] Methyl ester ethoxylates (MEEs) are described in Chapter 8, pages 287 - 301 of *Biobased Surfactants (Second Edition) Synthesis, Properties, and Applications* (AOCS press 2019), by G.A. Smith; *J. Am. Oil Chem. Soc.* vol 74 (1997) pages 847 - 859, by Cox M.E. and Weerasooriva U; *Tenside Surf. Det.* vol 28 (2001) pages 72 - 80, by Hreczuch et al.; C. Kolano, *Household and Personal Care Today* (2012) pages 52 - 55; A. Hama et al., *J. Am. Oil Chem. Soc.* vol 72 (1995) pages 781 - 784. 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 retained in the MEE.

[0124] Alternative routes of preparation are the transesterification of methyl esters, or the esterification of carboxylic acids with polyethylene glycol methyl - capped at one end of the chain.

[0125] Methyl esters can be produced 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, Article 101) and references therein. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide, and sodium methoxide. Esterases and lipases can also be used. Triglycerides 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 / oleic sunflower oil, high oleic sunflower oil, non - edible vegetable oils, tall oil, and any mixtures thereof, and any derivatives thereof. Oil from trees is called tall oil. Used food cooking oils can also be utilized. Triglycerides can also be obtained from algae, fungi, yeast, or bacteria. Vegetable sources are preferred.

[0126] Distillation and fractionation processes can be used in the production of methyl esters or carboxylic acids to produce the desired carbon chain distribution. Preferred sources of triglycerides are those containing less than 35 wt% polyunsaturated fatty acids in the oil before distillation, fractionation, or hydrogenation.

[0127] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, Unilever oleochemical Indonesia. Biodiesel is a methyl ester and these sources can be used.

[0128] When the ESB is MEE, it preferably has a molar average of 8 to 30 ethoxylate groups (EO), more preferably 10 to 20, and the most preferred ethoxylate contains 12 to 18 EO.

[0129] 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 an average molar of 10 EO, then at least 10% by weight of the MEE should consist of ethoxylates having 9, 10, and 11 ethoxylation groups.

[0130] The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO), the most preferred ethoxylate has 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 ethoxide groups.

[0131] In the case of a broader MEE distribution, it is preferred that at least 40% by weight of the total MEE in the composition is C18:1.

[0132] In addition, it is preferred that the MEE component also contains some C16 MEE.

[0133] Therefore, it is preferred that the total MEE component contains 5 to 50% by weight of C16 MEE of the total MEE. Preferably, the C16 MEE is greater than 90% by weight, more preferably greater than 95% by weight of C16:0.

[0134] Furthermore, 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, of the total MEE present. 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 level of polyunsaturation can be controlled by distillation, fractionation, or partial hydrogenation of the raw material (triglyceride or methyl ester) or MEE.

[0135] Furthermore, it is preferred that the C18:0 component is less than 10% by weight of the total MEE weight present.

[0136] Furthermore, it is preferred that the component having a carbon chain of 15 or shorter accounts for less than 4% by weight of the total MEE weight present.

[0137] Particularly preferred MEEs have 2 to 26 wt% C16:0 chains, 1 to 10 wt% C18:0 chains, 50 to 85 wt% C18:1 chains, and 1 to 12 wt% C18:2 chains of the MEE.

[0138] Preferred sources of the alkyl groups for MEE include methyl esters derived from distilled palm oil and distilled high oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters of 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.

[0139] High oleic oils are available from DuPont (Plenish high oleic soybean oil), Monsanto (Visitive Gold soybean oil), Dow (Omega-9 canola oil, Omega-9 sunflower oil), the National Sunflower Association, and Oilseeds International.

[0140] Preferably, more than 80 wt% of the double bonds in the MEE are in the cis configuration. Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0141] The methyl group of the methyl ester can be replaced by an ethyl or propyl group. The methyl group is most preferred.

[0142] Preferably, the methyl ester ethoxylate comprises 0.1 to 95 wt% of the methyl ester ethoxylate of the composition. More preferably, the composition comprises 2 to 40% of MEE, and most preferably 4 to 30 wt% of MEE.

[0143] Preferably, the composition comprises at least 50 wt% water, but this depends on the total surfactant level and is adjusted accordingly.

[0144] 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, preferably ether sulfates, linear alkylbenzene sulfonates, alkyl ether carboxylates, alkyl sulfates, rhamnolipids, and mixtures thereof.

[0145] The weight of the anionic surfactant is calculated in the protonated form.

[0146] Source of alkyl chain

[0147] The alkyl chain of the C16 / 18 surfactant is preferably obtained from renewable sources, preferably from triglycerides. Renewable sources refer to sources where the material is produced by the natural ecological cycle of living species, preferably by plants, algae, fungi, yeast or bacteria, more preferably plants, algae or yeast.

[0148] Preferred plant sources of oil are rapeseed, sunflower, corn, soybean, cottonseed, olive oil and trees. Oil from trees is called tall oil. Most preferably, palm oil and rapeseed oil are its sources.

[0149] Algal oil is discussed in Energies 2019, 12, 1920 Algal Biofuels: Current Status and Key Challenges, by Saad M.G. et al. The process for producing triglycerides from biomass using yeast is described in Masri M.A. et al., Energy Environ. Sci., 2019, 12, 2717 A sustainable, high-performance process for the economic production of waste-free microbial oils that can replace plant-based equivalents.

[0150] Non-edible vegetable oils can be used and are preferably selected from 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, Shorea robusta (sal), Terminalia belerica roxb, Cuphea, Camellia, Champaca, Simarouba glauca, Garcinia indica, rice bran, Hingan (balanites), Desert date, Cardoon, Asclepias syriaca (Milkweed), Guizotia abyssinica, Radish Ethiopian mustard, Syagrus, Tung, Idesia polycarpa var. vestita, algae, Argemone mexicana L.The fruits and seeds of (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, and Zanthoxylum bungeanum.

[0151] SLES and PAS

[0152] SLES and other such alkali metal alkyl ether sulfate anionic surfactants are typically obtained by sulfating alcohol ethoxylates. These alcohol ethoxylates are typically obtained by the ethoxylation of linear alcohols. Similarly, primary alkyl sulfate surfactants (PAS) can be obtained directly from linear alcohols by sulfating the linear alcohols. Thus, the formation of linear alcohols is a central step in obtaining both PAS and alkali-metal alkyl ether sulfate surfactants.

[0153] Linear alcohols suitable as an intermediate step in the manufacture of alcohol ethoxylates and thus anionic surfactants such as sodium lauryl ether sulfate can be obtained from many different sustainable sources. These include:

[0154] Primary sugar

[0155] Primary sugars are obtained from sources such as sugar cane 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.

[0156] Alternative methods that also use primary sugars to form linear alcohols can be employed, and in which the primary sugars are microbially converted by algae to form triglycerides. These triglycerides are then hydrolyzed to linear fatty acids, which are then reduced to form linear alcohols.

[0157] Biomass

[0158] Biomass, such as forest products, rice husks, and straw (by way of example) can be processed into syngas by gasification. By means of the Fischer-Tropsch reaction, these are processed into alkanes, which are in turn dehydrogenated to form olefins. These olefins can be processed in the same manner as the linear olefins described above [primary sugars].

[0159] Alternative methods convert the same biomass into polysaccharides via steam explosion, which can be enzymatically degraded into secondary sugars. These secondary sugars are then fermented to form bioethanol, which is in turn dehydrated to form bioethylene. This bioethylene is then processed into linear alcohols as described above [for primary sugars].

[0160] Waste plastics

[0161] Waste plastics are pyrolyzed to form pyrolysis oil. It is then fractionated to form linear alkanes, which are dehydrogenated to form olefins. These olefins are processed as described above [for primary sugars].

[0162] Alternatively, the pyrolysis oil is cracked to form ethylene, which is then processed via olefin metathesis to form the desired olefins. These are then processed into linear alcohols as described above [for primary sugars].

[0163] Municipal solid waste

[0164] MSW is converted into syngas via gasification. From the syngas, it can be processed as described above [for primary sugars] or it can be converted into ethanol via an enzymatic process before dehydrogenation to ethylene. The ethylene can then be converted into linear alcohols via the Zeigler process.

[0165] MSW can also be converted into pyrolysis oil via gasification, which is then fractionated to form alkanes. These alkanes are then dehydrogenated to form olefins and subsequently linear alcohols.

[0166] Marine carbon

[0167] There are various carbon sources from marine communities such as seaweed and kelp. From these marine communities, triglycerides can be separated from the source, and it is then hydrolyzed to form fatty acids, which are reduced to linear alcohols in the usual way.

[0168] Alternatively, the feedstock can be separated into polysaccharides, which are enzymatically degraded to form secondary sugars. These can be fermented to form bioethanol, which is then processed as described above [for primary sugars].

[0169] Waste oil

[0170] 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 are formed as described above.

[0171] Alternatively, used cooking oil can undergo the Neste process, whereby the oil is catalytically cracked to form bioethylene. It is then processed as described above.

[0172] Methane capture

[0173] The methane capture method captures methane from landfills or fossil fuel production. Methane can be converted into syngas by gasification. The syngas can be processed as described above, whereby the syngas is converted into methanol (Fischer-Tropsch reaction), and then oxidized through hydroformylation to form olefins and then converted into linear alcohols.

[0174] Alternatively, the syngas can be converted into alkanes by the Fischer-Tropsch method and then dehydrogenated and then into olefins.

[0175] Carbon capture

[0176] Carbon dioxide can be captured by any one of a variety of well-known methods. Carbon dioxide can be converted into carbon monoxide by the reverse water-gas shift reaction, which in turn can be used in an electrolysis reaction with hydrogen to form syngas. The syngas is then processed as described above and converted into methanol and / or alkanes before undergoing reactions to form olefins.

[0177] Alternatively, the captured carbon dioxide is mixed with hydrogen and then enzymatically processed to form ethanol. This is a process developed by Lanzatech. Thereby, ethanol is converted into ethylene, and then processed as described above into olefins and then linear alcohols.

[0178] The above methods can also be used to obtain C16 / 18 chains of C16 / 18 alcohol ethoxylates and / or C16 / 18 ether sulfates.

[0179] Linear alkylbenzene sulfonate

[0180] LAS (linear alkylbenzene sulfonate) is a preferred anionic surfactant.

[0181] The key intermediate compounds in LAS production are the relevant olefins. These olefins can be produced by any of the above methods and can be formed from primary sugars, biomass, waste plastics, MSW, carbon capture, methane capture, marine carbon (for example).

[0182] Instead of the olefins being processed through hydroformylation and oxidation to form linear alcohols in the above treatment, the olefins react with benzene and then are sulfonated to form LAS.

[0183] Linear alkylbenzene sulfonates have an alkyl chain length of 10 to 18 carbon atoms. Commercially available LAS is a mixture of closely related isomers and homologs of alkyl chains, each containing an aromatic ring sulfonated in the "p" 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 substance having a chain length of about C12. Except for the 1-phenyl isomer, each alkyl chain homolog consists of a mixture of all possible sulfophenyl isomers. LAS is typically formulated into compositions in the acid form (i.e., HLAS) and then at least partially neutralized in situ. Preferably, the linear alkylbenzene sulfonate surfactant is present in the composition at 1 to 20% by weight, more preferably 2 to 15% by weight, and most preferably 8 to 12% by weight.

[0184] Surfactant ratio

[0185] Preferably, the weight ratio of total nonionic surfactant to total anionic surfactant (nonionic surfactant weight / anionic surfactant weight) is from 0 to 2, preferably from 0.2 to 1.5, and most preferably from 0.3 to 1.

[0186] Preferably, the weight ratio of total nonionic surfactant to total alkyl ether sulfate surfactant (nonionic surfactant weight / alkyl ether sulfate weight) is from 0.5 to 2, preferably from 0.7 to 1.5, and most preferably from 0.9 to 1.1.

[0187] Preferably, the weight ratio of total C16 / 18 nonionic surfactant to total alkyl ether sulfate surfactant (nonionic surfactant weight / alkyl ether sulfate weight) is from 0.5 to 2, preferably from 0.7 to 1.5, and most preferably from 0.9 to 1.1.

[0188] Preferably, the weight ratio of total nonionic surfactant to linear alkylbenzene sulfonate (when present) (nonionic surfactant weight / linear alkylbenzene sulfonate weight) is from 0.1 to 2, preferably from 0.3 to 1, and most preferably from 0.45 to 0.85.

[0189] Preferably, the composition is visually clear.

[0190] Aminocarboxylate

[0191] Preferably, the composition contains an aminocarboxylate chelating agent. Preferably, the aminocarboxylate chelating agent is selected from GLDA and MGDA.

[0192] Preferably, the aminocarboxylate is present in the composition in an amount of from 0.1 to 15% by weight, more preferably from 0.1 to 10% by weight, even more preferably from 0.3 to 5% by weight, still more preferably from 0.8 to 3% by weight, and most preferably from 1 to 2.5% by weight (based on the weight of the composition).

[0193] Glutamic acid diacetic acid (GLDA)

[0194] GLDA can be present as the GDLA salt or as a mixture of GDLA and the GDLA salt. Preferred salt forms include the mono-, di-, tri- or tetra-alkali metal and mono-, di-, tri- or tetra-ammonium salts of GLDA. The alkali metal salts of glutamic acid diacetic acid GDLA are preferably selected from the lithium, potassium and more preferably sodium salts of GLDA.

[0195] Glutamic acid diacetic acid can be partially or preferably completely neutralized with the corresponding base portion. 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.

[0196] GLDA is at least partially neutralized with an alkali metal, more preferably with sodium or potassium, and most preferably with sodium.

[0197] 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.

[0198] Preferably, the composition comprises a mixture of L- and D-enantiomers of glutamic acid diacetic acid (GLDA) or its corresponding mono-, di-, tri- or tetra-alkali metal or mono-, di-, tri- or tetra-ammonium salts or mixtures thereof, said mixture predominantly containing the corresponding L-isomer and having an enantiomeric excess in the range of 10 to 95%.

[0199] Preferably, the GLDA salt is substantially L-glutamic acid diacetic acid at least partially neutralized with an alkali metal.

[0200] The sodium salt of GLDA is preferred.

[0201] A suitable commercial source of GLDA in the tetrasodium salt form is GL available from Nouryon.

[0202] Preferably, GLDA is present in the composition in an amount of from 0.1 to 15% by weight, more preferably from 0.1 to 10% by weight, even more preferably from 0.3 to 5% by weight, still more preferably from 0.8 to 3% by weight, and most preferably from 1 to 2.5% by weight (based on the weight of the composition).

[0203] Methylglycine diacetic acid (MGDA)

[0204] Preferred salt forms include 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 lithium salts, potassium salts, and more preferably the sodium salt of MGDA.

[0205] The sodium salt of methylglycine diacetic acid is preferred. Particularly preferred is the tri-sodium salt of MGDA.

[0206] MGDA can be partially or preferably completely neutralized with the corresponding alkali metal. Preferably, on average 2.7 to 3 COOH groups per molecule of MGDA are neutralized with an alkali metal, preferably sodium.

[0207] MGDA can be selected from racemic mixtures of alkali metal salts of MGDA and pure enantiomers, such as alkali metal salts of L-MGDA, alkali metal salts of D-MGDA, and mixtures of enantiomerically enriched isomers.

[0208] A suitable commercial source of MGDA in the trisodium salt form is M available from BASF and M-40 available from Nouryon.

[0209] Preferably, MGDA is present in the composition at 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).

[0210] Small amounts of aminocarboxylates can carry cations other than alkali metals. It is thus possible to carry small amounts, such as 0.01 to 5 mol% of alkaline earth metal cations (such as Mg 2+ or Ca 2+ , or Fe(II) or Fe(III) cations). GLDA can contain small amounts of impurities derived from its synthesis, such as lactic acid, alanine, propionic acid, etc. "Small amounts" in this context means a total of 0.1 to 1% by weight, referring to the chelating aminocarboxylate.

[0211] Organic acid

[0212] The composition preferably contains an organic acid. Preferably, the organic acid has the general structure R-CH(OH)-COOH, where R is a straight-chain C1-C5, more preferably C2-C4, and most preferably C4 alkyl.

[0213] Preferably, at least two, more preferably all, of the carbon atoms in the straight-chain C1-4 are substituted by OH groups. Preferably, R contains a terminal COOH group.

[0214] Preferred examples are lactic acid, tartaric acid, gluconic acid, mucic acid, glucoheptonic acid. Most preferably, the organic acid is gluconic acid.

[0215] The organic acid can be in its D or L form.

[0216] Gluconic acid can be selected from salts of gluconic acid (gluconates) and racemic mixtures of pure enantiomers, such as alkali metal salts of L - gluconic acid, alkali metal salts of D - gluconic acid, and mixtures of enantiomer - enriched isomers. The D - isomer form is preferred.

[0217] 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). Measured in its protonated form.

[0218] In the most preferred embodiment, the composition comprises GLDA and / or MGDA and gluconic acid, more preferably GLDA and gluconic acid.

[0219] Crystallizable glyceride

[0220] The composition preferably comprises a crystallizable glyceride.

[0221] 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 by reference. In the presence of ESS, preferably 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.

[0222] The crystallizable glyceride used herein preferably includes "hydrogenated castor oil" or "HCO". As used herein, HCO most commonly can be any hydrogenated castor oil, provided that it can crystallize in the ESS premix. Castor oil can include glycerides, especially triglycerides, which contain C10 - C22 alkyl or alkenyl moieties incorporating hydroxyl groups. Hydrogenation of castor oil to prepare HCO converts double bonds (which may be present in the starting oil, such as the alkenyl moiety of castor oil), thereby converting the alkenyl moiety of castor oil to a saturated hydroxyalkyl moiety, for example, hydroxystearyl. In some embodiments, HCO herein can be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO can be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. HCO is typically present in the ESS of the present invention in an amount of 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 percentage of the corresponding hydrogenated castor oil delivered to the finished laundry detergent product is less than about 1.0%, typically 0.1% to 0.8%.

[0223] Useful HCO may have the following characteristics: a melting point of from about 40°C to about 100°C, or from about 65°C to about 95°C; and / or an iodine value range of 0 to about 5, 0 to about 4 or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests utilize DSC: differential scanning calorimetry. The HCO used in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO used in the present invention include: THIXCIN(R) from Rheox, Inc. More 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, castor oil is hydrogenated using a noble metal, such as a palladium catalyst, and the hydrogenation temperature and pressure are controlled to optimize the hydrogenation of the double bonds of the original castor oil while avoiding unacceptable levels of dehydroxylation.

[0224] The present invention is not intended to be limited only to the use of hydrogenated castor oil. Any other suitable crystallizable glyceride can be used. In one example, the structurant is substantially pure triglyceride of 12-hydroxy stearic acid. This molecule represents the fully hydrogenated triglyceride of 12-hydroxy-9-cis-octadecenoic acid in pure form. In nature, the composition of castor oil is rather stable, but there can also be some variations. Similarly, the hydrogenation process can also vary. Any other suitable equivalent materials can also be used, such as a mixture of triglycerides in which 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 the same; 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 the same; or mainly contain any of the above 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 the same. The above precondition is that the major proportion of any of the said glycerides, usually at least 80 wt%, 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. It is also conceivable that hydrogenated castor oil can be incompletely hydrogenated. On the contrary, when poly(oxyalkylated) castor oil does not meet the melting criteria, the present invention excludes it.

[0225] The crystallizable glyceride used in the present invention may have a melting point ranging from about 40°C to about 100°C.

[0226] Fatty acid

[0227] Preferably, the fatty acid is present in the composition at 4 to 20% by weight (measured as the acid added to the composition), more preferably 5 to 12% by weight and most preferably 6 to 8% by weight.

[0228] Suitable fatty acids in the context of the present invention include aliphatic carboxylic acids of the formula RCOOH, where R is a straight or branched alkyl or alkenyl chain containing 6 to 24, more preferably 10 to 22, most preferably 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures can generally be derived from natural fats and / or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow).

[0229] The fatty acid can be present in the form of its sodium, potassium or ammonium salts and / or in the form of salts with organic bases (such as mono-, di- or triethanolamine).

[0230] Mixtures of any of the above materials can also be used.

[0231] For the purposes of formulating calculations, in the formulation, the fatty acid and / or its salts (as defined above) are not included in the content of surfactants or the content of builders.

[0232] Chelating agent

[0233] The detergent composition may also preferably contain chelating agent 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 , organic phosphonate type chelating agents, and alkane hydroxy phosphonates.

[0234] The preferred chelating agent is Dequest(R)2066 (diethylenetriamine penta(methylene phosphonic acid) or heptasodium DTPMP). HEDP (1-carboxyethylidene-1,1,-diphosphonic acid) is preferably absent.

[0235] In a preferred embodiment, the composition contains a fatty acid and a chelating agent.

[0236] The composition according to the invention is a low-water composition. Preferably, the composition contains less than 15% by weight of water, more preferably less than 10% by weight of water.

[0237] Alkoxylated cationic or zwitterionic polyamine polymer

[0238] Preferably, the composition comprises an alkoxylated cationic or zwitterionic diamine or polyamine polymer, wherein the positive charge is provided by quaternization of the nitrogen atom of the amine, and the anionic group (if present) is provided by sulfation or sulfonation of the alkoxylated group.

[0239] Preferably, the alkoxylate is selected from propoxylate and ethoxylate, most preferably ethoxylate.

[0240] Preferably, greater than or equal to 50 mol% of the nitrogen amines are quaternized, preferably 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 ethoxylate and propoxylate groups, most preferably ethoxylate.

[0241] Preferably, the polymer contains ester (COO) or amide (CONH) groups within the structure, preferably these groups are substituted such that when 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.

[0242] Preferably, the polymer is in the form of:

[0243]

[0244] wherein R 1 is a C3 to C8 alkyl group, X is a (C 2 H 4 O) n Y 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 SO 3 - , preferably SO 3 - groups and the number of OH groups. Preferably, there are 0, 1 or 2 OH groups. X and R 1 may contain ester groups therein. X may contain a carbonyl group, preferably an ester group. Preferably, there is 1 C 2 H 4 O unit separating the ester group and N such that the structural unit N-C 2 H 4 O-ester-(C 2 H 4 O) n-1 Y is preferred.

[0245] This polymer is described in WO2021239547 (Unilever). Example polymers are sulfated ethoxylated hexamethylenediamine, and Examples P1, P2, P3, P4, P5 and P6 of WO2021239547. The ester group can be included by adding a lactone or sodium chloroacetate (modified Williamson synthesis) to an OH or NH group, followed by ethoxylation.

[0246] An example reaction scheme for introducing an ester group is

[0247]

[0248] The addition of lactones is discussed in WO2021 / 165468.

[0249] Detergent polymer

[0250] The soil release polymer helps to improve the removal of soil from the fabric by modifying the fabric surface during the washing process. The adsorption of the SRP on the fabric surface is facilitated by the affinity between the chemical structure of the SRP and the target fiber.

[0251] The SRP for use in the present invention can include a variety of charged (e.g., anionic) as well as uncharged monomer units, and the structure can be linear, branched or star-shaped. The SRP structure can also include end groups to control the molecular weight or alter polymer properties such as surface activity. The weight average molecular weight (M w ) of the SRP can suitably be in the range of about 1000 to about 20,000, preferably in the range of about 1500 to about 10,000.

[0252] The SRP for use in the present invention can suitably be selected from copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid or terephthalic acid), diols (e.g., ethylene glycol or propylene glycol) and polyglycols (e.g., polyethylene glycol or polypropylene glycol). The copolyesters can also include monomer units substituted with anionic groups, such as 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-ionically-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.

[0253] Other types of SRP for use in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, C 1 -C 4 alkyl celluloses and C 4 hydroxyalkyl celluloses; polymers having poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl esters), for example C 1 -C 6 vinyl esters (such as poly(vinyl acetate)); poly(vinylcaprolactam) and related copolymers with monomers such as vinyl pyrrolidone and / or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam and polyethylene glycol.

[0254] Preferred SRP 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 formed by repeating units of alkylene oxides capped with alkyl groups. An example of such a material has a structure corresponding to the general formula (I):

[0255]

[0256] wherein R 1 and R 2 are each independently X-(OC 2 H 4 ) n -(OC 3 H 6 ) m ;

[0257] wherein X is C 1-4 alkyl and preferably methyl;

[0258] n is a number from 12 to 120, preferably from 40 to 50;

[0259] m is a number from 1 to 10, preferably from 1 to 7; and

[0260] a is a number from 4 to 9.

[0261] Since it is an average value, m, n and a are not necessarily integers for the overall polymer.

[0262] Mixtures of any of the above materials may also be used.

[0263] 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 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).

[0264] Suitable soil release polymers are described in more detail in U.S. Patent Nos. 5,574,179; 4,956,447; 4,861,512; 4,702,857, WO 2007 / 079850 and WO2016 / 005271. If used, the soil release polymer is 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.

[0265] Hydrotrope

[0266] The compositions of the present invention may incorporate non-aqueous carriers such as hydrotropes, co-solvents and 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 having a weight average molecular weight (M w ) in the range of about 200 to 600; C1 to C3 alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; and alkylaryl sulfonates having at most 3 carbon atoms in the lower alkyl group (for example, sodium and potassium xylene, toluene, ethylbenzene and cumene (isopropylbenzene) sulfonates).

[0267] Mixtures of any of the above materials may also be used.

[0268] The non-aqueous carriers preferably included may be present in an amount ranging from 1 to 50%, preferably 10 to 30%, and more preferably 15 to 25% (by weight based on the total weight of the composition). The level of hydrotrope used is related to the level of surfactant, and it is desirable to use the hydrotrope level to control the viscosity of these compositions. Preferred hydrotropes are monopropylene glycol and glycerol.

[0269] Cosurfactant

[0270] In addition to the non-soap anionic and / or nonionic detersive surfactants described above, the compositions of the present invention may contain one or more co-surfactants (such as amphoteric (zwitterionic) and / or cationic surfactants).

[0271] 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 may range from 0.1 - 5% (by weight based on the total weight of the composition).

[0272] 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).

[0273] Mixtures of any of the above materials may also be used.

[0274] Fluorescent agent

[0275] It may be advantageous to include fluorescent agents in the composition. These fluorescent agents are typically supplied and used in the form of their alkali metal salts, such as sodium salts. The total amount of one or more fluorescent agents used in the composition is generally from 0.005 to 2% by weight of the composition, more preferably 0.01 to 0.5% by weight.

[0276] Preferred classes of fluorescent agents are: stilbenylbiphenyl compounds such as CBS-X, diaminedistilbene disulfonic acid compounds such as Tinopal DMS pure Xtra, Tinopal 5BMGX and HRH, and pyrazoline compounds such as Blankophor SN.

[0277] 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.

[0278] Most preferably, the fluorescent agent is a stilbenylbiphenyl compound, preferably sodium 2,2'-([1,1'-biphenyl]-4,4'-diylbis(ethene-2,1-diyl))dibenzenesulfonate (CAS-No 27344-41-8).

[0279] Color toner dye

[0280] The colour - 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 colour - correcting dyes is that they can be used to mask any yellow hues in the composition itself.

[0281] Colour - correcting dyes are known in the field of liquid laundry detergent formulations.

[0282] Suitable and preferred dye classes include direct dyes, acid dyes, hydrophobic dyes, basic dyes, reactive dyes and dye conjugates. Preferred examples are Disperse Violet 28, Acid Violet 50, anthraquinone dyes covalently bound to ethoxylated or propoxylated polyethyleneimine as described in WO2011 / 047987 and WO2012 / 119859, alkoxylated mono - azo thiophenes, dyes with CAS - No 72749 - 80 - 5, Acid Blue 59 and phenazine dyes selected from:

[0283]

[0284] wherein:

[0285] X 3 is selected from: -H; -F; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and -OC 2 H 5 ;

[0286] X 4 is selected from: -H; -CH 3 ; -C 2 H 5 ; -OCH 3 ; and -OC 2 H 5 ;

[0287] Y 2 is selected from: -OH; -OCH 2 CH 2 OH; -CH(OH)CH 2 OH; -OC(O)CH 3 ; and C(O)OCH 3 .

[0288] Alkoxylated thiophene dyes are described in WO2013 / 142495 and WO2008 / 087497.

[0289] The color - adjusting dye is preferably present in the composition in the range of 0.0001 - 0.1% by weight. Depending on the nature of the color - adjusting dye, there are preferred ranges that depend on the efficacy of the color - adjusting dye, and the efficacy of the color - adjusting dye depends on the class and the specific efficacy within any particular class.

[0290] External structuring agent

[0291] The composition of the present invention can further modify its rheology by using one or more external structuring agents that form a structured network within the composition. Examples of such materials include crystallizable glycerides 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.

[0292] The composition preferably contains crystallizable glycerides.

[0293] Crystallizable glycerides 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 ESS, it is preferred that the ESS of the present invention preferably contains: (a) crystallizable glycerides; (b) alkanolamines; (c) anionic surfactants; (d) additional components; and (e) optional components. Each of these components is discussed in detail below.

[0294] The crystallizable glycerides used herein preferably include "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 - C22 alkyl or alkenyl moieties incorporating hydroxyl groups. The hydrogenation of the double bonds in the castor oil used to prepare HCO (which may be present in the starting oil such as the alkenyl moiety of castor oil) converts the alkenyl moiety of castor oil into a saturated hydroxyalkyl moiety, e.g., hydroxystearyl. In some embodiments, the HCO herein can be selected from: trihydroxystearin; dihydroxystearin; and mixtures thereof. HCO can be processed in any suitable starting form, including but not limited to those selected from solids, melts, and mixtures thereof. The 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%.

[0295] Useful HCO may have the following characteristics: a melting point of about 40 °C to about 100 °C, or about 65 °C to about 95 °C; and / or an iodine value range of 0 to about 5, 0 to about 4 or 0 to about 2.6. The melting point of HCO can be measured using ASTM D3418 or ISO 11357; both tests use DSC: differential scanning calorimetry. The HCO used in the present invention includes those that are commercially available. Non-limiting examples of commercially available HCO used in the present invention include: THIXCIN(R) from Rheox, Inc. Further examples of useful HCO can be found in U.S. Patent 5,340,390. The castor oil source used for hydrogenation to form HCO can be from 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.

[0296] 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 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 wt% is derived from castor oil. Exemplary equivalent materials mainly contain triglycerides or consist essentially of them; or mainly contain a mixture of diglycerides and triglycerides or consist essentially of them; 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 them; or mainly contain any of the above 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 them. The prerequisite for the above is that the major proportion (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 contemplated that the 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.

[0297] The crystallizable glyceride used in the present invention may have a melting point of about 40 °C to about 100 °C.

[0298] Enzyme

[0299] The composition preferably contains an enzyme selected from cellulase, protease, and an amylase / mannanase mixture.

[0300] In addition, other enzymes may also be present, such as those described below.

[0301] Preferably, the composition may contain 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 mixtures thereof.

[0302] Preferably, the enzyme content is 0.1 to 100, more preferably 0.5 to 50, and most preferably 5 to 30 mg of active enzyme protein / 100 g of the finished laundry liquid composition.

[0303] Preferred examples of enzymes are sold under the following trade names: Purafect (DuPont), Stainzyme

[0304] (Novozymes), Biotouch (AB Enzymes), (BASF).

[0305] Detergent enzymes are described in WO2020 / 186028 (Procter and Gamble), WO2020 / 200600 (Henkel), WO2020 / 070249 (Novozymes), WO2021 / 001244 (BASF), and WO2020 / 259949 (Unilever).

[0306] A nuclease is an enzyme capable of cleaving the phosphodiester bond between the nucleotide subunits of nucleic acids, and is preferably deoxyribonuclease or ribonuclease. Preferably, the nuclease is deoxyribonuclease, preferably selected from any one of the species 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, E.C. 3.1.31.1, and mixtures thereof.

[0307] 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.

[0308] Examples of subtilisins are those derived from: Bacillus species such as Bacillus lentus, Bacillus alcalophilus, 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 as described in WO 89 / 06279 and protease PD138 as described in (WO 93 / 18140). Other useful proteases can be those described in WO 92 / 175177, WO 01 / 016285, WO 02 / 026024, and WO02 / 016547. Examples of trypsin-like proteases are trypsin (such as 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).

[0309] Most preferably, the protease is subtilisin (EC 3.4.21.62).

[0310] 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 W009 / 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.

[0311] 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).

[0312] 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 BAN TM(Novozymes A / S), Rapidase TM and Purastar TM (from Genencor International Inc.).

[0313] Suitable cellulases include those of bacterial or fungal origin. This includes chemically modified or protein engineered mutants. Suitable cellulases include cellulases from the genus Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, 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.

[0314] Lipase

[0315] The lipase is a lipid esterase, and the terms lipid esterase and lipase are used synonymously herein.

[0316] The composition preferably contains 0.0005 to 0.5% by weight, preferably 0.005 to 0.2% by weight of lipase.

[0317] 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).

[0318] The lipid esterase can be selected from lipases of E.C. class 3.1 or 3.2 or a combination thereof.

[0319] Preferably the cleaning lipid esterase is selected from:

[0320] (1) Triacylglycerol lipase (E.C. 3.1.1.3)

[0321] (2) Carboxylic ester hydrolase (E.C. 3.1.1.1)

[0322] (3) Cutinase (E.C. 3.1.1.74)

[0323] (4) Sterol esterase (E.C. 3.1.1.13)

[0324] (5) Wax-ester hydrolase (E.C. 3.1.1.50)

[0325] The triacylglycerol lipase (E.C. 3.1.1.3) is most preferred.

[0326] Suitable triacylglycerol lipases can be selected from variants of the lipase of Humicola lanuginosa (Thermomyces lanuginosus). Other suitable triacylglycerol lipases can be selected from variants of Pseudomonas lipases, such as from Pseudomonas alcaligenes or Pseudomonas pseudoalcaligenes (EP 218 272), Pseudomonas cepacia (EP 331 376), Pseudomonas stutzeri (GB 1,372,034), Pseudomonas fluorescens, Pseudomonas strain SD 705 (WO 95 / 06720 and WO 96 / 27002), Pseudomonas wisconsinensis (WO 96 / 12012); variants of Bacillus lipases, such as from Bacillus subtilis (Dartois et al. (1993), Biochemica et Biophysica Acta, 1131, 253-360), Bacillus stearothermophilus (JP 64 / 744992) or Bacillus pumilus (WO 91 / 16422).

[0327] 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.

[0328] 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 culmorum, or Fusarium roseum sambucium; the genus Helminthosporium, particularly Helminthosporium 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.

[0329] 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.

[0330] 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. Microbiol., 2009, pp. 2148-2157.

[0331] In another preferred embodiment, the cutinase is the wild-type or variant of two endogenous cutinases of Trichoderma reesei described in WO2009007510 (VTT).

[0332] In a most preferred embodiment, the cutinase is derived from a strain of Humicola insolens, especially the 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. Preferred commercial cutinases include Novozym 51032 (available from Novozymes, Bagsvaerd, Denmark).

[0333] Suitable sterol esterases can be derived from Ophiostoma, such as strains of Ophiostoma piceae; Pseudomonas, such as strains of Pseudomonas aeruginosa; or Melanocarpus, such as strains of Melanocarpus albomyces.

[0334] 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.

[0335] Suitable wax-ester hydrolases can be derived from Simmondsia chinensis.

[0336] 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.

[0337] Examples of E.C. 3.1.1.3 lipases include those described in WIPO publications WO 00 / 60063, WO 99 / 42566, WO 02 / 062973, WO 97 / 04078, WO 97 / 04079 and US 5,869,438. Preferred lipases are from Absidia reflexa, Absidia corymbefera, Rhizomucor miehei, Rhizopus deleman, Aspergillus niger, Aspergillus tubigensis, Fusarium oxysporum produced by Fusarium oxysporum, Fusarium heterosporum, Aspergillus oryzae, Penicillium camembertii, Aspergillus foetidus, Aspergillus niger, Thermomyces lanoginosus (synonym: Humicola lanuginosa) and Landerina penisapora, especially Thermomyces lanoginosus. Certain preferred lipases are available from Novozymes under the trade name Lipolase and (registered trademark of Novozymes); and LIPASE P is available from Areario Pharmaceutical Co., Ltd., Nagoya, Japan; AMANO- is commercially available from ToyoJozo 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 the variant containing the T231R and N233R mutations, such a most preferred variant being sold under the trade name (Novozymes).

[0338] The above lipases can be used in combination (any mixture of lipases can be used). Suitable lipases are 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 prepared according to the examples included herein.

[0339] Lipid esterases with reduced potential for odor generation and good relative performance are particularly preferred, as described in WO 2007 / 087243. These include (Novozyme).

[0340] Preferred commercially available lipase enzymes include Lipolase TM and Lipolase Ultra TM , Lipex TM and LipocleanTM (Novozymes A / S).

[0341] Fragrance

[0342] The composition contains a fragrance, and preferably the fragrance is present in the composition at 0.01 to 5% by weight, more preferably 0.1 to 1% by weight.

[0343] Preferably, the fragrance comprises 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 brazileinate, and mixtures of these components.

[0344] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance component ethyl-2-methylvalerate (chrysanthemum ester).

[0345] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance component limonene.

[0346] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance component (4Z)-cyclopentadec-4-en-1-one.

[0347] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance component dimethylbenzyl carboacetate.

[0348] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance component dihydromyrcenol.

[0349] Preferably, the fragrance comprises 0.5 to 30% by weight, more preferably 2 to 15% by weight and particularly preferably 6 to 10% by weight of the fragrance component rose oxide.

[0350] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component tert-butylcyclohexyl acetate.

[0351] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component tricyclodecenyl acetate.

[0352] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component benzyl acetate.

[0353] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most 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)].

[0354] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component geraniol.

[0355] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component methyl nonyl acetaldehyde.

[0356] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component cyclamen aldehyde.

[0357] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component β-ionone.

[0358] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component hexyl salicylate.

[0359] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component tonalide.

[0360] Preferably, the fragrance contains from 0.5 to 30% by weight, more preferably from 2 to 15% by weight and most preferably from 6 to 10% by weight of the fragrance component [2-(cyclohexyloxy)ethyl]benzene.

[0361] Preferably, the fragrance contains components selected from benzene, toluene, xylene (BTX) feedstock classes. More preferably, the fragrance components are selected from 2-phenylethanol, phenylpentanol and mixtures thereof.

[0362] Preferably, the perfume contains a component selected from the group of cyclododecanone raw materials. More preferably, the perfume component is habolonolide.

[0363] Preferably, the perfume contains a component selected from the group of phenolic raw materials. More preferably, the perfume component is the ingredient of hexyl salicylate.

[0364] Preferably, the perfume contains a component selected from the group of C5 modules or oxygen-containing heterocyclic moiety raw materials. More preferably, the perfume components are selected from γ-decalactone, methyl dihydrojasmonate, and mixtures thereof.

[0365] Preferably, the perfume contains a component selected from the group of terpene raw materials. More preferably, the perfume components are selected from linalool, terpinolene, camphor, citronellol, and mixtures thereof.

[0366] Preferably, the perfume contains a component selected from the group of alkyl alcohol raw materials. More preferably, the perfume component is ethyl-2-methylbutyrate.

[0367] Preferably, the perfume contains a component selected from the group of diacid raw materials. More preferably, the perfume component is ethylene glycol brassylate.

[0368] Preferably, the above-listed perfume components are present in the final detergent composition in an amount of 0.0001 to 1% by weight of the composition.

[0369] Microcapsule

[0370] 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, thereby producing capsules with sizes in the range of less than 1 micron to several hundred microns. The material to be encapsulated can be referred to as the core, active ingredient or agent, filler, payload, nucleus, or internal phase. The material encapsulating the core can be referred to as the coating, membrane, shell, or wall material.

[0371] Microcapsules generally have at least one continuous, usually 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 core material droplets embedded throughout the microcapsule.

[0372] 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.

[0373] 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 typically 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 fragrance (f2) can be determined by obtaining a slurry of the microcapsules, extracting into ethanol, and measuring by liquid chromatography.

[0374] 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.

[0375] 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.

[0376] 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.

[0377] Polycondensation involves forming a dispersion or emulsion of the core material in an aqueous solution of a pre-condensate of a polymeric material under suitable stirring conditions to produce capsules of the desired size, and adjusting the reaction conditions to cause condensation of the pre-condensate 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. An example of a core-shell microcapsule produced by this method is an aminoplast microcapsule having a shell formed from a polycondensation product of melamine (2,4,6-triamino-1,3,5-triazine) or urea with formaldehyde. Suitable cross-linking agents (e.g., toluene diisocyanate, divinylbenzene, butanediol diacrylate) can also be used, and in appropriate cases, secondary wall polymers such as acid anhydrides and their derivatives, especially polymers and copolymers of maleic anhydride, can also be used.

[0378] 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 a fragrance formulation (f2). More preferably, such an aminoplast shell is formed from a polycondensation product of melamine with formaldehyde.

[0379] Polymeric microparticles suitable for use in the present invention generally 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 typically having a 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.

[0380] 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).

[0381] 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.

[0382] 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 inherent 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 the xylan family containing glucuronosyl-, arabinosyl- 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).

[0383] 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.

[0384] 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 nonionic 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.

[0385] Mixtures of any of the above materials may also be suitable.

[0386] 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.

[0387] 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 a fragrance formulation (f2); wherein the deposition aid is attached to the outside 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.

[0388] The inventors have surprisingly observed that it is possible to reduce the total content of the fragrance contained in the compositions of the present invention without sacrificing the overall aromatic experience provided to the consumer at the critical stages of the laundry process. Reducing the total content of the fragrance is advantageous for cost and environmental reasons.

[0389] Accordingly, the total amount of fragrance formulation (f1) and fragrance 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%, and most preferably 0.6 - 0.9% (by weight based on the total weight of the composition).

[0390] The weight ratio range of fragrance formulation (f1) to fragrance 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 fragrance formulation (f1) to fragrance formulation (f2) is about 50:50.

[0391] Fragrance (f1) and fragrance (f2) are typically incorporated at different stages of forming the compositions of the present invention. Generally, discrete polymer particles (such as microcapsules) encapsulating fragrance 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, fragrance (f1) is typically post - added after the base formulation has cooled.

[0392] Further optional ingredients

[0393] The compositions of the present invention may contain 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, pearlescent agents and / or opacifying agents, and color - adjusting dyes. Each of these ingredients is present in an amount effective to achieve its purpose. Generally, 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.

[0394] 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 raw materials described herein is provided below.

[0395] Preferably, the unit dose detergent is packaged in a container such as a plastic bucket. Such plastic buckets are generally hermetically sealable and include child-resistant closures.

[0396] More preferably, the liquid unit dose detergent is packaged in a container comprising at least 80% by weight of a biodegradable material. Suitable biodegradable materials include cardboard and other pulp-based materials. Such biodegradable materials can be virgin materials or recycled materials, but preferably they are recycled.

[0397] Preferably, the container comprises at least 90% by weight of a biodegradable material.

[0398] Preferred pulp includes cardboard, especially corrugated cardboard. Examples

[0399] We tested the performance of two laundry capsules which were identical except for the test parameters (maleic v acrylic modified PVA) and high or low dye content.

[0400] The formulation used in the capsules was the standard Persil 3 in 1 non-bio commercially available on the day of testing.

[0401] The aesthetic performance of the capsules was determined by observation.

[0402]

[0403]

[0404] Data shows that regardless of the amount and nature of the dye present, the acrylic-based film produces a dull or matte film; while the maleic-based film can produce a shiny film surface (present invention) when the absorbance of the total dye in the wash liquor of the capsule measured at 1 cm in the range of 400 to 700 nm is less than 1, and does not produce a shiny film surface when the absorbance is greater than 1 (comparative example).

Claims

1. A liquid unit dose composition comprising 5% to 15% water and a dye, wherein the composition is contained in a capsule comprising a water-soluble film, wherein the film comprises maleic acid-modified polyvinyl alcohol, and wherein the absorbance of the total dye in the washing liquid of the capsule, measured at 1 cm, in the range of 400 to 700 nm is less than 1.

2. The composition according to claim 1, which comprises less than 3% by weight of propylene glycol.

3. The composition according to claim 1 or 2, which comprises at least 5% by weight of glycerol.

4. The composition according to any one of the preceding claims, wherein the film comprises less than 10% by weight of acrylic acid-modified PVA.

5. The composition according to any one of the preceding claims, wherein the absorbance of the total dye in the washing liquid of the capsule, measured at 1 cm, in the range of 400 to 700 nm is from 0.05 to less than 1.

6. The composition according to any one of the preceding claims, wherein the absorbance of the total dye in the washing liquid of the capsule, measured at 1 cm, in the range of 400 to 700 nm is from 0.1 to 0.

6.

7. The composition according to any one of the preceding claims, wherein the absorbance of the total dye in the washing liquid of the capsule, measured at 1 cm, in the range of 400 to 700 nm is from 0.2 to 0.4.

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